Hindawi Publishing CorporationBioinorganic Chemistry and ApplicationsVolume 2013 Article ID 351262 7 pageshttpdxdoiorg1011552013351262

Research ArticlePreparation Characterization and Antimicrobial Activities ofBimetallic Complexes of Sarcosine with Zn(II) and Sn(IV)

Yasir Arafat1 Saqib Ali2 Saira Shahzadi1 and Muhammad Shahid3

1 Department of Chemistry GC University Faisalabad 38000 Pakistan2Department of Chemistry Quaid-i-Azam University Islamabad 45320 Pakistan3Department of Chemistry and Biochemistry University of Agriculture Faisalabad 38000 Pakistan

Correspondence should be addressed to Saqib Ali drsa54yahoocom and Saira Shahzadi sairashahzadihotmailcom

Received 29 April 2013 Accepted 30 August 2013

Academic Editor Claudio Pettinari

Copyright copy 2013 Yasir Arafat et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Heterobimetallic complexes of Zn(II) and Sn(IV) with sarcosine have been synthesized at room temperature under stirringconditions by the reaction of sarcosine and zinc acetate in 2 1 molar ratio followed by the stepwise addition of CS

2and

organotin(IV) halides where R =Me n-Bu and PhThe complexes were characterized by elemental analysis FT-IR and NMR (1H13C) spectroscopy IR data showed that the ligand acts in a bidentate manner NMR data revealed the four coordinate geometry insolution state In vitro antimicrobial activities data showed that complexes (3) and (4) were effective against bacterial and fungalstrains with few exceptions

1 Introduction

Organotin compounds are amongst the most widely usedorganometallic compounds Over the last several decadesthey have been utilized for a variety of industrial andagricultural applications including pesticides fungicide andantifouling agents [1] In general the biochemical activityof organotin(IV) carboxylates is greatly influenced by thestructure of the molecule and the coordination number ofthe tin atom [2 3] Therefore the recognition of the impor-tance between the biological properties and the structure oforganotin(IV) carboxylates [4] has stimulated the study ofcarboxylates of tin

The diverse structural motifs are known in organotincompounds and attributed to the ambidentate character ofthe carboxylate ligands [5] Steric and electronic attributesof organic substituents on tin andor the carboxylate moietyimpart significant influence on the structural characteristicsin tin carboxylatesTherefore synthesis of new organotin car-boxylates with different structural features will be beneficialin the development of pharmaceutical organotin and in otherproperties and applications

Meanwhile dithiocarbamate (DTC) is the ligand whichstrongly bonds with metal ions and can stabilize metalcomplexes with high oxidation number [6] Organotin(IV)dithiocarbamate complexes have been widely studied due toSn-S bond in their structure and the effects of the bonding ondiversified applications basically in biological field [7 8]

Zinc chloride is chiefly used as a catalyst for the Fischerindole synthesis and Friedel-Craft acylation reaction thatwas involved in the synthesis of organic compounds usedin the laboratory [9] The medical applications of Zn(II)compounds include treatments of parasitic diseases (eczemaringworm fungus and athletes foot) and in many biologicalprocesses zinc plays an important role as metalloenzymesin which Zn(II) is coordinated by a ligand that leads to astructural as well as functional model [10]

In our previous work we reported several organotincomplexes with oxygen and sulfur donor atoms [11ndash15]As an extension of this research program we report herethe complexes of sarcosine (Figure 1) containing Zn(II) andSn(IV) to study the effect of Zn along with tin on biologicalactivities and compare these results with already reportedorganotin complexes of sarcosine [16ndash18]

2 Bioinorganic Chemistry and Applications

H

N

CH3

HOOC

Figure 1 Chemical structure of sarcosine

These complexes were characterized by elemental anal-ysis IR and multinuclear NMR (1H 13C) These were alsoexamined to check their antibacterial and antifungal activityin vitro

2 Experimental

21 Materials and Methods N-Methyl glycine (sarcosine)zinc acetate carbon disulfide and organotin(IV) halides wereof Sigma-Aldrich (UK) origin The organic solvents (chlo-roform n-hexane ethanol methanol DMSO and acetone)were procured from Merck (Germany) The solvents weredried [19] prior to use Nutrient broth nutrient agar andpotato dextrose agar were of oxide (UK) origin Autoclaveand laminar air flow were purchased from Omron andDalton companies of Japan respectively Micropipettes werepurchased from Gilson (France) The melting points weredetermined on an electrothermal melting point apparatusmodel Staurt SMP3 by using capillary tubes Elemental analy-sis was done for carbon hydrogen nitrogen and sulphur on aCHNS-932 elemental analyzer Leco Corporation (USA)Theinfrared spectrawere recorded asKBr pellets on Perkin Elmer1000 spectrometer in the frequency range of 4000ndash250 cmminus1NMR (1H and 13C) spectra were recorded on Bruker AM-300MHz FT-NMR spectrometer (Germany) using CDCl

3as

an internal reference

22 General Procedure for the Synthesis of Complexes Sar-cosine (0178 g 2mmol) was dissolved in methanol (25mL)in a round bottom flask with continuous stirring at roomtemperatureThen solution of zinc acetate (022 g 1mmol) inmethanol (3mL) was added dropwise to the above solutionand mixture was stirred continuously for 20 minutes Afterthat CS

2(0120mL 20mmol) in methanol (5mL) was added

dropwise to the reaction mixture and stirred for 05 hr atroom temperature Subsequently the solution of diorgan-otin dichloridetriorganotin chloride (2mmol) in methanol(50mL) was added and the mixture was continuously stirredfor 4 hr Solvent was slowly evaporated at room temperatureand product obtained was dried in air Purity was checked byTLC and recrystallization was done in methanol n-hexane(1 1) (see Scheme 1)

3 Results and Discussion

The ligand and synthesized complexes are solid and stable inair They have sharp melting points Elemental analysis wasdone to compare the observed values with predicted valuesof percentage of the carbon hydrogen nitrogen and sulfur

The physical data of ligand and synthesized complexes issummarized in Table 1

31 Infrared Spectroscopy IR spectra of the ligand and itsnewly synthesized complexes (1)ndash(6) were recorded as KBrpellets in the range of 4000ndash250 cmminus1 The characteristicinfrared absorption frequencies (cmminus1) have been listed inTable 2

The IR spectrum of the ligand exhibited a band at3365 cmminus1 which was attributed to the NH stretching modeDeprotonation of carboxylic group is confirmed by theabsence of OH band in the spectra of the complexesRegarding the carboxyl vibrational modes there are differentbinding possibilities [20 21]

(1) bridged structure ]119904(COO) = 1560ndash1540 cmminus1

(2) dimer and monomer chelate structures ]119886(COO) =

1640ndash1560 cmminus1(3) ldquofree esterrdquo monodentate structure ](CndashO) = 1680ndash

1640 cmminus1 and ](C=O) = 1770 1700 cmminus1The carboxylate group gives strong asymmetric and symmet-ric stretching bands in the range of 1602ndash1650 cmminus1 and 1433ndash1470 cmminus1 respectively and it is assignable to a chelate ormonodentate structure however the absence of ]C=O bandin expected range is indicative of the presence of the chelateform Bidentate nature of ligand is also confirmed byΔ]COOvalue that is less than 200 cmminus1 in all complexes [22] Presenceof ]ZnndashO vibrational bands in the range of 310ndash385 cmminus1in all the complexes [23] confirms the zinc carboxylateinteraction It has been reported [15] that the observationof a single ]C=S absorption in the region around 1000 cmminus1is indicative of dithiocarbamate groups that are bondedsymmetrically or bidentate in nature A strong absorptionband of ](C=S) lies in the range of 1013ndash1043 cmminus1 while](CndashS) band appears in the lower frequency range 942ndash988 cmminus1 [24] The SnndashS bond formation is confirmed bythe appearance of a new band in the range of 456ndash480 cmminus1[25] The strong band at 302ndash318 cmminus1 was assigned to ](SnndashCl) absorption The SnndashC band was observed in the rangeof 530ndash547 cmminus1 for complexes (1) and (2)ndash(5) but at 272and 280 cmminus1 for complexes (3) and (4) respectively whichare di- and triphenyltin derivatives The absence of the bandin the range 440ndash420 cmminus1 which is commonly assignedto the ](SnndashN) mode in analogous compounds [26 27]rules out amino coordination to tin thus leading support tothe proposed carboxylate carboxyl atom [16] and dithiolatesulphur atom coordination in all synthesized complexes

32 1H NMR Spectroscopy 1H NMR spectra of the ligandand complexes (1)ndash(6) were recorded in deuterated DMSOto find the behaviour of magnetically nonequivalent protonsThe data is presented in Table 3

The number of protons calculated by integration of peaksis in excellent agreement with those theoretically calculatedby incremental method [28] The absence of OH signal inthe complex suggested the deprotonation of carboxylic acidgroup for O rarr Zn coordination through COOminus anions

Bioinorganic Chemistry and Applications 3

H

H H

N

N

N

N N

N

N

CH3

CH3

CH3

CH3 CH3

CH3

CH3

HOOC + Zn(CH3COO)2

O

O

O

O

O

O

O O

O

O

OO

Zn

Zn

Zn

2CS2

S S

HS SH

2R2SnCl2R3SnCl

R R

RR Sn SnS

S S

S

C

C CC

C C CC

C

C

XX

Compound number

Compound number

R3

R2Cl Me

Me

n-Bu

n-Bu

Ph

Ph

X Cl for diorganotin

X R for triorganotin

R Me n-Bu Ph

2

(1) (2) (3)

(4) (5) (6)

Scheme 1

Table 1 Physical data of heterobimetallic complexes with sarcosine

Compno Molecular formula Mol weight yield mp (∘C)

Elemental analysis CCalcd(found)

HCalcd(found)

NCalcd(found)

SCalcd(found)

HL C3H7O2N 8909 mdash 208 4045 792 1571 mdash(4042) (795) (1568)

(1) C12H22O4N2S4Cl2ZnSn2 76031 75 121-122 1895 291 368 1687(1899) (295) (364) (1689)

(2) C24H46O4N2S4Cl2ZnSn2 92863 68 87ndash91 3104 499 301 1381(3107) (496) (304) (1378)

(3) C32H30O4N2S4Cl2ZnSn2 100853 57 107ndash109 3810 299 277 1271(3912) (296) (274) (1274)

(4) C14H28O4N2S4ZnSn2 71961 67 145-146 2336 392 389 1782(2339) (396) (392) (1778)

(5) C32H64O4N2S4ZnSn2 97153 51 224-225 3955 664 288 1320(3950) (668) (285) (1317)

(6) C44H40O4N2S4ZnSn2 109189 73 86ndash88 4839 369 256 1174(4836) (365) (259) (1178)

4 Bioinorganic Chemistry and Applications

Table 2 IR spectral data (cmminus1) of heterobimetallic complexes with sarcosine

Comp no ](NH) ](COO)Δ] ](C=S) ](CndashS) ](SnndashC) ](SnndashS) ](SnndashCl) ](ZnndashO)

](COO) (asym) ](COO) (sym)HL 3365 1621 1407 214 mdash mdash mdash mdash mdash mdash(1) mdash 1642 1462 180 1033 955 526 461 311 364(2) mdash 1618 1433 185 1013 942 530 472 302 352(3) mdash 1602 1440 162 1025 988 272 466 318 347(4) mdash 1622 1456 166 1023 938 538 485 mdash 371(5) mdash 1635 1468 167 1043 965 547 456 mdash 385(6) mdash 1650 1470 180 1030 970 280 480 mdash 310

Table 3 1H NMR dataandashd (ppm) of heterobimetallic complexes with sarcosine

Proton no HL (1) (2) (3) (4) (5) (6)2 21015840 315s 397s 399s 388s 374s 363s 395s3 31015840 248s 289s 280s 296s 285s 294s 279saCompound (1) Sn-CH3Cl 127s

2J[96] compound (2) Sn-CH2CH2CH2CH3Cl 088ndash093m 023t (72) compound (3) Sn-C6H5Cl 791d2J[82] 750ndash753m

742ndash750m compound (4) Sn-CH3 051s2J[82] compound (5) Sn-CH2CH2CH2CH3 064ndash11m 023t (72) compound (6) Sn-C6H5 791d

2J[82] 750ndash753m742ndash750mbMultiplicity is given as s singlet d doublet t triplet m multipletcCoupling constant 119899J[119Sn 1H] and 119899J[1H 1H] in Hz are given in square bracket and parenthesis respectivelyd

NN

CH3CH3

3998400

1998400

2998400

CCOO

OOZn

1

2

3

Table 4 13C NMR dataab (ppm) of heterobimetallic Zn(II) andSn(IV) complexes with sarcosine

Carbon HL (1) (2) (3) (4) (5) (6)1 11015840 1792 1863 1819 1837 1854 1843 18382 21015840 566 568 563 569 567 566 5683 31015840 415 413 413 415 414 412 415ndashCSS mdash 2026 2025 2028 2017 2028 2027aCompound (1) Sn-CH3Cl (C-120572) 21 1J[397] compound (2) Sn-CH2CH2CH2CH3Cl (C-120572) 295 (C-120573) 274 (C-120574) 262 (C-120575) 139compound (3) Sn-C6H5Cl (C-120572) 1376

1J[640] (C-120573) 1328 2J[490] (C-120574)1299 (C-120575) 1248 compound (4) Sn-CH3 (C-120572) 23 1J[396] compound(5) Sn-CH2CH2CH2CH3 (C-120572) 311 [349] (C-120573) 271 2J[21] (C-120574) 2823J[63] (C-120575) 141 compound (6) Sn-C6H5 (C-120572) 1380

1J[640] (C-120573) 13302J[490] (C-120574) 1300 (C-120575) 1251bChemical shifts (120575) in ppm 119899J[119Sn 13C] in Hz is listed in parenthesis

Two resonance signals appeared as a singlet at 315 ppm and248 ppm for the methylene andmethyl protons respectivelyin the free ligand These signals exhibited downfield shift to363ndash399 ppm and 279ndash296 ppm in the complexes (1)ndash(6)for methylene and methyl protons respectively

The CH3protons in compound (1) appear as a singlet

at 127 ppm with tin satellites having 2J[119Snndash1H] = 96HzIn compound (2) the protons of butyl group appear as amultiplet in the region 088ndash093 ppm The terminal CH

3

group of butyl gives triplet at 023 ppm with 3J[1Hndash1H] valueof 72Hz The proton chemical shift of the methyl group incompound (3) attached to the Sn gives a singlet at 051 ppm

The phenyl moieties of di- and triphenyltin(IV) derivativesshow a complex pattern and were assigned according to theliterature [29] The 2J[119Snndash1H] value for di- and triph-enyltin(IV) derivatives is 82Hz in the range expected forpentacoordinated tin atom and consistent with CndashSnndashCangle of 1265∘

33 13C NMR The assignments of ndashCSS group in investi-gated compounds is straightforward which are observed inthe range of 2025ndash2028 ppm indicating the coordination ofsulfur to the tin atom

Table 4 lists the chemical shifts of 13C and tin-carboncoupling constants for the reported complexes (1)ndash(6) The13C NMR chemical shifts due to the phenyl groups areobserved at positions comparable to other similar com-pounds [30 31] The 13C NMR chemical shift due to ndashCOOcarbon atom is observed at 1792 ppm in the free ligandwhile in the complexes it exhibits downfield shift in therange 1819ndash1863 ppm Coordination of the tin atom in di-and triorganotin has been related to 119899J(119Snndash13C) couplingconstants The 119899J(119Snndash13C) coupling for complexes (1) and(6) is 397 and 640Hz respectively which is indicative of fourcoordinate geometry [30] in solution state

34 Antibacterial Activity Sarcosine and synthesized com-plexes (1)ndash(6) were tested in vitro for their antibacterialactivity against gram positive and gram negative bacterial

Bioinorganic Chemistry and Applications 5

Table 5 Antibacterial activity dataandashe of complexes and ligand against selected bacterial strains

Compound no Bacterial inhibition zone (mm)S aureus B subtilis E coli P multocida

HL 125c plusmn 086 130c plusmn 100 125c plusmn 086 120c plusmn 141(1) 208bc plusmn 100 180c plusmn 100 252c plusmn 086 210ab plusmn 100(2) 210bc plusmn 100 205bc plusmn 086 275bc plusmn 086 245ab plusmn 086(3) 208bc plusmn 100 186c plusmn 100 262c plusmn 086 213ab plusmn 100(4) 300ab plusmn 141 215bc plusmn 165 280bc plusmn 141 230ab plusmn 100(5) 325ab plusmn 165 545a plusmn 086 510a plusmn 100 325a plusmn 165(6) 315ab plusmn 086 330bc plusmn 141 320ab plusmn 100 300ab plusmn 141Ampicillin 385a plusmn 086 400ab plusmn 141 395ab plusmn 086 320ab plusmn 141aConcentration 1mgmL in DMSObStandard ampicillinc0 no activity 5ndash10 activity present 11ndash25 moderate activity 26ndash40 strong activitydAntibacterial values are mean plusmn SD of samples analyzed individually in triplicate at 119875 lt 01eDifferent letters in superscript indicate significant differences

Table 6 Antifungal activity dataandashe of complexes and ligand against selected fungal strains

Compound no Fungal inhibition zone (mm)A alternata 119866 lucidum A flavus 119860 niger

HL 270ab plusmn 100 115c plusmn 086 375ab plusmn 086 145bc plusmn 165(1) 264ab plusmn 100 193bc plusmn 100 202bc plusmn 165 203ab plusmn 086(2) 200c plusmn 141 190bc plusmn 100 205bc plusmn 165 205bc plusmn 086(3) 269bc plusmn 141 202ab plusmn 165 352bc plusmn 165 212bc plusmn 086(4) 300ab plusmn 141 185bc plusmn 086 195c plusmn 165 185bc plusmn 086(5) 300ab plusmn 141 395ab plusmn 165 370

abplusmn 165 335 a

plusmn 165(6) 285ab plusmn 086 250bc plusmn 100 320bc plusmn 141 195bc plusmn 086Fluconazole 305a plusmn 086 415a plusmn 086 540a plusmn 141 125c plusmn 086aConcentration 1mgmL in DMSObStandard fluconazolec0 no activity 5ndash10 activity present 11ndash25 moderate activity 26ndash40 strong activitydAntibacterial values are mean plusmn SD of samples analyzed individually in triplicate at 119875 lt 01eDifferent letters in superscript indicate significant differences

strains including B subtilis and S aureus and P multocidaand E coli respectively and the results are given in Table 5Ampicillin was used as a standard drug The results revealedthat all the newly synthesized complexes show higher activitythan the ligand but markedly lower than the standard drugwith few exceptions

Complex (5) showed maximum inhibitory action againstB subtilis (545 plusmn 086) and E coli (510 plusmn 100) probablymore than standard drug (4000 plusmn 141) and (395 plusmn 086)respectively Complex (2) displayed lowest inhibition zone incase of B subtilis (205plusmn086) and S aureus (210plusmn100)Theligand exhibited low activities while the complexes exhibitedmoderate activities as compared to standard drug towards allthe bacterial strains Complex (6) showed moderate antibac-terial activity against all the bacterial strains Among all thecomplexes the tributyltin complex (5) showed significantantibacterial activity It was clear from the data that antimi-crobial activities varied according to substitution (increasein substitution on the Sn(IV) enhances the antimicrobialactivity) [32]

Data revealed that the synthesized complexes showedmore activity against gram positive bacterial strain thangram negative strains It was due to the difference in thecomposition of cell wall of both the gram positive and gramnegative strains [33] It was also suggested that the anti-microbial activity of the complexes was either due to killingofmicrobes or inhibiting their reproduction by blocking theiractive sites [34]

The results show that all compounds exhibit antibacterialactivity and in many cases complexes are more potent intheir inhibition properties than the free ligand This canbe explained in terms of the greater lipid solubility andcellular penetration of the complexes [35] It is clear that thecoordination enhances the antibacterial activity and clearlyindicates that the newly synthesized complexes in the presentstudies are more active against gram positive than gramnegative bacteria The preliminary results achieved have ledus to conclude that these types of complexes should bestudied in detail for their applications in diverse area

The screening data of a particular ligand and its metalcomplexes show that the former has greater activity than

6 Bioinorganic Chemistry and Applications

the latter from the biochemical point of view On comparingthe results in general it may be concluded that complexescontaining Zn(II) and Sn(IV) have greater inhibiting powerthan the free ligands as compared to organotin complexeswith sarcosine [16 17] against all the microbes

35 Antifungal Activity The synthesized compounds (1)ndash(6)and sarcosine were tested for antifungal activity by usingfluconazole as standard drug against four fungal strainsincluding A flavus A niger A alternate and G lucidum bydisc diffusion method [36] The results are summarized inTable 6 It was evident from tabulated data that the sarcosineas well as the synthesized complexes exhibited variety offungicidal activity Sarcosine exhibited maximum activityagainst A flavus (375 plusmn 086) while complex (5) exhibitedmaximum activity (395 plusmn 165) against G lucidum Complex(2) showed the lowest inhibition zone (190 plusmn 100) againstG lucidum It is noted that tributyltin complexes showed thegreatest inhibitory effect against fungi as compared to otheralkyl groupsThus the presence of butyl groups in compound(5) bonded with tin atom was responsible for the rise ofantifungal activity [37] The increased activity of complexesmight be due to the coordination of zinc and tin with oxygenand sulfur respectively [38] From the data it might beconcluded that triorganotin compounds were usually moreeffective against the fungi than diorganotin compounds [39]in contrast to earlier reported compounds in the literature[16] This might be due to the presence of Zn(II) along withSn(IV) which enhances the fungicidal activity of triorganotincomplexes

36 Structure Activity Relationship Although it is difficult tomake out an exact structure-activity relationship between theantimicrobial activity and the structure of these complexesit can possibly be concluded that the chelation as well as theaddition of a substrate enhances the activity of the complexesThe variation in the toxicity of different antibacterial agentsagainst various organisms depends on either the imperme-ability of the cell or differences in site of action or ability tocause mutations in the microorganism Though the resultssuggest that the ligand has a remarkable toxic property theircomplexes of tin inhibit the growth of microorganisms toa greater extent This is in accordance with earlier reports[40] Further the greater activity of the complexes can alsobe explained on the basis of their higher solubility of theparticles

4 Conclusion

The FT-IR data of synthesized complexes clearly demon-strate that the zinc and tin become attached with theoxygen and sulphur of the ligand in a bidentate modeIn solid state chlorodiorganotin complexes exhibit thepentahexacoordinated geometry whereas the triorgan-otin(IV) complexes show the five-coordinate geometry Bio-logical activity data showed that all the complexes werebiologically active with few exceptionsThese complexes were

found to be more potent inhibitors toward fungal culture ascompared to bacterial strains

Acknowledgment

Higher EducationCommission of Pakistan (HEC) is acknow-ledged for support under the Project no 20-1623RampD104402

References

[1] K E Appel ldquoOrganotin compounds toxicokinetic aspectsrdquoDrug Metabolism Reviews vol 36 no 3-4 pp 763ndash786 2004

[2] K C Molloy T G Purcell E Hahn H Schumann and J JZuckerman ldquoOrganotin biocides 4 Crystal and molecularstructure of tricyclohexylstannyl 3-indolylacetate incorporat-ing the first monodentate carboxylate group bonded to atriorganotin(IV)rdquoOrganometallics vol 5 no 1 pp 85ndash89 1986

[3] R R Holmes ldquoOrganotin cluster chemistryrdquoAccounts of Chem-ical Research vol 22 no 5 pp 190ndash197 1989

[4] R Barbieri A Silvestri M T L Giudice G Ruisi and M TMusmeci ldquoThe binding of trialkyltin(IV) moieties to rathaemoglobin and the structure of model systems studiedby tin-119 Mossbauer spectroscopyrdquo Journal of the ChemicalSociety Dalton Transactions no 3 pp 519ndash525 1989

[5] S Sadiq-Ur-Rehman K Shahid S Ali M H Bhatti and MParvez ldquoOrganotin esterification of (E)-3-(3-fluoro-phenyl)-2-(4-chlorophenyl)-2-propenoic acid synthesis spectroscopiccharacterization and in vitro biological activities Crystal struc-ture of [Ph

3Sn(OC(O)C(4-ClC

6H4) =CH(3-FC

6H4))]rdquo Journal

of Organometallic Chemistry vol 690 no 5 pp 1396ndash14082005

[6] P J Heard Progress in Inorganic Chemistry vol 53 John Wileyamp Sons New York NY USA 2005 edited by D Karlin

[7] S H LThoonen B Deelman and G van Koten ldquoSynthetic as-pects of tetraorganotins and organotin(IV) halidesrdquo Journal ofOrganometallic Chemistry vol 689 no 13 pp 2145ndash2157 2004

[8] H Hussain V U Ahmad I R Green K Krohn J Hussain andA Badshah ldquoAntibacterial organotin(IV) compounds theirsynthesis and spectral characterizationrdquo Arkivoc vol 2007 no14 pp 289ndash299 2007

[9] S Y Dike J R Merchant and N Y Sapre ldquoA new and efficientgeneral method for the synthesis of 2-spirobenzopyrans firstsynthesis of cyclic analogues of precocene I and related com-poundrdquo Tetrahedron vol 47 no 26 pp 4775ndash4786 1991

[10] L E da Silva P T de Sousa Jr A C Joussef C Piovezan andANeves ldquoSynthesis structure and physicochemical properties ofzinc and copper complexes based on sulfonamides containing8-aminoquinoline ligandsrdquo Quımica Nova vol 31 no 5 pp1161ndash1164 2008

[11] J Anwer S Ali S Shahzadi M Shahid S K Sharma and KQanungo ldquoSynthesis characterization semi-empirical studyand biological activities of homobimetallic complexes of tranex-amic acid with organotin(IV)rdquo Journal of Coordination Chem-istry vol 66 no 7 pp 1142ndash1152 2013

[12] S Jabbar I Shahzadi R Rehman et al ldquoSynthesis character-ization semi-empirical study and biological activities of organ-otin(IV) complexes with cyclohexylcarbamodithioic acid asbiological active ligandrdquo Journal of Coordination Chemistry vol65 no 4 pp 572ndash590 2012

Bioinorganic Chemistry and Applications 7

[13] H N Khan S Ali S Shahzadi and M Helliwell ldquoSynthesisspectroscopy and antimicrobial activity of chloro-organotin(IV) complexes of S-donor ligand crystal structureof chloro-t-dibutyltin[4-methyl-1-piperidine]thiocarboxylaterdquoRussian Journal of Inorganic Chemistry vol 57 no 5 pp665ndash670 2012

[14] F A Shah A Ali S Shahzadi C Rizzoli and A Ahmad ldquoSyn-thesis spectral characterization and X-ray crystal struc-ture of biologically active organotin(IV) 3-[(31015840 51015840-dimethyl-phenylamido)]propanoatesrdquo Journal of Iranian Chemical Soci-ety vol 9 no 6 pp 923ndash932 2012

[15] MM Amin S Ali S Shahzadi S K Sharma and K QanungoldquoDi- and triorganotin(IV) complexes of 2-aminobenzoic acidwith and without triphenylphosphine synthesis spectroscopysemi-empirical study and antimicrobial activitiesrdquo Journal ofCoordination Chemistry vol 64 no 2 pp 337ndash350 2011

[16] E Khoo N K Goh G Eng D J Whalen andA Hzell ldquoSynthesis characterization and fungicidalactivity of triphenyl derivatives of sarcosine crystalstructures of [Ph

3Sn(OCOCH

2NH2CHB)

2]Cl and

[Ph3(OCOCH

2NH2CH3)2]NCSrdquo Applied Organometallic

Chemistry vol 9 no 8 pp 699ndash706 1995[17] DKovala-Demertzi P TauridouAMoukarika JMTsangaris

C P Raptopoulou and A Terzis ldquoSynthesis and characteriza-tion of tin(IV) and organotin(IV) 14-dimethylpiperazine-25-dione (cyclosarcosylsarcosine) adductsrdquo Journal of the ChemicalSociety Dalton Transactions no 1 pp 123ndash128 1995

[18] L Ronconi C Marzano U Russo S Sitran R Graziani and DFregona ldquoSynthesis characterization and in vitro cytotoxicityof new organotin(IV) derivatives of N-methylglycinerdquo Journalof Inorganic Biochemistry vol 91 no 2 pp 413ndash420 2002

[19] W L F Armarego and C L L Chai Purification of LaboratoryChemicals Elsevier Burlington Vt USA 6th edition 2000

[20] W D Honnick and J J Zuckerman ldquoDiorganotin halide car-boxylates thiocarboxylates and halide haloacetatesrdquo Journal ofOrganometallic Chemistry vol 178 no 1 pp 133ndash155 1979

[21] E R T Tiekink ldquoStructural chemistry of organotin carboxyl-ates a review of the crystallographic literaturerdquo Applied Organ-ometallic Chemistry vol 5 no 1 pp 1ndash23 1991

[22] M Nath R Jairath G Eng X Song and A Kumar ldquoSynthesisspectral characterization and biological studies of some organ-otin(IV) complexes of l-proline trans-hydroxy-l-proline and l-glutaminerdquo SpectrochimicaActaA vol 62 no 4-5 pp 1179ndash11872005

[23] B S Hammes M T Kieber-Emmons J A Letizia et al ldquoSyn-thesis and characterization of several zinc(II) complexes con-taining the bulky heteroscorpionate ligand bis(5-tert-butyl-3-methylpyrazol-2-yl)acetate relevance to the resting states ofthe zinc(II) enzymes thermolysin and carboxypeptidase ArdquoInorganica Chimica Acta vol 346 pp 227ndash238 2003

[24] R Singh and N K Kaushik ldquoSpectral and thermal studies withanti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta A vol 71 no 2 pp669ndash675 2008

[25] H L Singh and J B Singh ldquoSynthesis and characterization ofnew lead(II) and organotin(IV) complexes of schiff basesderived fromhistidine andmethioninerdquo International Journal ofInorganic Chemistry vol 2012 Article ID 568797 7 pages 2012

[26] A Saxena J P Tandon K C Molloy and J J ZuckermanldquoTin(IV) complexes of tridentate schiff bases having ONS

donor systemsrdquo Inorganica Chimica Acta vol 63 no C pp 71ndash74 1982

[27] A K Saxena H B Singh and J P Tandon ldquoSynthesis andcharacterization of tin(IV) complexes of azinesrdquo SynthesisReactivity Inorganic and Metal-Organic Chemistry vol 10 pp117ndash136 1980

[28] H O Kalinowski S Berger and S Brown 13C NMR Spectro-skopie Thieme Stuttgart Germany 1984

[29] S Ali F Ahmad M Mazhar A Munir and M T MasoodldquoSynthesis and spectral studies of di- and triorganotin(IV) com-plexes with 2-(6-methoxynaphthyl)propionic acid (naproxen)rdquoSynthesis and Reactivity in Inorganic and Metal-Organic Chem-istry vol 32 no 2 pp 357ndash372 2002

[30] J Holecek M Nadvornık K Handlır and A Lycka ldquo13C and119Sn NMR spectra of Di-n-butyltin(IV) compoundsrdquo Journalof Organometallic Chemistry vol 315 no 3 pp 299ndash308 1986

[31] DHWilliams and I Fleming SpectroscopicMethods inOrganicChemistry McGraw-Hill London UK 4th edition 1987

[32] S S Konstantinovic B C Radovanovic S P Sovilj and SStanojevic ldquoAntimicrobial activity of some isatin-3-thiosemi-carbazone complexesrdquo Journal of the Serbian Chemical Societyvol 73 no 1 pp 7ndash13 2008

[33] R V Singh P Chaudhary S Chauhan and M Swami ldquoMicro-wave-assisted synthesis characterization and biological activi-ties of organotin (IV) complexes with some thio schiff basesrdquoSpectrochimica Acta A vol 72 no 2 pp 260ndash268 2009

[34] W Rehman M K Baloch A Badshah and S Ali ldquoSynthesischaracterization and biological study of diorganotin(IV) com-plexes ofmonomethyl phthalaterdquo SpectrochimicaActaA vol 65no 3-4 pp 689ndash694 2006

[35] K K Chaturvedi and M Goyal ldquoAntibacterial studies of7-(120572-substituted sulphonamido)methyl- and 7-(120572-substitutedsulphonamido)phenyl-8-hydroxyquinolinesrdquo Journal of theIndian Chemical Society vol 61 no 2 pp 175ndash176 1984

[36] H L Singh B Khungar U D Tripaathi and A K VarshneyldquoSpectral and antimicrobial studies of organotin(IV) complexesof bidentate schiff bases having nitrogen and sulphur donorsystemsrdquo Main Group Metal Chemistry vol 24 no 1 pp 5ndash122001

[37] T R Fritsche P F McDermott T R Shryock and R DWalkerldquoAgar dilution and disk diffusion susceptibility testing ofCampylobacter spprdquo Journal of Clinical Microbiology vol 45no 8 pp 2758ndash2759 2007

[38] M Jabeen S Ali S Shahzadi et al ldquoHomobimetallic complexesof ligand having O and S donor sites with same and differentdi- and trialkylaryltin(IV) moiety their synthesis spectralcharacterization and biological activitiesrdquo Journal of IranianChemical Society vol 9 no 3 pp 307ndash320 2012

[39] S Shahzadi K Shahid S Ali and M Bakhtiar ldquoCharacteri-zation and antimicrobial activity of organotin(IV) complexes of2-[(2101584061015840-diethylphenylamido)]benzoates and 3-[(2101584061015840-diethyl-phenylamido)]propanoatesrdquo Turkish Journal of Chemistry vol32 no 3 pp 333ndash353 2008

[40] MAshfaqM I KhanMK Baloch andAMalik ldquoBiologicallypotent organotin(IV) complexes of 2-maleimidoacetic acidrdquoJournal of Organometallic Chemistry vol 689 no 1 pp 238ndash245 2004

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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CatalystsJournal of

2 Bioinorganic Chemistry and Applications

H

N

CH3

HOOC

Figure 1 Chemical structure of sarcosine

These complexes were characterized by elemental anal-ysis IR and multinuclear NMR (1H 13C) These were alsoexamined to check their antibacterial and antifungal activityin vitro

2 Experimental

21 Materials and Methods N-Methyl glycine (sarcosine)zinc acetate carbon disulfide and organotin(IV) halides wereof Sigma-Aldrich (UK) origin The organic solvents (chlo-roform n-hexane ethanol methanol DMSO and acetone)were procured from Merck (Germany) The solvents weredried [19] prior to use Nutrient broth nutrient agar andpotato dextrose agar were of oxide (UK) origin Autoclaveand laminar air flow were purchased from Omron andDalton companies of Japan respectively Micropipettes werepurchased from Gilson (France) The melting points weredetermined on an electrothermal melting point apparatusmodel Staurt SMP3 by using capillary tubes Elemental analy-sis was done for carbon hydrogen nitrogen and sulphur on aCHNS-932 elemental analyzer Leco Corporation (USA)Theinfrared spectrawere recorded asKBr pellets on Perkin Elmer1000 spectrometer in the frequency range of 4000ndash250 cmminus1NMR (1H and 13C) spectra were recorded on Bruker AM-300MHz FT-NMR spectrometer (Germany) using CDCl

3as

an internal reference

22 General Procedure for the Synthesis of Complexes Sar-cosine (0178 g 2mmol) was dissolved in methanol (25mL)in a round bottom flask with continuous stirring at roomtemperatureThen solution of zinc acetate (022 g 1mmol) inmethanol (3mL) was added dropwise to the above solutionand mixture was stirred continuously for 20 minutes Afterthat CS

2(0120mL 20mmol) in methanol (5mL) was added

dropwise to the reaction mixture and stirred for 05 hr atroom temperature Subsequently the solution of diorgan-otin dichloridetriorganotin chloride (2mmol) in methanol(50mL) was added and the mixture was continuously stirredfor 4 hr Solvent was slowly evaporated at room temperatureand product obtained was dried in air Purity was checked byTLC and recrystallization was done in methanol n-hexane(1 1) (see Scheme 1)

3 Results and Discussion

The ligand and synthesized complexes are solid and stable inair They have sharp melting points Elemental analysis wasdone to compare the observed values with predicted valuesof percentage of the carbon hydrogen nitrogen and sulfur

The physical data of ligand and synthesized complexes issummarized in Table 1

31 Infrared Spectroscopy IR spectra of the ligand and itsnewly synthesized complexes (1)ndash(6) were recorded as KBrpellets in the range of 4000ndash250 cmminus1 The characteristicinfrared absorption frequencies (cmminus1) have been listed inTable 2

The IR spectrum of the ligand exhibited a band at3365 cmminus1 which was attributed to the NH stretching modeDeprotonation of carboxylic group is confirmed by theabsence of OH band in the spectra of the complexesRegarding the carboxyl vibrational modes there are differentbinding possibilities [20 21]

(1) bridged structure ]119904(COO) = 1560ndash1540 cmminus1

(2) dimer and monomer chelate structures ]119886(COO) =

1640ndash1560 cmminus1(3) ldquofree esterrdquo monodentate structure ](CndashO) = 1680ndash

1640 cmminus1 and ](C=O) = 1770 1700 cmminus1The carboxylate group gives strong asymmetric and symmet-ric stretching bands in the range of 1602ndash1650 cmminus1 and 1433ndash1470 cmminus1 respectively and it is assignable to a chelate ormonodentate structure however the absence of ]C=O bandin expected range is indicative of the presence of the chelateform Bidentate nature of ligand is also confirmed byΔ]COOvalue that is less than 200 cmminus1 in all complexes [22] Presenceof ]ZnndashO vibrational bands in the range of 310ndash385 cmminus1in all the complexes [23] confirms the zinc carboxylateinteraction It has been reported [15] that the observationof a single ]C=S absorption in the region around 1000 cmminus1is indicative of dithiocarbamate groups that are bondedsymmetrically or bidentate in nature A strong absorptionband of ](C=S) lies in the range of 1013ndash1043 cmminus1 while](CndashS) band appears in the lower frequency range 942ndash988 cmminus1 [24] The SnndashS bond formation is confirmed bythe appearance of a new band in the range of 456ndash480 cmminus1[25] The strong band at 302ndash318 cmminus1 was assigned to ](SnndashCl) absorption The SnndashC band was observed in the rangeof 530ndash547 cmminus1 for complexes (1) and (2)ndash(5) but at 272and 280 cmminus1 for complexes (3) and (4) respectively whichare di- and triphenyltin derivatives The absence of the bandin the range 440ndash420 cmminus1 which is commonly assignedto the ](SnndashN) mode in analogous compounds [26 27]rules out amino coordination to tin thus leading support tothe proposed carboxylate carboxyl atom [16] and dithiolatesulphur atom coordination in all synthesized complexes

32 1H NMR Spectroscopy 1H NMR spectra of the ligandand complexes (1)ndash(6) were recorded in deuterated DMSOto find the behaviour of magnetically nonequivalent protonsThe data is presented in Table 3

The number of protons calculated by integration of peaksis in excellent agreement with those theoretically calculatedby incremental method [28] The absence of OH signal inthe complex suggested the deprotonation of carboxylic acidgroup for O rarr Zn coordination through COOminus anions

Bioinorganic Chemistry and Applications 3

H

H H

N

N

N

N N

N

N

CH3

CH3

CH3

CH3 CH3

CH3

CH3

HOOC + Zn(CH3COO)2

O

O

O

O

O

O

O O

O

O

OO

Zn

Zn

Zn

2CS2

S S

HS SH

2R2SnCl2R3SnCl

R R

RR Sn SnS

S S

S

C

C CC

C C CC

C

C

XX

Compound number

Compound number

R3

R2Cl Me

Me

n-Bu

n-Bu

Ph

Ph

X Cl for diorganotin

X R for triorganotin

R Me n-Bu Ph

2

(1) (2) (3)

(4) (5) (6)

Scheme 1

Table 1 Physical data of heterobimetallic complexes with sarcosine

Compno Molecular formula Mol weight yield mp (∘C)

Elemental analysis CCalcd(found)

HCalcd(found)

NCalcd(found)

SCalcd(found)

HL C3H7O2N 8909 mdash 208 4045 792 1571 mdash(4042) (795) (1568)

(1) C12H22O4N2S4Cl2ZnSn2 76031 75 121-122 1895 291 368 1687(1899) (295) (364) (1689)

(2) C24H46O4N2S4Cl2ZnSn2 92863 68 87ndash91 3104 499 301 1381(3107) (496) (304) (1378)

(3) C32H30O4N2S4Cl2ZnSn2 100853 57 107ndash109 3810 299 277 1271(3912) (296) (274) (1274)

(4) C14H28O4N2S4ZnSn2 71961 67 145-146 2336 392 389 1782(2339) (396) (392) (1778)

(5) C32H64O4N2S4ZnSn2 97153 51 224-225 3955 664 288 1320(3950) (668) (285) (1317)

(6) C44H40O4N2S4ZnSn2 109189 73 86ndash88 4839 369 256 1174(4836) (365) (259) (1178)

4 Bioinorganic Chemistry and Applications

Table 2 IR spectral data (cmminus1) of heterobimetallic complexes with sarcosine

Comp no ](NH) ](COO)Δ] ](C=S) ](CndashS) ](SnndashC) ](SnndashS) ](SnndashCl) ](ZnndashO)

](COO) (asym) ](COO) (sym)HL 3365 1621 1407 214 mdash mdash mdash mdash mdash mdash(1) mdash 1642 1462 180 1033 955 526 461 311 364(2) mdash 1618 1433 185 1013 942 530 472 302 352(3) mdash 1602 1440 162 1025 988 272 466 318 347(4) mdash 1622 1456 166 1023 938 538 485 mdash 371(5) mdash 1635 1468 167 1043 965 547 456 mdash 385(6) mdash 1650 1470 180 1030 970 280 480 mdash 310

Table 3 1H NMR dataandashd (ppm) of heterobimetallic complexes with sarcosine

Proton no HL (1) (2) (3) (4) (5) (6)2 21015840 315s 397s 399s 388s 374s 363s 395s3 31015840 248s 289s 280s 296s 285s 294s 279saCompound (1) Sn-CH3Cl 127s

2J[96] compound (2) Sn-CH2CH2CH2CH3Cl 088ndash093m 023t (72) compound (3) Sn-C6H5Cl 791d2J[82] 750ndash753m

742ndash750m compound (4) Sn-CH3 051s2J[82] compound (5) Sn-CH2CH2CH2CH3 064ndash11m 023t (72) compound (6) Sn-C6H5 791d

2J[82] 750ndash753m742ndash750mbMultiplicity is given as s singlet d doublet t triplet m multipletcCoupling constant 119899J[119Sn 1H] and 119899J[1H 1H] in Hz are given in square bracket and parenthesis respectivelyd

NN

CH3CH3

3998400

1998400

2998400

CCOO

OOZn

1

2

3

Table 4 13C NMR dataab (ppm) of heterobimetallic Zn(II) andSn(IV) complexes with sarcosine

Carbon HL (1) (2) (3) (4) (5) (6)1 11015840 1792 1863 1819 1837 1854 1843 18382 21015840 566 568 563 569 567 566 5683 31015840 415 413 413 415 414 412 415ndashCSS mdash 2026 2025 2028 2017 2028 2027aCompound (1) Sn-CH3Cl (C-120572) 21 1J[397] compound (2) Sn-CH2CH2CH2CH3Cl (C-120572) 295 (C-120573) 274 (C-120574) 262 (C-120575) 139compound (3) Sn-C6H5Cl (C-120572) 1376

1J[640] (C-120573) 1328 2J[490] (C-120574)1299 (C-120575) 1248 compound (4) Sn-CH3 (C-120572) 23 1J[396] compound(5) Sn-CH2CH2CH2CH3 (C-120572) 311 [349] (C-120573) 271 2J[21] (C-120574) 2823J[63] (C-120575) 141 compound (6) Sn-C6H5 (C-120572) 1380

1J[640] (C-120573) 13302J[490] (C-120574) 1300 (C-120575) 1251bChemical shifts (120575) in ppm 119899J[119Sn 13C] in Hz is listed in parenthesis

Two resonance signals appeared as a singlet at 315 ppm and248 ppm for the methylene andmethyl protons respectivelyin the free ligand These signals exhibited downfield shift to363ndash399 ppm and 279ndash296 ppm in the complexes (1)ndash(6)for methylene and methyl protons respectively

The CH3protons in compound (1) appear as a singlet

at 127 ppm with tin satellites having 2J[119Snndash1H] = 96HzIn compound (2) the protons of butyl group appear as amultiplet in the region 088ndash093 ppm The terminal CH

3

group of butyl gives triplet at 023 ppm with 3J[1Hndash1H] valueof 72Hz The proton chemical shift of the methyl group incompound (3) attached to the Sn gives a singlet at 051 ppm

The phenyl moieties of di- and triphenyltin(IV) derivativesshow a complex pattern and were assigned according to theliterature [29] The 2J[119Snndash1H] value for di- and triph-enyltin(IV) derivatives is 82Hz in the range expected forpentacoordinated tin atom and consistent with CndashSnndashCangle of 1265∘

33 13C NMR The assignments of ndashCSS group in investi-gated compounds is straightforward which are observed inthe range of 2025ndash2028 ppm indicating the coordination ofsulfur to the tin atom

Table 4 lists the chemical shifts of 13C and tin-carboncoupling constants for the reported complexes (1)ndash(6) The13C NMR chemical shifts due to the phenyl groups areobserved at positions comparable to other similar com-pounds [30 31] The 13C NMR chemical shift due to ndashCOOcarbon atom is observed at 1792 ppm in the free ligandwhile in the complexes it exhibits downfield shift in therange 1819ndash1863 ppm Coordination of the tin atom in di-and triorganotin has been related to 119899J(119Snndash13C) couplingconstants The 119899J(119Snndash13C) coupling for complexes (1) and(6) is 397 and 640Hz respectively which is indicative of fourcoordinate geometry [30] in solution state

34 Antibacterial Activity Sarcosine and synthesized com-plexes (1)ndash(6) were tested in vitro for their antibacterialactivity against gram positive and gram negative bacterial

Bioinorganic Chemistry and Applications 5

Table 5 Antibacterial activity dataandashe of complexes and ligand against selected bacterial strains

Compound no Bacterial inhibition zone (mm)S aureus B subtilis E coli P multocida

HL 125c plusmn 086 130c plusmn 100 125c plusmn 086 120c plusmn 141(1) 208bc plusmn 100 180c plusmn 100 252c plusmn 086 210ab plusmn 100(2) 210bc plusmn 100 205bc plusmn 086 275bc plusmn 086 245ab plusmn 086(3) 208bc plusmn 100 186c plusmn 100 262c plusmn 086 213ab plusmn 100(4) 300ab plusmn 141 215bc plusmn 165 280bc plusmn 141 230ab plusmn 100(5) 325ab plusmn 165 545a plusmn 086 510a plusmn 100 325a plusmn 165(6) 315ab plusmn 086 330bc plusmn 141 320ab plusmn 100 300ab plusmn 141Ampicillin 385a plusmn 086 400ab plusmn 141 395ab plusmn 086 320ab plusmn 141aConcentration 1mgmL in DMSObStandard ampicillinc0 no activity 5ndash10 activity present 11ndash25 moderate activity 26ndash40 strong activitydAntibacterial values are mean plusmn SD of samples analyzed individually in triplicate at 119875 lt 01eDifferent letters in superscript indicate significant differences

Table 6 Antifungal activity dataandashe of complexes and ligand against selected fungal strains

Compound no Fungal inhibition zone (mm)A alternata 119866 lucidum A flavus 119860 niger

HL 270ab plusmn 100 115c plusmn 086 375ab plusmn 086 145bc plusmn 165(1) 264ab plusmn 100 193bc plusmn 100 202bc plusmn 165 203ab plusmn 086(2) 200c plusmn 141 190bc plusmn 100 205bc plusmn 165 205bc plusmn 086(3) 269bc plusmn 141 202ab plusmn 165 352bc plusmn 165 212bc plusmn 086(4) 300ab plusmn 141 185bc plusmn 086 195c plusmn 165 185bc plusmn 086(5) 300ab plusmn 141 395ab plusmn 165 370

abplusmn 165 335 a

plusmn 165(6) 285ab plusmn 086 250bc plusmn 100 320bc plusmn 141 195bc plusmn 086Fluconazole 305a plusmn 086 415a plusmn 086 540a plusmn 141 125c plusmn 086aConcentration 1mgmL in DMSObStandard fluconazolec0 no activity 5ndash10 activity present 11ndash25 moderate activity 26ndash40 strong activitydAntibacterial values are mean plusmn SD of samples analyzed individually in triplicate at 119875 lt 01eDifferent letters in superscript indicate significant differences

strains including B subtilis and S aureus and P multocidaand E coli respectively and the results are given in Table 5Ampicillin was used as a standard drug The results revealedthat all the newly synthesized complexes show higher activitythan the ligand but markedly lower than the standard drugwith few exceptions

Complex (5) showed maximum inhibitory action againstB subtilis (545 plusmn 086) and E coli (510 plusmn 100) probablymore than standard drug (4000 plusmn 141) and (395 plusmn 086)respectively Complex (2) displayed lowest inhibition zone incase of B subtilis (205plusmn086) and S aureus (210plusmn100)Theligand exhibited low activities while the complexes exhibitedmoderate activities as compared to standard drug towards allthe bacterial strains Complex (6) showed moderate antibac-terial activity against all the bacterial strains Among all thecomplexes the tributyltin complex (5) showed significantantibacterial activity It was clear from the data that antimi-crobial activities varied according to substitution (increasein substitution on the Sn(IV) enhances the antimicrobialactivity) [32]

Data revealed that the synthesized complexes showedmore activity against gram positive bacterial strain thangram negative strains It was due to the difference in thecomposition of cell wall of both the gram positive and gramnegative strains [33] It was also suggested that the anti-microbial activity of the complexes was either due to killingofmicrobes or inhibiting their reproduction by blocking theiractive sites [34]

The results show that all compounds exhibit antibacterialactivity and in many cases complexes are more potent intheir inhibition properties than the free ligand This canbe explained in terms of the greater lipid solubility andcellular penetration of the complexes [35] It is clear that thecoordination enhances the antibacterial activity and clearlyindicates that the newly synthesized complexes in the presentstudies are more active against gram positive than gramnegative bacteria The preliminary results achieved have ledus to conclude that these types of complexes should bestudied in detail for their applications in diverse area

The screening data of a particular ligand and its metalcomplexes show that the former has greater activity than

6 Bioinorganic Chemistry and Applications

the latter from the biochemical point of view On comparingthe results in general it may be concluded that complexescontaining Zn(II) and Sn(IV) have greater inhibiting powerthan the free ligands as compared to organotin complexeswith sarcosine [16 17] against all the microbes

35 Antifungal Activity The synthesized compounds (1)ndash(6)and sarcosine were tested for antifungal activity by usingfluconazole as standard drug against four fungal strainsincluding A flavus A niger A alternate and G lucidum bydisc diffusion method [36] The results are summarized inTable 6 It was evident from tabulated data that the sarcosineas well as the synthesized complexes exhibited variety offungicidal activity Sarcosine exhibited maximum activityagainst A flavus (375 plusmn 086) while complex (5) exhibitedmaximum activity (395 plusmn 165) against G lucidum Complex(2) showed the lowest inhibition zone (190 plusmn 100) againstG lucidum It is noted that tributyltin complexes showed thegreatest inhibitory effect against fungi as compared to otheralkyl groupsThus the presence of butyl groups in compound(5) bonded with tin atom was responsible for the rise ofantifungal activity [37] The increased activity of complexesmight be due to the coordination of zinc and tin with oxygenand sulfur respectively [38] From the data it might beconcluded that triorganotin compounds were usually moreeffective against the fungi than diorganotin compounds [39]in contrast to earlier reported compounds in the literature[16] This might be due to the presence of Zn(II) along withSn(IV) which enhances the fungicidal activity of triorganotincomplexes

36 Structure Activity Relationship Although it is difficult tomake out an exact structure-activity relationship between theantimicrobial activity and the structure of these complexesit can possibly be concluded that the chelation as well as theaddition of a substrate enhances the activity of the complexesThe variation in the toxicity of different antibacterial agentsagainst various organisms depends on either the imperme-ability of the cell or differences in site of action or ability tocause mutations in the microorganism Though the resultssuggest that the ligand has a remarkable toxic property theircomplexes of tin inhibit the growth of microorganisms toa greater extent This is in accordance with earlier reports[40] Further the greater activity of the complexes can alsobe explained on the basis of their higher solubility of theparticles

4 Conclusion

The FT-IR data of synthesized complexes clearly demon-strate that the zinc and tin become attached with theoxygen and sulphur of the ligand in a bidentate modeIn solid state chlorodiorganotin complexes exhibit thepentahexacoordinated geometry whereas the triorgan-otin(IV) complexes show the five-coordinate geometry Bio-logical activity data showed that all the complexes werebiologically active with few exceptionsThese complexes were

found to be more potent inhibitors toward fungal culture ascompared to bacterial strains

Acknowledgment

Higher EducationCommission of Pakistan (HEC) is acknow-ledged for support under the Project no 20-1623RampD104402

References

[1] K E Appel ldquoOrganotin compounds toxicokinetic aspectsrdquoDrug Metabolism Reviews vol 36 no 3-4 pp 763ndash786 2004

[2] K C Molloy T G Purcell E Hahn H Schumann and J JZuckerman ldquoOrganotin biocides 4 Crystal and molecularstructure of tricyclohexylstannyl 3-indolylacetate incorporat-ing the first monodentate carboxylate group bonded to atriorganotin(IV)rdquoOrganometallics vol 5 no 1 pp 85ndash89 1986

[3] R R Holmes ldquoOrganotin cluster chemistryrdquoAccounts of Chem-ical Research vol 22 no 5 pp 190ndash197 1989

[4] R Barbieri A Silvestri M T L Giudice G Ruisi and M TMusmeci ldquoThe binding of trialkyltin(IV) moieties to rathaemoglobin and the structure of model systems studiedby tin-119 Mossbauer spectroscopyrdquo Journal of the ChemicalSociety Dalton Transactions no 3 pp 519ndash525 1989

[5] S Sadiq-Ur-Rehman K Shahid S Ali M H Bhatti and MParvez ldquoOrganotin esterification of (E)-3-(3-fluoro-phenyl)-2-(4-chlorophenyl)-2-propenoic acid synthesis spectroscopiccharacterization and in vitro biological activities Crystal struc-ture of [Ph

3Sn(OC(O)C(4-ClC

6H4) =CH(3-FC

6H4))]rdquo Journal

of Organometallic Chemistry vol 690 no 5 pp 1396ndash14082005

[6] P J Heard Progress in Inorganic Chemistry vol 53 John Wileyamp Sons New York NY USA 2005 edited by D Karlin

[7] S H LThoonen B Deelman and G van Koten ldquoSynthetic as-pects of tetraorganotins and organotin(IV) halidesrdquo Journal ofOrganometallic Chemistry vol 689 no 13 pp 2145ndash2157 2004

[8] H Hussain V U Ahmad I R Green K Krohn J Hussain andA Badshah ldquoAntibacterial organotin(IV) compounds theirsynthesis and spectral characterizationrdquo Arkivoc vol 2007 no14 pp 289ndash299 2007

[9] S Y Dike J R Merchant and N Y Sapre ldquoA new and efficientgeneral method for the synthesis of 2-spirobenzopyrans firstsynthesis of cyclic analogues of precocene I and related com-poundrdquo Tetrahedron vol 47 no 26 pp 4775ndash4786 1991

[10] L E da Silva P T de Sousa Jr A C Joussef C Piovezan andANeves ldquoSynthesis structure and physicochemical properties ofzinc and copper complexes based on sulfonamides containing8-aminoquinoline ligandsrdquo Quımica Nova vol 31 no 5 pp1161ndash1164 2008

[11] J Anwer S Ali S Shahzadi M Shahid S K Sharma and KQanungo ldquoSynthesis characterization semi-empirical studyand biological activities of homobimetallic complexes of tranex-amic acid with organotin(IV)rdquo Journal of Coordination Chem-istry vol 66 no 7 pp 1142ndash1152 2013

[12] S Jabbar I Shahzadi R Rehman et al ldquoSynthesis character-ization semi-empirical study and biological activities of organ-otin(IV) complexes with cyclohexylcarbamodithioic acid asbiological active ligandrdquo Journal of Coordination Chemistry vol65 no 4 pp 572ndash590 2012

Bioinorganic Chemistry and Applications 7

[13] H N Khan S Ali S Shahzadi and M Helliwell ldquoSynthesisspectroscopy and antimicrobial activity of chloro-organotin(IV) complexes of S-donor ligand crystal structureof chloro-t-dibutyltin[4-methyl-1-piperidine]thiocarboxylaterdquoRussian Journal of Inorganic Chemistry vol 57 no 5 pp665ndash670 2012

[14] F A Shah A Ali S Shahzadi C Rizzoli and A Ahmad ldquoSyn-thesis spectral characterization and X-ray crystal struc-ture of biologically active organotin(IV) 3-[(31015840 51015840-dimethyl-phenylamido)]propanoatesrdquo Journal of Iranian Chemical Soci-ety vol 9 no 6 pp 923ndash932 2012

[15] MM Amin S Ali S Shahzadi S K Sharma and K QanungoldquoDi- and triorganotin(IV) complexes of 2-aminobenzoic acidwith and without triphenylphosphine synthesis spectroscopysemi-empirical study and antimicrobial activitiesrdquo Journal ofCoordination Chemistry vol 64 no 2 pp 337ndash350 2011

[16] E Khoo N K Goh G Eng D J Whalen andA Hzell ldquoSynthesis characterization and fungicidalactivity of triphenyl derivatives of sarcosine crystalstructures of [Ph

3Sn(OCOCH

2NH2CHB)

2]Cl and

[Ph3(OCOCH

2NH2CH3)2]NCSrdquo Applied Organometallic

Chemistry vol 9 no 8 pp 699ndash706 1995[17] DKovala-Demertzi P TauridouAMoukarika JMTsangaris

C P Raptopoulou and A Terzis ldquoSynthesis and characteriza-tion of tin(IV) and organotin(IV) 14-dimethylpiperazine-25-dione (cyclosarcosylsarcosine) adductsrdquo Journal of the ChemicalSociety Dalton Transactions no 1 pp 123ndash128 1995

[18] L Ronconi C Marzano U Russo S Sitran R Graziani and DFregona ldquoSynthesis characterization and in vitro cytotoxicityof new organotin(IV) derivatives of N-methylglycinerdquo Journalof Inorganic Biochemistry vol 91 no 2 pp 413ndash420 2002

[19] W L F Armarego and C L L Chai Purification of LaboratoryChemicals Elsevier Burlington Vt USA 6th edition 2000

[20] W D Honnick and J J Zuckerman ldquoDiorganotin halide car-boxylates thiocarboxylates and halide haloacetatesrdquo Journal ofOrganometallic Chemistry vol 178 no 1 pp 133ndash155 1979

[21] E R T Tiekink ldquoStructural chemistry of organotin carboxyl-ates a review of the crystallographic literaturerdquo Applied Organ-ometallic Chemistry vol 5 no 1 pp 1ndash23 1991

[22] M Nath R Jairath G Eng X Song and A Kumar ldquoSynthesisspectral characterization and biological studies of some organ-otin(IV) complexes of l-proline trans-hydroxy-l-proline and l-glutaminerdquo SpectrochimicaActaA vol 62 no 4-5 pp 1179ndash11872005

[23] B S Hammes M T Kieber-Emmons J A Letizia et al ldquoSyn-thesis and characterization of several zinc(II) complexes con-taining the bulky heteroscorpionate ligand bis(5-tert-butyl-3-methylpyrazol-2-yl)acetate relevance to the resting states ofthe zinc(II) enzymes thermolysin and carboxypeptidase ArdquoInorganica Chimica Acta vol 346 pp 227ndash238 2003

[24] R Singh and N K Kaushik ldquoSpectral and thermal studies withanti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta A vol 71 no 2 pp669ndash675 2008

[25] H L Singh and J B Singh ldquoSynthesis and characterization ofnew lead(II) and organotin(IV) complexes of schiff basesderived fromhistidine andmethioninerdquo International Journal ofInorganic Chemistry vol 2012 Article ID 568797 7 pages 2012

[26] A Saxena J P Tandon K C Molloy and J J ZuckermanldquoTin(IV) complexes of tridentate schiff bases having ONS

donor systemsrdquo Inorganica Chimica Acta vol 63 no C pp 71ndash74 1982

[27] A K Saxena H B Singh and J P Tandon ldquoSynthesis andcharacterization of tin(IV) complexes of azinesrdquo SynthesisReactivity Inorganic and Metal-Organic Chemistry vol 10 pp117ndash136 1980

[28] H O Kalinowski S Berger and S Brown 13C NMR Spectro-skopie Thieme Stuttgart Germany 1984

[29] S Ali F Ahmad M Mazhar A Munir and M T MasoodldquoSynthesis and spectral studies of di- and triorganotin(IV) com-plexes with 2-(6-methoxynaphthyl)propionic acid (naproxen)rdquoSynthesis and Reactivity in Inorganic and Metal-Organic Chem-istry vol 32 no 2 pp 357ndash372 2002

[30] J Holecek M Nadvornık K Handlır and A Lycka ldquo13C and119Sn NMR spectra of Di-n-butyltin(IV) compoundsrdquo Journalof Organometallic Chemistry vol 315 no 3 pp 299ndash308 1986

[31] DHWilliams and I Fleming SpectroscopicMethods inOrganicChemistry McGraw-Hill London UK 4th edition 1987

[32] S S Konstantinovic B C Radovanovic S P Sovilj and SStanojevic ldquoAntimicrobial activity of some isatin-3-thiosemi-carbazone complexesrdquo Journal of the Serbian Chemical Societyvol 73 no 1 pp 7ndash13 2008

[33] R V Singh P Chaudhary S Chauhan and M Swami ldquoMicro-wave-assisted synthesis characterization and biological activi-ties of organotin (IV) complexes with some thio schiff basesrdquoSpectrochimica Acta A vol 72 no 2 pp 260ndash268 2009

[34] W Rehman M K Baloch A Badshah and S Ali ldquoSynthesischaracterization and biological study of diorganotin(IV) com-plexes ofmonomethyl phthalaterdquo SpectrochimicaActaA vol 65no 3-4 pp 689ndash694 2006

[35] K K Chaturvedi and M Goyal ldquoAntibacterial studies of7-(120572-substituted sulphonamido)methyl- and 7-(120572-substitutedsulphonamido)phenyl-8-hydroxyquinolinesrdquo Journal of theIndian Chemical Society vol 61 no 2 pp 175ndash176 1984

[36] H L Singh B Khungar U D Tripaathi and A K VarshneyldquoSpectral and antimicrobial studies of organotin(IV) complexesof bidentate schiff bases having nitrogen and sulphur donorsystemsrdquo Main Group Metal Chemistry vol 24 no 1 pp 5ndash122001

[37] T R Fritsche P F McDermott T R Shryock and R DWalkerldquoAgar dilution and disk diffusion susceptibility testing ofCampylobacter spprdquo Journal of Clinical Microbiology vol 45no 8 pp 2758ndash2759 2007

[38] M Jabeen S Ali S Shahzadi et al ldquoHomobimetallic complexesof ligand having O and S donor sites with same and differentdi- and trialkylaryltin(IV) moiety their synthesis spectralcharacterization and biological activitiesrdquo Journal of IranianChemical Society vol 9 no 3 pp 307ndash320 2012

[39] S Shahzadi K Shahid S Ali and M Bakhtiar ldquoCharacteri-zation and antimicrobial activity of organotin(IV) complexes of2-[(2101584061015840-diethylphenylamido)]benzoates and 3-[(2101584061015840-diethyl-phenylamido)]propanoatesrdquo Turkish Journal of Chemistry vol32 no 3 pp 333ndash353 2008

[40] MAshfaqM I KhanMK Baloch andAMalik ldquoBiologicallypotent organotin(IV) complexes of 2-maleimidoacetic acidrdquoJournal of Organometallic Chemistry vol 689 no 1 pp 238ndash245 2004

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

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Analytical ChemistryInternational Journal of

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Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Bioinorganic Chemistry and Applications 3

H

H H

N

N

N

N N

N

N

CH3

CH3

CH3

CH3 CH3

CH3

CH3

HOOC + Zn(CH3COO)2

O

O

O

O

O

O

O O

O

O

OO

Zn

Zn

Zn

2CS2

S S

HS SH

2R2SnCl2R3SnCl

R R

RR Sn SnS

S S

S

C

C CC

C C CC

C

C

XX

Compound number

Compound number

R3

R2Cl Me

Me

n-Bu

n-Bu

Ph

Ph

X Cl for diorganotin

X R for triorganotin

R Me n-Bu Ph

2

(1) (2) (3)

(4) (5) (6)

Scheme 1

Table 1 Physical data of heterobimetallic complexes with sarcosine

Compno Molecular formula Mol weight yield mp (∘C)

Elemental analysis CCalcd(found)

HCalcd(found)

NCalcd(found)

SCalcd(found)

HL C3H7O2N 8909 mdash 208 4045 792 1571 mdash(4042) (795) (1568)

(1) C12H22O4N2S4Cl2ZnSn2 76031 75 121-122 1895 291 368 1687(1899) (295) (364) (1689)

(2) C24H46O4N2S4Cl2ZnSn2 92863 68 87ndash91 3104 499 301 1381(3107) (496) (304) (1378)

(3) C32H30O4N2S4Cl2ZnSn2 100853 57 107ndash109 3810 299 277 1271(3912) (296) (274) (1274)

(4) C14H28O4N2S4ZnSn2 71961 67 145-146 2336 392 389 1782(2339) (396) (392) (1778)

(5) C32H64O4N2S4ZnSn2 97153 51 224-225 3955 664 288 1320(3950) (668) (285) (1317)

(6) C44H40O4N2S4ZnSn2 109189 73 86ndash88 4839 369 256 1174(4836) (365) (259) (1178)

4 Bioinorganic Chemistry and Applications

Table 2 IR spectral data (cmminus1) of heterobimetallic complexes with sarcosine

Comp no ](NH) ](COO)Δ] ](C=S) ](CndashS) ](SnndashC) ](SnndashS) ](SnndashCl) ](ZnndashO)

](COO) (asym) ](COO) (sym)HL 3365 1621 1407 214 mdash mdash mdash mdash mdash mdash(1) mdash 1642 1462 180 1033 955 526 461 311 364(2) mdash 1618 1433 185 1013 942 530 472 302 352(3) mdash 1602 1440 162 1025 988 272 466 318 347(4) mdash 1622 1456 166 1023 938 538 485 mdash 371(5) mdash 1635 1468 167 1043 965 547 456 mdash 385(6) mdash 1650 1470 180 1030 970 280 480 mdash 310

Table 3 1H NMR dataandashd (ppm) of heterobimetallic complexes with sarcosine

Proton no HL (1) (2) (3) (4) (5) (6)2 21015840 315s 397s 399s 388s 374s 363s 395s3 31015840 248s 289s 280s 296s 285s 294s 279saCompound (1) Sn-CH3Cl 127s

2J[96] compound (2) Sn-CH2CH2CH2CH3Cl 088ndash093m 023t (72) compound (3) Sn-C6H5Cl 791d2J[82] 750ndash753m

742ndash750m compound (4) Sn-CH3 051s2J[82] compound (5) Sn-CH2CH2CH2CH3 064ndash11m 023t (72) compound (6) Sn-C6H5 791d

2J[82] 750ndash753m742ndash750mbMultiplicity is given as s singlet d doublet t triplet m multipletcCoupling constant 119899J[119Sn 1H] and 119899J[1H 1H] in Hz are given in square bracket and parenthesis respectivelyd

NN

CH3CH3

3998400

1998400

2998400

CCOO

OOZn

1

2

3

Table 4 13C NMR dataab (ppm) of heterobimetallic Zn(II) andSn(IV) complexes with sarcosine

Carbon HL (1) (2) (3) (4) (5) (6)1 11015840 1792 1863 1819 1837 1854 1843 18382 21015840 566 568 563 569 567 566 5683 31015840 415 413 413 415 414 412 415ndashCSS mdash 2026 2025 2028 2017 2028 2027aCompound (1) Sn-CH3Cl (C-120572) 21 1J[397] compound (2) Sn-CH2CH2CH2CH3Cl (C-120572) 295 (C-120573) 274 (C-120574) 262 (C-120575) 139compound (3) Sn-C6H5Cl (C-120572) 1376

1J[640] (C-120573) 1328 2J[490] (C-120574)1299 (C-120575) 1248 compound (4) Sn-CH3 (C-120572) 23 1J[396] compound(5) Sn-CH2CH2CH2CH3 (C-120572) 311 [349] (C-120573) 271 2J[21] (C-120574) 2823J[63] (C-120575) 141 compound (6) Sn-C6H5 (C-120572) 1380

1J[640] (C-120573) 13302J[490] (C-120574) 1300 (C-120575) 1251bChemical shifts (120575) in ppm 119899J[119Sn 13C] in Hz is listed in parenthesis

Two resonance signals appeared as a singlet at 315 ppm and248 ppm for the methylene andmethyl protons respectivelyin the free ligand These signals exhibited downfield shift to363ndash399 ppm and 279ndash296 ppm in the complexes (1)ndash(6)for methylene and methyl protons respectively

The CH3protons in compound (1) appear as a singlet

at 127 ppm with tin satellites having 2J[119Snndash1H] = 96HzIn compound (2) the protons of butyl group appear as amultiplet in the region 088ndash093 ppm The terminal CH

3

group of butyl gives triplet at 023 ppm with 3J[1Hndash1H] valueof 72Hz The proton chemical shift of the methyl group incompound (3) attached to the Sn gives a singlet at 051 ppm

The phenyl moieties of di- and triphenyltin(IV) derivativesshow a complex pattern and were assigned according to theliterature [29] The 2J[119Snndash1H] value for di- and triph-enyltin(IV) derivatives is 82Hz in the range expected forpentacoordinated tin atom and consistent with CndashSnndashCangle of 1265∘

33 13C NMR The assignments of ndashCSS group in investi-gated compounds is straightforward which are observed inthe range of 2025ndash2028 ppm indicating the coordination ofsulfur to the tin atom

Table 4 lists the chemical shifts of 13C and tin-carboncoupling constants for the reported complexes (1)ndash(6) The13C NMR chemical shifts due to the phenyl groups areobserved at positions comparable to other similar com-pounds [30 31] The 13C NMR chemical shift due to ndashCOOcarbon atom is observed at 1792 ppm in the free ligandwhile in the complexes it exhibits downfield shift in therange 1819ndash1863 ppm Coordination of the tin atom in di-and triorganotin has been related to 119899J(119Snndash13C) couplingconstants The 119899J(119Snndash13C) coupling for complexes (1) and(6) is 397 and 640Hz respectively which is indicative of fourcoordinate geometry [30] in solution state

34 Antibacterial Activity Sarcosine and synthesized com-plexes (1)ndash(6) were tested in vitro for their antibacterialactivity against gram positive and gram negative bacterial

Bioinorganic Chemistry and Applications 5

Table 5 Antibacterial activity dataandashe of complexes and ligand against selected bacterial strains

Compound no Bacterial inhibition zone (mm)S aureus B subtilis E coli P multocida

HL 125c plusmn 086 130c plusmn 100 125c plusmn 086 120c plusmn 141(1) 208bc plusmn 100 180c plusmn 100 252c plusmn 086 210ab plusmn 100(2) 210bc plusmn 100 205bc plusmn 086 275bc plusmn 086 245ab plusmn 086(3) 208bc plusmn 100 186c plusmn 100 262c plusmn 086 213ab plusmn 100(4) 300ab plusmn 141 215bc plusmn 165 280bc plusmn 141 230ab plusmn 100(5) 325ab plusmn 165 545a plusmn 086 510a plusmn 100 325a plusmn 165(6) 315ab plusmn 086 330bc plusmn 141 320ab plusmn 100 300ab plusmn 141Ampicillin 385a plusmn 086 400ab plusmn 141 395ab plusmn 086 320ab plusmn 141aConcentration 1mgmL in DMSObStandard ampicillinc0 no activity 5ndash10 activity present 11ndash25 moderate activity 26ndash40 strong activitydAntibacterial values are mean plusmn SD of samples analyzed individually in triplicate at 119875 lt 01eDifferent letters in superscript indicate significant differences

Table 6 Antifungal activity dataandashe of complexes and ligand against selected fungal strains

Compound no Fungal inhibition zone (mm)A alternata 119866 lucidum A flavus 119860 niger

HL 270ab plusmn 100 115c plusmn 086 375ab plusmn 086 145bc plusmn 165(1) 264ab plusmn 100 193bc plusmn 100 202bc plusmn 165 203ab plusmn 086(2) 200c plusmn 141 190bc plusmn 100 205bc plusmn 165 205bc plusmn 086(3) 269bc plusmn 141 202ab plusmn 165 352bc plusmn 165 212bc plusmn 086(4) 300ab plusmn 141 185bc plusmn 086 195c plusmn 165 185bc plusmn 086(5) 300ab plusmn 141 395ab plusmn 165 370

abplusmn 165 335 a

plusmn 165(6) 285ab plusmn 086 250bc plusmn 100 320bc plusmn 141 195bc plusmn 086Fluconazole 305a plusmn 086 415a plusmn 086 540a plusmn 141 125c plusmn 086aConcentration 1mgmL in DMSObStandard fluconazolec0 no activity 5ndash10 activity present 11ndash25 moderate activity 26ndash40 strong activitydAntibacterial values are mean plusmn SD of samples analyzed individually in triplicate at 119875 lt 01eDifferent letters in superscript indicate significant differences

strains including B subtilis and S aureus and P multocidaand E coli respectively and the results are given in Table 5Ampicillin was used as a standard drug The results revealedthat all the newly synthesized complexes show higher activitythan the ligand but markedly lower than the standard drugwith few exceptions

Complex (5) showed maximum inhibitory action againstB subtilis (545 plusmn 086) and E coli (510 plusmn 100) probablymore than standard drug (4000 plusmn 141) and (395 plusmn 086)respectively Complex (2) displayed lowest inhibition zone incase of B subtilis (205plusmn086) and S aureus (210plusmn100)Theligand exhibited low activities while the complexes exhibitedmoderate activities as compared to standard drug towards allthe bacterial strains Complex (6) showed moderate antibac-terial activity against all the bacterial strains Among all thecomplexes the tributyltin complex (5) showed significantantibacterial activity It was clear from the data that antimi-crobial activities varied according to substitution (increasein substitution on the Sn(IV) enhances the antimicrobialactivity) [32]

Data revealed that the synthesized complexes showedmore activity against gram positive bacterial strain thangram negative strains It was due to the difference in thecomposition of cell wall of both the gram positive and gramnegative strains [33] It was also suggested that the anti-microbial activity of the complexes was either due to killingofmicrobes or inhibiting their reproduction by blocking theiractive sites [34]

The results show that all compounds exhibit antibacterialactivity and in many cases complexes are more potent intheir inhibition properties than the free ligand This canbe explained in terms of the greater lipid solubility andcellular penetration of the complexes [35] It is clear that thecoordination enhances the antibacterial activity and clearlyindicates that the newly synthesized complexes in the presentstudies are more active against gram positive than gramnegative bacteria The preliminary results achieved have ledus to conclude that these types of complexes should bestudied in detail for their applications in diverse area

The screening data of a particular ligand and its metalcomplexes show that the former has greater activity than

6 Bioinorganic Chemistry and Applications

the latter from the biochemical point of view On comparingthe results in general it may be concluded that complexescontaining Zn(II) and Sn(IV) have greater inhibiting powerthan the free ligands as compared to organotin complexeswith sarcosine [16 17] against all the microbes

35 Antifungal Activity The synthesized compounds (1)ndash(6)and sarcosine were tested for antifungal activity by usingfluconazole as standard drug against four fungal strainsincluding A flavus A niger A alternate and G lucidum bydisc diffusion method [36] The results are summarized inTable 6 It was evident from tabulated data that the sarcosineas well as the synthesized complexes exhibited variety offungicidal activity Sarcosine exhibited maximum activityagainst A flavus (375 plusmn 086) while complex (5) exhibitedmaximum activity (395 plusmn 165) against G lucidum Complex(2) showed the lowest inhibition zone (190 plusmn 100) againstG lucidum It is noted that tributyltin complexes showed thegreatest inhibitory effect against fungi as compared to otheralkyl groupsThus the presence of butyl groups in compound(5) bonded with tin atom was responsible for the rise ofantifungal activity [37] The increased activity of complexesmight be due to the coordination of zinc and tin with oxygenand sulfur respectively [38] From the data it might beconcluded that triorganotin compounds were usually moreeffective against the fungi than diorganotin compounds [39]in contrast to earlier reported compounds in the literature[16] This might be due to the presence of Zn(II) along withSn(IV) which enhances the fungicidal activity of triorganotincomplexes

36 Structure Activity Relationship Although it is difficult tomake out an exact structure-activity relationship between theantimicrobial activity and the structure of these complexesit can possibly be concluded that the chelation as well as theaddition of a substrate enhances the activity of the complexesThe variation in the toxicity of different antibacterial agentsagainst various organisms depends on either the imperme-ability of the cell or differences in site of action or ability tocause mutations in the microorganism Though the resultssuggest that the ligand has a remarkable toxic property theircomplexes of tin inhibit the growth of microorganisms toa greater extent This is in accordance with earlier reports[40] Further the greater activity of the complexes can alsobe explained on the basis of their higher solubility of theparticles

4 Conclusion

The FT-IR data of synthesized complexes clearly demon-strate that the zinc and tin become attached with theoxygen and sulphur of the ligand in a bidentate modeIn solid state chlorodiorganotin complexes exhibit thepentahexacoordinated geometry whereas the triorgan-otin(IV) complexes show the five-coordinate geometry Bio-logical activity data showed that all the complexes werebiologically active with few exceptionsThese complexes were

found to be more potent inhibitors toward fungal culture ascompared to bacterial strains

Acknowledgment

Higher EducationCommission of Pakistan (HEC) is acknow-ledged for support under the Project no 20-1623RampD104402

References

[1] K E Appel ldquoOrganotin compounds toxicokinetic aspectsrdquoDrug Metabolism Reviews vol 36 no 3-4 pp 763ndash786 2004

[2] K C Molloy T G Purcell E Hahn H Schumann and J JZuckerman ldquoOrganotin biocides 4 Crystal and molecularstructure of tricyclohexylstannyl 3-indolylacetate incorporat-ing the first monodentate carboxylate group bonded to atriorganotin(IV)rdquoOrganometallics vol 5 no 1 pp 85ndash89 1986

[3] R R Holmes ldquoOrganotin cluster chemistryrdquoAccounts of Chem-ical Research vol 22 no 5 pp 190ndash197 1989

[4] R Barbieri A Silvestri M T L Giudice G Ruisi and M TMusmeci ldquoThe binding of trialkyltin(IV) moieties to rathaemoglobin and the structure of model systems studiedby tin-119 Mossbauer spectroscopyrdquo Journal of the ChemicalSociety Dalton Transactions no 3 pp 519ndash525 1989

[5] S Sadiq-Ur-Rehman K Shahid S Ali M H Bhatti and MParvez ldquoOrganotin esterification of (E)-3-(3-fluoro-phenyl)-2-(4-chlorophenyl)-2-propenoic acid synthesis spectroscopiccharacterization and in vitro biological activities Crystal struc-ture of [Ph

3Sn(OC(O)C(4-ClC

6H4) =CH(3-FC

6H4))]rdquo Journal

of Organometallic Chemistry vol 690 no 5 pp 1396ndash14082005

[6] P J Heard Progress in Inorganic Chemistry vol 53 John Wileyamp Sons New York NY USA 2005 edited by D Karlin

[7] S H LThoonen B Deelman and G van Koten ldquoSynthetic as-pects of tetraorganotins and organotin(IV) halidesrdquo Journal ofOrganometallic Chemistry vol 689 no 13 pp 2145ndash2157 2004

[8] H Hussain V U Ahmad I R Green K Krohn J Hussain andA Badshah ldquoAntibacterial organotin(IV) compounds theirsynthesis and spectral characterizationrdquo Arkivoc vol 2007 no14 pp 289ndash299 2007

[9] S Y Dike J R Merchant and N Y Sapre ldquoA new and efficientgeneral method for the synthesis of 2-spirobenzopyrans firstsynthesis of cyclic analogues of precocene I and related com-poundrdquo Tetrahedron vol 47 no 26 pp 4775ndash4786 1991

[10] L E da Silva P T de Sousa Jr A C Joussef C Piovezan andANeves ldquoSynthesis structure and physicochemical properties ofzinc and copper complexes based on sulfonamides containing8-aminoquinoline ligandsrdquo Quımica Nova vol 31 no 5 pp1161ndash1164 2008

[11] J Anwer S Ali S Shahzadi M Shahid S K Sharma and KQanungo ldquoSynthesis characterization semi-empirical studyand biological activities of homobimetallic complexes of tranex-amic acid with organotin(IV)rdquo Journal of Coordination Chem-istry vol 66 no 7 pp 1142ndash1152 2013

[12] S Jabbar I Shahzadi R Rehman et al ldquoSynthesis character-ization semi-empirical study and biological activities of organ-otin(IV) complexes with cyclohexylcarbamodithioic acid asbiological active ligandrdquo Journal of Coordination Chemistry vol65 no 4 pp 572ndash590 2012

Bioinorganic Chemistry and Applications 7

[13] H N Khan S Ali S Shahzadi and M Helliwell ldquoSynthesisspectroscopy and antimicrobial activity of chloro-organotin(IV) complexes of S-donor ligand crystal structureof chloro-t-dibutyltin[4-methyl-1-piperidine]thiocarboxylaterdquoRussian Journal of Inorganic Chemistry vol 57 no 5 pp665ndash670 2012

[14] F A Shah A Ali S Shahzadi C Rizzoli and A Ahmad ldquoSyn-thesis spectral characterization and X-ray crystal struc-ture of biologically active organotin(IV) 3-[(31015840 51015840-dimethyl-phenylamido)]propanoatesrdquo Journal of Iranian Chemical Soci-ety vol 9 no 6 pp 923ndash932 2012

[15] MM Amin S Ali S Shahzadi S K Sharma and K QanungoldquoDi- and triorganotin(IV) complexes of 2-aminobenzoic acidwith and without triphenylphosphine synthesis spectroscopysemi-empirical study and antimicrobial activitiesrdquo Journal ofCoordination Chemistry vol 64 no 2 pp 337ndash350 2011

[16] E Khoo N K Goh G Eng D J Whalen andA Hzell ldquoSynthesis characterization and fungicidalactivity of triphenyl derivatives of sarcosine crystalstructures of [Ph

3Sn(OCOCH

2NH2CHB)

2]Cl and

[Ph3(OCOCH

2NH2CH3)2]NCSrdquo Applied Organometallic

Chemistry vol 9 no 8 pp 699ndash706 1995[17] DKovala-Demertzi P TauridouAMoukarika JMTsangaris

C P Raptopoulou and A Terzis ldquoSynthesis and characteriza-tion of tin(IV) and organotin(IV) 14-dimethylpiperazine-25-dione (cyclosarcosylsarcosine) adductsrdquo Journal of the ChemicalSociety Dalton Transactions no 1 pp 123ndash128 1995

[18] L Ronconi C Marzano U Russo S Sitran R Graziani and DFregona ldquoSynthesis characterization and in vitro cytotoxicityof new organotin(IV) derivatives of N-methylglycinerdquo Journalof Inorganic Biochemistry vol 91 no 2 pp 413ndash420 2002

[19] W L F Armarego and C L L Chai Purification of LaboratoryChemicals Elsevier Burlington Vt USA 6th edition 2000

[20] W D Honnick and J J Zuckerman ldquoDiorganotin halide car-boxylates thiocarboxylates and halide haloacetatesrdquo Journal ofOrganometallic Chemistry vol 178 no 1 pp 133ndash155 1979

[21] E R T Tiekink ldquoStructural chemistry of organotin carboxyl-ates a review of the crystallographic literaturerdquo Applied Organ-ometallic Chemistry vol 5 no 1 pp 1ndash23 1991

[22] M Nath R Jairath G Eng X Song and A Kumar ldquoSynthesisspectral characterization and biological studies of some organ-otin(IV) complexes of l-proline trans-hydroxy-l-proline and l-glutaminerdquo SpectrochimicaActaA vol 62 no 4-5 pp 1179ndash11872005

[23] B S Hammes M T Kieber-Emmons J A Letizia et al ldquoSyn-thesis and characterization of several zinc(II) complexes con-taining the bulky heteroscorpionate ligand bis(5-tert-butyl-3-methylpyrazol-2-yl)acetate relevance to the resting states ofthe zinc(II) enzymes thermolysin and carboxypeptidase ArdquoInorganica Chimica Acta vol 346 pp 227ndash238 2003

[24] R Singh and N K Kaushik ldquoSpectral and thermal studies withanti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta A vol 71 no 2 pp669ndash675 2008

[25] H L Singh and J B Singh ldquoSynthesis and characterization ofnew lead(II) and organotin(IV) complexes of schiff basesderived fromhistidine andmethioninerdquo International Journal ofInorganic Chemistry vol 2012 Article ID 568797 7 pages 2012

[26] A Saxena J P Tandon K C Molloy and J J ZuckermanldquoTin(IV) complexes of tridentate schiff bases having ONS

donor systemsrdquo Inorganica Chimica Acta vol 63 no C pp 71ndash74 1982

[27] A K Saxena H B Singh and J P Tandon ldquoSynthesis andcharacterization of tin(IV) complexes of azinesrdquo SynthesisReactivity Inorganic and Metal-Organic Chemistry vol 10 pp117ndash136 1980

[28] H O Kalinowski S Berger and S Brown 13C NMR Spectro-skopie Thieme Stuttgart Germany 1984

[29] S Ali F Ahmad M Mazhar A Munir and M T MasoodldquoSynthesis and spectral studies of di- and triorganotin(IV) com-plexes with 2-(6-methoxynaphthyl)propionic acid (naproxen)rdquoSynthesis and Reactivity in Inorganic and Metal-Organic Chem-istry vol 32 no 2 pp 357ndash372 2002

[30] J Holecek M Nadvornık K Handlır and A Lycka ldquo13C and119Sn NMR spectra of Di-n-butyltin(IV) compoundsrdquo Journalof Organometallic Chemistry vol 315 no 3 pp 299ndash308 1986

[31] DHWilliams and I Fleming SpectroscopicMethods inOrganicChemistry McGraw-Hill London UK 4th edition 1987

[32] S S Konstantinovic B C Radovanovic S P Sovilj and SStanojevic ldquoAntimicrobial activity of some isatin-3-thiosemi-carbazone complexesrdquo Journal of the Serbian Chemical Societyvol 73 no 1 pp 7ndash13 2008

[33] R V Singh P Chaudhary S Chauhan and M Swami ldquoMicro-wave-assisted synthesis characterization and biological activi-ties of organotin (IV) complexes with some thio schiff basesrdquoSpectrochimica Acta A vol 72 no 2 pp 260ndash268 2009

[34] W Rehman M K Baloch A Badshah and S Ali ldquoSynthesischaracterization and biological study of diorganotin(IV) com-plexes ofmonomethyl phthalaterdquo SpectrochimicaActaA vol 65no 3-4 pp 689ndash694 2006

[35] K K Chaturvedi and M Goyal ldquoAntibacterial studies of7-(120572-substituted sulphonamido)methyl- and 7-(120572-substitutedsulphonamido)phenyl-8-hydroxyquinolinesrdquo Journal of theIndian Chemical Society vol 61 no 2 pp 175ndash176 1984

[36] H L Singh B Khungar U D Tripaathi and A K VarshneyldquoSpectral and antimicrobial studies of organotin(IV) complexesof bidentate schiff bases having nitrogen and sulphur donorsystemsrdquo Main Group Metal Chemistry vol 24 no 1 pp 5ndash122001

[37] T R Fritsche P F McDermott T R Shryock and R DWalkerldquoAgar dilution and disk diffusion susceptibility testing ofCampylobacter spprdquo Journal of Clinical Microbiology vol 45no 8 pp 2758ndash2759 2007

[38] M Jabeen S Ali S Shahzadi et al ldquoHomobimetallic complexesof ligand having O and S donor sites with same and differentdi- and trialkylaryltin(IV) moiety their synthesis spectralcharacterization and biological activitiesrdquo Journal of IranianChemical Society vol 9 no 3 pp 307ndash320 2012

[39] S Shahzadi K Shahid S Ali and M Bakhtiar ldquoCharacteri-zation and antimicrobial activity of organotin(IV) complexes of2-[(2101584061015840-diethylphenylamido)]benzoates and 3-[(2101584061015840-diethyl-phenylamido)]propanoatesrdquo Turkish Journal of Chemistry vol32 no 3 pp 333ndash353 2008

[40] MAshfaqM I KhanMK Baloch andAMalik ldquoBiologicallypotent organotin(IV) complexes of 2-maleimidoacetic acidrdquoJournal of Organometallic Chemistry vol 689 no 1 pp 238ndash245 2004

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

4 Bioinorganic Chemistry and Applications

Table 2 IR spectral data (cmminus1) of heterobimetallic complexes with sarcosine

Comp no ](NH) ](COO)Δ] ](C=S) ](CndashS) ](SnndashC) ](SnndashS) ](SnndashCl) ](ZnndashO)

](COO) (asym) ](COO) (sym)HL 3365 1621 1407 214 mdash mdash mdash mdash mdash mdash(1) mdash 1642 1462 180 1033 955 526 461 311 364(2) mdash 1618 1433 185 1013 942 530 472 302 352(3) mdash 1602 1440 162 1025 988 272 466 318 347(4) mdash 1622 1456 166 1023 938 538 485 mdash 371(5) mdash 1635 1468 167 1043 965 547 456 mdash 385(6) mdash 1650 1470 180 1030 970 280 480 mdash 310

Table 3 1H NMR dataandashd (ppm) of heterobimetallic complexes with sarcosine

Proton no HL (1) (2) (3) (4) (5) (6)2 21015840 315s 397s 399s 388s 374s 363s 395s3 31015840 248s 289s 280s 296s 285s 294s 279saCompound (1) Sn-CH3Cl 127s

2J[96] compound (2) Sn-CH2CH2CH2CH3Cl 088ndash093m 023t (72) compound (3) Sn-C6H5Cl 791d2J[82] 750ndash753m

742ndash750m compound (4) Sn-CH3 051s2J[82] compound (5) Sn-CH2CH2CH2CH3 064ndash11m 023t (72) compound (6) Sn-C6H5 791d

2J[82] 750ndash753m742ndash750mbMultiplicity is given as s singlet d doublet t triplet m multipletcCoupling constant 119899J[119Sn 1H] and 119899J[1H 1H] in Hz are given in square bracket and parenthesis respectivelyd

NN

CH3CH3

3998400

1998400

2998400

CCOO

OOZn

1

2

3

Table 4 13C NMR dataab (ppm) of heterobimetallic Zn(II) andSn(IV) complexes with sarcosine

Carbon HL (1) (2) (3) (4) (5) (6)1 11015840 1792 1863 1819 1837 1854 1843 18382 21015840 566 568 563 569 567 566 5683 31015840 415 413 413 415 414 412 415ndashCSS mdash 2026 2025 2028 2017 2028 2027aCompound (1) Sn-CH3Cl (C-120572) 21 1J[397] compound (2) Sn-CH2CH2CH2CH3Cl (C-120572) 295 (C-120573) 274 (C-120574) 262 (C-120575) 139compound (3) Sn-C6H5Cl (C-120572) 1376

1J[640] (C-120573) 1328 2J[490] (C-120574)1299 (C-120575) 1248 compound (4) Sn-CH3 (C-120572) 23 1J[396] compound(5) Sn-CH2CH2CH2CH3 (C-120572) 311 [349] (C-120573) 271 2J[21] (C-120574) 2823J[63] (C-120575) 141 compound (6) Sn-C6H5 (C-120572) 1380

1J[640] (C-120573) 13302J[490] (C-120574) 1300 (C-120575) 1251bChemical shifts (120575) in ppm 119899J[119Sn 13C] in Hz is listed in parenthesis

Two resonance signals appeared as a singlet at 315 ppm and248 ppm for the methylene andmethyl protons respectivelyin the free ligand These signals exhibited downfield shift to363ndash399 ppm and 279ndash296 ppm in the complexes (1)ndash(6)for methylene and methyl protons respectively

The CH3protons in compound (1) appear as a singlet

at 127 ppm with tin satellites having 2J[119Snndash1H] = 96HzIn compound (2) the protons of butyl group appear as amultiplet in the region 088ndash093 ppm The terminal CH

3

group of butyl gives triplet at 023 ppm with 3J[1Hndash1H] valueof 72Hz The proton chemical shift of the methyl group incompound (3) attached to the Sn gives a singlet at 051 ppm

The phenyl moieties of di- and triphenyltin(IV) derivativesshow a complex pattern and were assigned according to theliterature [29] The 2J[119Snndash1H] value for di- and triph-enyltin(IV) derivatives is 82Hz in the range expected forpentacoordinated tin atom and consistent with CndashSnndashCangle of 1265∘

33 13C NMR The assignments of ndashCSS group in investi-gated compounds is straightforward which are observed inthe range of 2025ndash2028 ppm indicating the coordination ofsulfur to the tin atom

Table 4 lists the chemical shifts of 13C and tin-carboncoupling constants for the reported complexes (1)ndash(6) The13C NMR chemical shifts due to the phenyl groups areobserved at positions comparable to other similar com-pounds [30 31] The 13C NMR chemical shift due to ndashCOOcarbon atom is observed at 1792 ppm in the free ligandwhile in the complexes it exhibits downfield shift in therange 1819ndash1863 ppm Coordination of the tin atom in di-and triorganotin has been related to 119899J(119Snndash13C) couplingconstants The 119899J(119Snndash13C) coupling for complexes (1) and(6) is 397 and 640Hz respectively which is indicative of fourcoordinate geometry [30] in solution state

34 Antibacterial Activity Sarcosine and synthesized com-plexes (1)ndash(6) were tested in vitro for their antibacterialactivity against gram positive and gram negative bacterial

Bioinorganic Chemistry and Applications 5

Table 5 Antibacterial activity dataandashe of complexes and ligand against selected bacterial strains

Compound no Bacterial inhibition zone (mm)S aureus B subtilis E coli P multocida

HL 125c plusmn 086 130c plusmn 100 125c plusmn 086 120c plusmn 141(1) 208bc plusmn 100 180c plusmn 100 252c plusmn 086 210ab plusmn 100(2) 210bc plusmn 100 205bc plusmn 086 275bc plusmn 086 245ab plusmn 086(3) 208bc plusmn 100 186c plusmn 100 262c plusmn 086 213ab plusmn 100(4) 300ab plusmn 141 215bc plusmn 165 280bc plusmn 141 230ab plusmn 100(5) 325ab plusmn 165 545a plusmn 086 510a plusmn 100 325a plusmn 165(6) 315ab plusmn 086 330bc plusmn 141 320ab plusmn 100 300ab plusmn 141Ampicillin 385a plusmn 086 400ab plusmn 141 395ab plusmn 086 320ab plusmn 141aConcentration 1mgmL in DMSObStandard ampicillinc0 no activity 5ndash10 activity present 11ndash25 moderate activity 26ndash40 strong activitydAntibacterial values are mean plusmn SD of samples analyzed individually in triplicate at 119875 lt 01eDifferent letters in superscript indicate significant differences

Table 6 Antifungal activity dataandashe of complexes and ligand against selected fungal strains

Compound no Fungal inhibition zone (mm)A alternata 119866 lucidum A flavus 119860 niger

HL 270ab plusmn 100 115c plusmn 086 375ab plusmn 086 145bc plusmn 165(1) 264ab plusmn 100 193bc plusmn 100 202bc plusmn 165 203ab plusmn 086(2) 200c plusmn 141 190bc plusmn 100 205bc plusmn 165 205bc plusmn 086(3) 269bc plusmn 141 202ab plusmn 165 352bc plusmn 165 212bc plusmn 086(4) 300ab plusmn 141 185bc plusmn 086 195c plusmn 165 185bc plusmn 086(5) 300ab plusmn 141 395ab plusmn 165 370

abplusmn 165 335 a

plusmn 165(6) 285ab plusmn 086 250bc plusmn 100 320bc plusmn 141 195bc plusmn 086Fluconazole 305a plusmn 086 415a plusmn 086 540a plusmn 141 125c plusmn 086aConcentration 1mgmL in DMSObStandard fluconazolec0 no activity 5ndash10 activity present 11ndash25 moderate activity 26ndash40 strong activitydAntibacterial values are mean plusmn SD of samples analyzed individually in triplicate at 119875 lt 01eDifferent letters in superscript indicate significant differences

strains including B subtilis and S aureus and P multocidaand E coli respectively and the results are given in Table 5Ampicillin was used as a standard drug The results revealedthat all the newly synthesized complexes show higher activitythan the ligand but markedly lower than the standard drugwith few exceptions

Complex (5) showed maximum inhibitory action againstB subtilis (545 plusmn 086) and E coli (510 plusmn 100) probablymore than standard drug (4000 plusmn 141) and (395 plusmn 086)respectively Complex (2) displayed lowest inhibition zone incase of B subtilis (205plusmn086) and S aureus (210plusmn100)Theligand exhibited low activities while the complexes exhibitedmoderate activities as compared to standard drug towards allthe bacterial strains Complex (6) showed moderate antibac-terial activity against all the bacterial strains Among all thecomplexes the tributyltin complex (5) showed significantantibacterial activity It was clear from the data that antimi-crobial activities varied according to substitution (increasein substitution on the Sn(IV) enhances the antimicrobialactivity) [32]

Data revealed that the synthesized complexes showedmore activity against gram positive bacterial strain thangram negative strains It was due to the difference in thecomposition of cell wall of both the gram positive and gramnegative strains [33] It was also suggested that the anti-microbial activity of the complexes was either due to killingofmicrobes or inhibiting their reproduction by blocking theiractive sites [34]

The results show that all compounds exhibit antibacterialactivity and in many cases complexes are more potent intheir inhibition properties than the free ligand This canbe explained in terms of the greater lipid solubility andcellular penetration of the complexes [35] It is clear that thecoordination enhances the antibacterial activity and clearlyindicates that the newly synthesized complexes in the presentstudies are more active against gram positive than gramnegative bacteria The preliminary results achieved have ledus to conclude that these types of complexes should bestudied in detail for their applications in diverse area

The screening data of a particular ligand and its metalcomplexes show that the former has greater activity than

6 Bioinorganic Chemistry and Applications

the latter from the biochemical point of view On comparingthe results in general it may be concluded that complexescontaining Zn(II) and Sn(IV) have greater inhibiting powerthan the free ligands as compared to organotin complexeswith sarcosine [16 17] against all the microbes

35 Antifungal Activity The synthesized compounds (1)ndash(6)and sarcosine were tested for antifungal activity by usingfluconazole as standard drug against four fungal strainsincluding A flavus A niger A alternate and G lucidum bydisc diffusion method [36] The results are summarized inTable 6 It was evident from tabulated data that the sarcosineas well as the synthesized complexes exhibited variety offungicidal activity Sarcosine exhibited maximum activityagainst A flavus (375 plusmn 086) while complex (5) exhibitedmaximum activity (395 plusmn 165) against G lucidum Complex(2) showed the lowest inhibition zone (190 plusmn 100) againstG lucidum It is noted that tributyltin complexes showed thegreatest inhibitory effect against fungi as compared to otheralkyl groupsThus the presence of butyl groups in compound(5) bonded with tin atom was responsible for the rise ofantifungal activity [37] The increased activity of complexesmight be due to the coordination of zinc and tin with oxygenand sulfur respectively [38] From the data it might beconcluded that triorganotin compounds were usually moreeffective against the fungi than diorganotin compounds [39]in contrast to earlier reported compounds in the literature[16] This might be due to the presence of Zn(II) along withSn(IV) which enhances the fungicidal activity of triorganotincomplexes

36 Structure Activity Relationship Although it is difficult tomake out an exact structure-activity relationship between theantimicrobial activity and the structure of these complexesit can possibly be concluded that the chelation as well as theaddition of a substrate enhances the activity of the complexesThe variation in the toxicity of different antibacterial agentsagainst various organisms depends on either the imperme-ability of the cell or differences in site of action or ability tocause mutations in the microorganism Though the resultssuggest that the ligand has a remarkable toxic property theircomplexes of tin inhibit the growth of microorganisms toa greater extent This is in accordance with earlier reports[40] Further the greater activity of the complexes can alsobe explained on the basis of their higher solubility of theparticles

4 Conclusion

The FT-IR data of synthesized complexes clearly demon-strate that the zinc and tin become attached with theoxygen and sulphur of the ligand in a bidentate modeIn solid state chlorodiorganotin complexes exhibit thepentahexacoordinated geometry whereas the triorgan-otin(IV) complexes show the five-coordinate geometry Bio-logical activity data showed that all the complexes werebiologically active with few exceptionsThese complexes were

found to be more potent inhibitors toward fungal culture ascompared to bacterial strains

Acknowledgment

Higher EducationCommission of Pakistan (HEC) is acknow-ledged for support under the Project no 20-1623RampD104402

References

[1] K E Appel ldquoOrganotin compounds toxicokinetic aspectsrdquoDrug Metabolism Reviews vol 36 no 3-4 pp 763ndash786 2004

[2] K C Molloy T G Purcell E Hahn H Schumann and J JZuckerman ldquoOrganotin biocides 4 Crystal and molecularstructure of tricyclohexylstannyl 3-indolylacetate incorporat-ing the first monodentate carboxylate group bonded to atriorganotin(IV)rdquoOrganometallics vol 5 no 1 pp 85ndash89 1986

[3] R R Holmes ldquoOrganotin cluster chemistryrdquoAccounts of Chem-ical Research vol 22 no 5 pp 190ndash197 1989

[4] R Barbieri A Silvestri M T L Giudice G Ruisi and M TMusmeci ldquoThe binding of trialkyltin(IV) moieties to rathaemoglobin and the structure of model systems studiedby tin-119 Mossbauer spectroscopyrdquo Journal of the ChemicalSociety Dalton Transactions no 3 pp 519ndash525 1989

[5] S Sadiq-Ur-Rehman K Shahid S Ali M H Bhatti and MParvez ldquoOrganotin esterification of (E)-3-(3-fluoro-phenyl)-2-(4-chlorophenyl)-2-propenoic acid synthesis spectroscopiccharacterization and in vitro biological activities Crystal struc-ture of [Ph

3Sn(OC(O)C(4-ClC

6H4) =CH(3-FC

6H4))]rdquo Journal

of Organometallic Chemistry vol 690 no 5 pp 1396ndash14082005

[6] P J Heard Progress in Inorganic Chemistry vol 53 John Wileyamp Sons New York NY USA 2005 edited by D Karlin

[7] S H LThoonen B Deelman and G van Koten ldquoSynthetic as-pects of tetraorganotins and organotin(IV) halidesrdquo Journal ofOrganometallic Chemistry vol 689 no 13 pp 2145ndash2157 2004

[8] H Hussain V U Ahmad I R Green K Krohn J Hussain andA Badshah ldquoAntibacterial organotin(IV) compounds theirsynthesis and spectral characterizationrdquo Arkivoc vol 2007 no14 pp 289ndash299 2007

[9] S Y Dike J R Merchant and N Y Sapre ldquoA new and efficientgeneral method for the synthesis of 2-spirobenzopyrans firstsynthesis of cyclic analogues of precocene I and related com-poundrdquo Tetrahedron vol 47 no 26 pp 4775ndash4786 1991

[10] L E da Silva P T de Sousa Jr A C Joussef C Piovezan andANeves ldquoSynthesis structure and physicochemical properties ofzinc and copper complexes based on sulfonamides containing8-aminoquinoline ligandsrdquo Quımica Nova vol 31 no 5 pp1161ndash1164 2008

[11] J Anwer S Ali S Shahzadi M Shahid S K Sharma and KQanungo ldquoSynthesis characterization semi-empirical studyand biological activities of homobimetallic complexes of tranex-amic acid with organotin(IV)rdquo Journal of Coordination Chem-istry vol 66 no 7 pp 1142ndash1152 2013

[12] S Jabbar I Shahzadi R Rehman et al ldquoSynthesis character-ization semi-empirical study and biological activities of organ-otin(IV) complexes with cyclohexylcarbamodithioic acid asbiological active ligandrdquo Journal of Coordination Chemistry vol65 no 4 pp 572ndash590 2012

Bioinorganic Chemistry and Applications 7

[13] H N Khan S Ali S Shahzadi and M Helliwell ldquoSynthesisspectroscopy and antimicrobial activity of chloro-organotin(IV) complexes of S-donor ligand crystal structureof chloro-t-dibutyltin[4-methyl-1-piperidine]thiocarboxylaterdquoRussian Journal of Inorganic Chemistry vol 57 no 5 pp665ndash670 2012

[14] F A Shah A Ali S Shahzadi C Rizzoli and A Ahmad ldquoSyn-thesis spectral characterization and X-ray crystal struc-ture of biologically active organotin(IV) 3-[(31015840 51015840-dimethyl-phenylamido)]propanoatesrdquo Journal of Iranian Chemical Soci-ety vol 9 no 6 pp 923ndash932 2012

[15] MM Amin S Ali S Shahzadi S K Sharma and K QanungoldquoDi- and triorganotin(IV) complexes of 2-aminobenzoic acidwith and without triphenylphosphine synthesis spectroscopysemi-empirical study and antimicrobial activitiesrdquo Journal ofCoordination Chemistry vol 64 no 2 pp 337ndash350 2011

[16] E Khoo N K Goh G Eng D J Whalen andA Hzell ldquoSynthesis characterization and fungicidalactivity of triphenyl derivatives of sarcosine crystalstructures of [Ph

3Sn(OCOCH

2NH2CHB)

2]Cl and

[Ph3(OCOCH

2NH2CH3)2]NCSrdquo Applied Organometallic

Chemistry vol 9 no 8 pp 699ndash706 1995[17] DKovala-Demertzi P TauridouAMoukarika JMTsangaris

C P Raptopoulou and A Terzis ldquoSynthesis and characteriza-tion of tin(IV) and organotin(IV) 14-dimethylpiperazine-25-dione (cyclosarcosylsarcosine) adductsrdquo Journal of the ChemicalSociety Dalton Transactions no 1 pp 123ndash128 1995

[18] L Ronconi C Marzano U Russo S Sitran R Graziani and DFregona ldquoSynthesis characterization and in vitro cytotoxicityof new organotin(IV) derivatives of N-methylglycinerdquo Journalof Inorganic Biochemistry vol 91 no 2 pp 413ndash420 2002

[19] W L F Armarego and C L L Chai Purification of LaboratoryChemicals Elsevier Burlington Vt USA 6th edition 2000

[20] W D Honnick and J J Zuckerman ldquoDiorganotin halide car-boxylates thiocarboxylates and halide haloacetatesrdquo Journal ofOrganometallic Chemistry vol 178 no 1 pp 133ndash155 1979

[21] E R T Tiekink ldquoStructural chemistry of organotin carboxyl-ates a review of the crystallographic literaturerdquo Applied Organ-ometallic Chemistry vol 5 no 1 pp 1ndash23 1991

[22] M Nath R Jairath G Eng X Song and A Kumar ldquoSynthesisspectral characterization and biological studies of some organ-otin(IV) complexes of l-proline trans-hydroxy-l-proline and l-glutaminerdquo SpectrochimicaActaA vol 62 no 4-5 pp 1179ndash11872005

[23] B S Hammes M T Kieber-Emmons J A Letizia et al ldquoSyn-thesis and characterization of several zinc(II) complexes con-taining the bulky heteroscorpionate ligand bis(5-tert-butyl-3-methylpyrazol-2-yl)acetate relevance to the resting states ofthe zinc(II) enzymes thermolysin and carboxypeptidase ArdquoInorganica Chimica Acta vol 346 pp 227ndash238 2003

[24] R Singh and N K Kaushik ldquoSpectral and thermal studies withanti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta A vol 71 no 2 pp669ndash675 2008

[25] H L Singh and J B Singh ldquoSynthesis and characterization ofnew lead(II) and organotin(IV) complexes of schiff basesderived fromhistidine andmethioninerdquo International Journal ofInorganic Chemistry vol 2012 Article ID 568797 7 pages 2012

[26] A Saxena J P Tandon K C Molloy and J J ZuckermanldquoTin(IV) complexes of tridentate schiff bases having ONS

donor systemsrdquo Inorganica Chimica Acta vol 63 no C pp 71ndash74 1982

[27] A K Saxena H B Singh and J P Tandon ldquoSynthesis andcharacterization of tin(IV) complexes of azinesrdquo SynthesisReactivity Inorganic and Metal-Organic Chemistry vol 10 pp117ndash136 1980

[28] H O Kalinowski S Berger and S Brown 13C NMR Spectro-skopie Thieme Stuttgart Germany 1984

[29] S Ali F Ahmad M Mazhar A Munir and M T MasoodldquoSynthesis and spectral studies of di- and triorganotin(IV) com-plexes with 2-(6-methoxynaphthyl)propionic acid (naproxen)rdquoSynthesis and Reactivity in Inorganic and Metal-Organic Chem-istry vol 32 no 2 pp 357ndash372 2002

[30] J Holecek M Nadvornık K Handlır and A Lycka ldquo13C and119Sn NMR spectra of Di-n-butyltin(IV) compoundsrdquo Journalof Organometallic Chemistry vol 315 no 3 pp 299ndash308 1986

[31] DHWilliams and I Fleming SpectroscopicMethods inOrganicChemistry McGraw-Hill London UK 4th edition 1987

[32] S S Konstantinovic B C Radovanovic S P Sovilj and SStanojevic ldquoAntimicrobial activity of some isatin-3-thiosemi-carbazone complexesrdquo Journal of the Serbian Chemical Societyvol 73 no 1 pp 7ndash13 2008

[33] R V Singh P Chaudhary S Chauhan and M Swami ldquoMicro-wave-assisted synthesis characterization and biological activi-ties of organotin (IV) complexes with some thio schiff basesrdquoSpectrochimica Acta A vol 72 no 2 pp 260ndash268 2009

[34] W Rehman M K Baloch A Badshah and S Ali ldquoSynthesischaracterization and biological study of diorganotin(IV) com-plexes ofmonomethyl phthalaterdquo SpectrochimicaActaA vol 65no 3-4 pp 689ndash694 2006

[35] K K Chaturvedi and M Goyal ldquoAntibacterial studies of7-(120572-substituted sulphonamido)methyl- and 7-(120572-substitutedsulphonamido)phenyl-8-hydroxyquinolinesrdquo Journal of theIndian Chemical Society vol 61 no 2 pp 175ndash176 1984

[36] H L Singh B Khungar U D Tripaathi and A K VarshneyldquoSpectral and antimicrobial studies of organotin(IV) complexesof bidentate schiff bases having nitrogen and sulphur donorsystemsrdquo Main Group Metal Chemistry vol 24 no 1 pp 5ndash122001

[37] T R Fritsche P F McDermott T R Shryock and R DWalkerldquoAgar dilution and disk diffusion susceptibility testing ofCampylobacter spprdquo Journal of Clinical Microbiology vol 45no 8 pp 2758ndash2759 2007

[38] M Jabeen S Ali S Shahzadi et al ldquoHomobimetallic complexesof ligand having O and S donor sites with same and differentdi- and trialkylaryltin(IV) moiety their synthesis spectralcharacterization and biological activitiesrdquo Journal of IranianChemical Society vol 9 no 3 pp 307ndash320 2012

[39] S Shahzadi K Shahid S Ali and M Bakhtiar ldquoCharacteri-zation and antimicrobial activity of organotin(IV) complexes of2-[(2101584061015840-diethylphenylamido)]benzoates and 3-[(2101584061015840-diethyl-phenylamido)]propanoatesrdquo Turkish Journal of Chemistry vol32 no 3 pp 333ndash353 2008

[40] MAshfaqM I KhanMK Baloch andAMalik ldquoBiologicallypotent organotin(IV) complexes of 2-maleimidoacetic acidrdquoJournal of Organometallic Chemistry vol 689 no 1 pp 238ndash245 2004

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Bioinorganic Chemistry and Applications 5

Table 5 Antibacterial activity dataandashe of complexes and ligand against selected bacterial strains

Compound no Bacterial inhibition zone (mm)S aureus B subtilis E coli P multocida

HL 125c plusmn 086 130c plusmn 100 125c plusmn 086 120c plusmn 141(1) 208bc plusmn 100 180c plusmn 100 252c plusmn 086 210ab plusmn 100(2) 210bc plusmn 100 205bc plusmn 086 275bc plusmn 086 245ab plusmn 086(3) 208bc plusmn 100 186c plusmn 100 262c plusmn 086 213ab plusmn 100(4) 300ab plusmn 141 215bc plusmn 165 280bc plusmn 141 230ab plusmn 100(5) 325ab plusmn 165 545a plusmn 086 510a plusmn 100 325a plusmn 165(6) 315ab plusmn 086 330bc plusmn 141 320ab plusmn 100 300ab plusmn 141Ampicillin 385a plusmn 086 400ab plusmn 141 395ab plusmn 086 320ab plusmn 141aConcentration 1mgmL in DMSObStandard ampicillinc0 no activity 5ndash10 activity present 11ndash25 moderate activity 26ndash40 strong activitydAntibacterial values are mean plusmn SD of samples analyzed individually in triplicate at 119875 lt 01eDifferent letters in superscript indicate significant differences

Table 6 Antifungal activity dataandashe of complexes and ligand against selected fungal strains

Compound no Fungal inhibition zone (mm)A alternata 119866 lucidum A flavus 119860 niger

HL 270ab plusmn 100 115c plusmn 086 375ab plusmn 086 145bc plusmn 165(1) 264ab plusmn 100 193bc plusmn 100 202bc plusmn 165 203ab plusmn 086(2) 200c plusmn 141 190bc plusmn 100 205bc plusmn 165 205bc plusmn 086(3) 269bc plusmn 141 202ab plusmn 165 352bc plusmn 165 212bc plusmn 086(4) 300ab plusmn 141 185bc plusmn 086 195c plusmn 165 185bc plusmn 086(5) 300ab plusmn 141 395ab plusmn 165 370

abplusmn 165 335 a

plusmn 165(6) 285ab plusmn 086 250bc plusmn 100 320bc plusmn 141 195bc plusmn 086Fluconazole 305a plusmn 086 415a plusmn 086 540a plusmn 141 125c plusmn 086aConcentration 1mgmL in DMSObStandard fluconazolec0 no activity 5ndash10 activity present 11ndash25 moderate activity 26ndash40 strong activitydAntibacterial values are mean plusmn SD of samples analyzed individually in triplicate at 119875 lt 01eDifferent letters in superscript indicate significant differences

strains including B subtilis and S aureus and P multocidaand E coli respectively and the results are given in Table 5Ampicillin was used as a standard drug The results revealedthat all the newly synthesized complexes show higher activitythan the ligand but markedly lower than the standard drugwith few exceptions

Complex (5) showed maximum inhibitory action againstB subtilis (545 plusmn 086) and E coli (510 plusmn 100) probablymore than standard drug (4000 plusmn 141) and (395 plusmn 086)respectively Complex (2) displayed lowest inhibition zone incase of B subtilis (205plusmn086) and S aureus (210plusmn100)Theligand exhibited low activities while the complexes exhibitedmoderate activities as compared to standard drug towards allthe bacterial strains Complex (6) showed moderate antibac-terial activity against all the bacterial strains Among all thecomplexes the tributyltin complex (5) showed significantantibacterial activity It was clear from the data that antimi-crobial activities varied according to substitution (increasein substitution on the Sn(IV) enhances the antimicrobialactivity) [32]

Data revealed that the synthesized complexes showedmore activity against gram positive bacterial strain thangram negative strains It was due to the difference in thecomposition of cell wall of both the gram positive and gramnegative strains [33] It was also suggested that the anti-microbial activity of the complexes was either due to killingofmicrobes or inhibiting their reproduction by blocking theiractive sites [34]

The results show that all compounds exhibit antibacterialactivity and in many cases complexes are more potent intheir inhibition properties than the free ligand This canbe explained in terms of the greater lipid solubility andcellular penetration of the complexes [35] It is clear that thecoordination enhances the antibacterial activity and clearlyindicates that the newly synthesized complexes in the presentstudies are more active against gram positive than gramnegative bacteria The preliminary results achieved have ledus to conclude that these types of complexes should bestudied in detail for their applications in diverse area

The screening data of a particular ligand and its metalcomplexes show that the former has greater activity than

6 Bioinorganic Chemistry and Applications

the latter from the biochemical point of view On comparingthe results in general it may be concluded that complexescontaining Zn(II) and Sn(IV) have greater inhibiting powerthan the free ligands as compared to organotin complexeswith sarcosine [16 17] against all the microbes

35 Antifungal Activity The synthesized compounds (1)ndash(6)and sarcosine were tested for antifungal activity by usingfluconazole as standard drug against four fungal strainsincluding A flavus A niger A alternate and G lucidum bydisc diffusion method [36] The results are summarized inTable 6 It was evident from tabulated data that the sarcosineas well as the synthesized complexes exhibited variety offungicidal activity Sarcosine exhibited maximum activityagainst A flavus (375 plusmn 086) while complex (5) exhibitedmaximum activity (395 plusmn 165) against G lucidum Complex(2) showed the lowest inhibition zone (190 plusmn 100) againstG lucidum It is noted that tributyltin complexes showed thegreatest inhibitory effect against fungi as compared to otheralkyl groupsThus the presence of butyl groups in compound(5) bonded with tin atom was responsible for the rise ofantifungal activity [37] The increased activity of complexesmight be due to the coordination of zinc and tin with oxygenand sulfur respectively [38] From the data it might beconcluded that triorganotin compounds were usually moreeffective against the fungi than diorganotin compounds [39]in contrast to earlier reported compounds in the literature[16] This might be due to the presence of Zn(II) along withSn(IV) which enhances the fungicidal activity of triorganotincomplexes

36 Structure Activity Relationship Although it is difficult tomake out an exact structure-activity relationship between theantimicrobial activity and the structure of these complexesit can possibly be concluded that the chelation as well as theaddition of a substrate enhances the activity of the complexesThe variation in the toxicity of different antibacterial agentsagainst various organisms depends on either the imperme-ability of the cell or differences in site of action or ability tocause mutations in the microorganism Though the resultssuggest that the ligand has a remarkable toxic property theircomplexes of tin inhibit the growth of microorganisms toa greater extent This is in accordance with earlier reports[40] Further the greater activity of the complexes can alsobe explained on the basis of their higher solubility of theparticles

4 Conclusion

The FT-IR data of synthesized complexes clearly demon-strate that the zinc and tin become attached with theoxygen and sulphur of the ligand in a bidentate modeIn solid state chlorodiorganotin complexes exhibit thepentahexacoordinated geometry whereas the triorgan-otin(IV) complexes show the five-coordinate geometry Bio-logical activity data showed that all the complexes werebiologically active with few exceptionsThese complexes were

found to be more potent inhibitors toward fungal culture ascompared to bacterial strains

Acknowledgment

Higher EducationCommission of Pakistan (HEC) is acknow-ledged for support under the Project no 20-1623RampD104402

References

[1] K E Appel ldquoOrganotin compounds toxicokinetic aspectsrdquoDrug Metabolism Reviews vol 36 no 3-4 pp 763ndash786 2004

[2] K C Molloy T G Purcell E Hahn H Schumann and J JZuckerman ldquoOrganotin biocides 4 Crystal and molecularstructure of tricyclohexylstannyl 3-indolylacetate incorporat-ing the first monodentate carboxylate group bonded to atriorganotin(IV)rdquoOrganometallics vol 5 no 1 pp 85ndash89 1986

[3] R R Holmes ldquoOrganotin cluster chemistryrdquoAccounts of Chem-ical Research vol 22 no 5 pp 190ndash197 1989

[4] R Barbieri A Silvestri M T L Giudice G Ruisi and M TMusmeci ldquoThe binding of trialkyltin(IV) moieties to rathaemoglobin and the structure of model systems studiedby tin-119 Mossbauer spectroscopyrdquo Journal of the ChemicalSociety Dalton Transactions no 3 pp 519ndash525 1989

[5] S Sadiq-Ur-Rehman K Shahid S Ali M H Bhatti and MParvez ldquoOrganotin esterification of (E)-3-(3-fluoro-phenyl)-2-(4-chlorophenyl)-2-propenoic acid synthesis spectroscopiccharacterization and in vitro biological activities Crystal struc-ture of [Ph

3Sn(OC(O)C(4-ClC

6H4) =CH(3-FC

6H4))]rdquo Journal

of Organometallic Chemistry vol 690 no 5 pp 1396ndash14082005

[6] P J Heard Progress in Inorganic Chemistry vol 53 John Wileyamp Sons New York NY USA 2005 edited by D Karlin

[7] S H LThoonen B Deelman and G van Koten ldquoSynthetic as-pects of tetraorganotins and organotin(IV) halidesrdquo Journal ofOrganometallic Chemistry vol 689 no 13 pp 2145ndash2157 2004

[8] H Hussain V U Ahmad I R Green K Krohn J Hussain andA Badshah ldquoAntibacterial organotin(IV) compounds theirsynthesis and spectral characterizationrdquo Arkivoc vol 2007 no14 pp 289ndash299 2007

[9] S Y Dike J R Merchant and N Y Sapre ldquoA new and efficientgeneral method for the synthesis of 2-spirobenzopyrans firstsynthesis of cyclic analogues of precocene I and related com-poundrdquo Tetrahedron vol 47 no 26 pp 4775ndash4786 1991

[10] L E da Silva P T de Sousa Jr A C Joussef C Piovezan andANeves ldquoSynthesis structure and physicochemical properties ofzinc and copper complexes based on sulfonamides containing8-aminoquinoline ligandsrdquo Quımica Nova vol 31 no 5 pp1161ndash1164 2008

[11] J Anwer S Ali S Shahzadi M Shahid S K Sharma and KQanungo ldquoSynthesis characterization semi-empirical studyand biological activities of homobimetallic complexes of tranex-amic acid with organotin(IV)rdquo Journal of Coordination Chem-istry vol 66 no 7 pp 1142ndash1152 2013

[12] S Jabbar I Shahzadi R Rehman et al ldquoSynthesis character-ization semi-empirical study and biological activities of organ-otin(IV) complexes with cyclohexylcarbamodithioic acid asbiological active ligandrdquo Journal of Coordination Chemistry vol65 no 4 pp 572ndash590 2012

Bioinorganic Chemistry and Applications 7

[13] H N Khan S Ali S Shahzadi and M Helliwell ldquoSynthesisspectroscopy and antimicrobial activity of chloro-organotin(IV) complexes of S-donor ligand crystal structureof chloro-t-dibutyltin[4-methyl-1-piperidine]thiocarboxylaterdquoRussian Journal of Inorganic Chemistry vol 57 no 5 pp665ndash670 2012

[14] F A Shah A Ali S Shahzadi C Rizzoli and A Ahmad ldquoSyn-thesis spectral characterization and X-ray crystal struc-ture of biologically active organotin(IV) 3-[(31015840 51015840-dimethyl-phenylamido)]propanoatesrdquo Journal of Iranian Chemical Soci-ety vol 9 no 6 pp 923ndash932 2012

[15] MM Amin S Ali S Shahzadi S K Sharma and K QanungoldquoDi- and triorganotin(IV) complexes of 2-aminobenzoic acidwith and without triphenylphosphine synthesis spectroscopysemi-empirical study and antimicrobial activitiesrdquo Journal ofCoordination Chemistry vol 64 no 2 pp 337ndash350 2011

[16] E Khoo N K Goh G Eng D J Whalen andA Hzell ldquoSynthesis characterization and fungicidalactivity of triphenyl derivatives of sarcosine crystalstructures of [Ph

3Sn(OCOCH

2NH2CHB)

2]Cl and

[Ph3(OCOCH

2NH2CH3)2]NCSrdquo Applied Organometallic

Chemistry vol 9 no 8 pp 699ndash706 1995[17] DKovala-Demertzi P TauridouAMoukarika JMTsangaris

C P Raptopoulou and A Terzis ldquoSynthesis and characteriza-tion of tin(IV) and organotin(IV) 14-dimethylpiperazine-25-dione (cyclosarcosylsarcosine) adductsrdquo Journal of the ChemicalSociety Dalton Transactions no 1 pp 123ndash128 1995

[18] L Ronconi C Marzano U Russo S Sitran R Graziani and DFregona ldquoSynthesis characterization and in vitro cytotoxicityof new organotin(IV) derivatives of N-methylglycinerdquo Journalof Inorganic Biochemistry vol 91 no 2 pp 413ndash420 2002

[19] W L F Armarego and C L L Chai Purification of LaboratoryChemicals Elsevier Burlington Vt USA 6th edition 2000

[20] W D Honnick and J J Zuckerman ldquoDiorganotin halide car-boxylates thiocarboxylates and halide haloacetatesrdquo Journal ofOrganometallic Chemistry vol 178 no 1 pp 133ndash155 1979

[21] E R T Tiekink ldquoStructural chemistry of organotin carboxyl-ates a review of the crystallographic literaturerdquo Applied Organ-ometallic Chemistry vol 5 no 1 pp 1ndash23 1991

[22] M Nath R Jairath G Eng X Song and A Kumar ldquoSynthesisspectral characterization and biological studies of some organ-otin(IV) complexes of l-proline trans-hydroxy-l-proline and l-glutaminerdquo SpectrochimicaActaA vol 62 no 4-5 pp 1179ndash11872005

[23] B S Hammes M T Kieber-Emmons J A Letizia et al ldquoSyn-thesis and characterization of several zinc(II) complexes con-taining the bulky heteroscorpionate ligand bis(5-tert-butyl-3-methylpyrazol-2-yl)acetate relevance to the resting states ofthe zinc(II) enzymes thermolysin and carboxypeptidase ArdquoInorganica Chimica Acta vol 346 pp 227ndash238 2003

[24] R Singh and N K Kaushik ldquoSpectral and thermal studies withanti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta A vol 71 no 2 pp669ndash675 2008

[25] H L Singh and J B Singh ldquoSynthesis and characterization ofnew lead(II) and organotin(IV) complexes of schiff basesderived fromhistidine andmethioninerdquo International Journal ofInorganic Chemistry vol 2012 Article ID 568797 7 pages 2012

[26] A Saxena J P Tandon K C Molloy and J J ZuckermanldquoTin(IV) complexes of tridentate schiff bases having ONS

donor systemsrdquo Inorganica Chimica Acta vol 63 no C pp 71ndash74 1982

[27] A K Saxena H B Singh and J P Tandon ldquoSynthesis andcharacterization of tin(IV) complexes of azinesrdquo SynthesisReactivity Inorganic and Metal-Organic Chemistry vol 10 pp117ndash136 1980

[28] H O Kalinowski S Berger and S Brown 13C NMR Spectro-skopie Thieme Stuttgart Germany 1984

[29] S Ali F Ahmad M Mazhar A Munir and M T MasoodldquoSynthesis and spectral studies of di- and triorganotin(IV) com-plexes with 2-(6-methoxynaphthyl)propionic acid (naproxen)rdquoSynthesis and Reactivity in Inorganic and Metal-Organic Chem-istry vol 32 no 2 pp 357ndash372 2002

[30] J Holecek M Nadvornık K Handlır and A Lycka ldquo13C and119Sn NMR spectra of Di-n-butyltin(IV) compoundsrdquo Journalof Organometallic Chemistry vol 315 no 3 pp 299ndash308 1986

[31] DHWilliams and I Fleming SpectroscopicMethods inOrganicChemistry McGraw-Hill London UK 4th edition 1987

[32] S S Konstantinovic B C Radovanovic S P Sovilj and SStanojevic ldquoAntimicrobial activity of some isatin-3-thiosemi-carbazone complexesrdquo Journal of the Serbian Chemical Societyvol 73 no 1 pp 7ndash13 2008

[33] R V Singh P Chaudhary S Chauhan and M Swami ldquoMicro-wave-assisted synthesis characterization and biological activi-ties of organotin (IV) complexes with some thio schiff basesrdquoSpectrochimica Acta A vol 72 no 2 pp 260ndash268 2009

[34] W Rehman M K Baloch A Badshah and S Ali ldquoSynthesischaracterization and biological study of diorganotin(IV) com-plexes ofmonomethyl phthalaterdquo SpectrochimicaActaA vol 65no 3-4 pp 689ndash694 2006

[35] K K Chaturvedi and M Goyal ldquoAntibacterial studies of7-(120572-substituted sulphonamido)methyl- and 7-(120572-substitutedsulphonamido)phenyl-8-hydroxyquinolinesrdquo Journal of theIndian Chemical Society vol 61 no 2 pp 175ndash176 1984

[36] H L Singh B Khungar U D Tripaathi and A K VarshneyldquoSpectral and antimicrobial studies of organotin(IV) complexesof bidentate schiff bases having nitrogen and sulphur donorsystemsrdquo Main Group Metal Chemistry vol 24 no 1 pp 5ndash122001

[37] T R Fritsche P F McDermott T R Shryock and R DWalkerldquoAgar dilution and disk diffusion susceptibility testing ofCampylobacter spprdquo Journal of Clinical Microbiology vol 45no 8 pp 2758ndash2759 2007

[38] M Jabeen S Ali S Shahzadi et al ldquoHomobimetallic complexesof ligand having O and S donor sites with same and differentdi- and trialkylaryltin(IV) moiety their synthesis spectralcharacterization and biological activitiesrdquo Journal of IranianChemical Society vol 9 no 3 pp 307ndash320 2012

[39] S Shahzadi K Shahid S Ali and M Bakhtiar ldquoCharacteri-zation and antimicrobial activity of organotin(IV) complexes of2-[(2101584061015840-diethylphenylamido)]benzoates and 3-[(2101584061015840-diethyl-phenylamido)]propanoatesrdquo Turkish Journal of Chemistry vol32 no 3 pp 333ndash353 2008

[40] MAshfaqM I KhanMK Baloch andAMalik ldquoBiologicallypotent organotin(IV) complexes of 2-maleimidoacetic acidrdquoJournal of Organometallic Chemistry vol 689 no 1 pp 238ndash245 2004

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

6 Bioinorganic Chemistry and Applications

the latter from the biochemical point of view On comparingthe results in general it may be concluded that complexescontaining Zn(II) and Sn(IV) have greater inhibiting powerthan the free ligands as compared to organotin complexeswith sarcosine [16 17] against all the microbes

35 Antifungal Activity The synthesized compounds (1)ndash(6)and sarcosine were tested for antifungal activity by usingfluconazole as standard drug against four fungal strainsincluding A flavus A niger A alternate and G lucidum bydisc diffusion method [36] The results are summarized inTable 6 It was evident from tabulated data that the sarcosineas well as the synthesized complexes exhibited variety offungicidal activity Sarcosine exhibited maximum activityagainst A flavus (375 plusmn 086) while complex (5) exhibitedmaximum activity (395 plusmn 165) against G lucidum Complex(2) showed the lowest inhibition zone (190 plusmn 100) againstG lucidum It is noted that tributyltin complexes showed thegreatest inhibitory effect against fungi as compared to otheralkyl groupsThus the presence of butyl groups in compound(5) bonded with tin atom was responsible for the rise ofantifungal activity [37] The increased activity of complexesmight be due to the coordination of zinc and tin with oxygenand sulfur respectively [38] From the data it might beconcluded that triorganotin compounds were usually moreeffective against the fungi than diorganotin compounds [39]in contrast to earlier reported compounds in the literature[16] This might be due to the presence of Zn(II) along withSn(IV) which enhances the fungicidal activity of triorganotincomplexes

36 Structure Activity Relationship Although it is difficult tomake out an exact structure-activity relationship between theantimicrobial activity and the structure of these complexesit can possibly be concluded that the chelation as well as theaddition of a substrate enhances the activity of the complexesThe variation in the toxicity of different antibacterial agentsagainst various organisms depends on either the imperme-ability of the cell or differences in site of action or ability tocause mutations in the microorganism Though the resultssuggest that the ligand has a remarkable toxic property theircomplexes of tin inhibit the growth of microorganisms toa greater extent This is in accordance with earlier reports[40] Further the greater activity of the complexes can alsobe explained on the basis of their higher solubility of theparticles

4 Conclusion

The FT-IR data of synthesized complexes clearly demon-strate that the zinc and tin become attached with theoxygen and sulphur of the ligand in a bidentate modeIn solid state chlorodiorganotin complexes exhibit thepentahexacoordinated geometry whereas the triorgan-otin(IV) complexes show the five-coordinate geometry Bio-logical activity data showed that all the complexes werebiologically active with few exceptionsThese complexes were

found to be more potent inhibitors toward fungal culture ascompared to bacterial strains

Acknowledgment

Higher EducationCommission of Pakistan (HEC) is acknow-ledged for support under the Project no 20-1623RampD104402

References

[1] K E Appel ldquoOrganotin compounds toxicokinetic aspectsrdquoDrug Metabolism Reviews vol 36 no 3-4 pp 763ndash786 2004

[2] K C Molloy T G Purcell E Hahn H Schumann and J JZuckerman ldquoOrganotin biocides 4 Crystal and molecularstructure of tricyclohexylstannyl 3-indolylacetate incorporat-ing the first monodentate carboxylate group bonded to atriorganotin(IV)rdquoOrganometallics vol 5 no 1 pp 85ndash89 1986

[3] R R Holmes ldquoOrganotin cluster chemistryrdquoAccounts of Chem-ical Research vol 22 no 5 pp 190ndash197 1989

[4] R Barbieri A Silvestri M T L Giudice G Ruisi and M TMusmeci ldquoThe binding of trialkyltin(IV) moieties to rathaemoglobin and the structure of model systems studiedby tin-119 Mossbauer spectroscopyrdquo Journal of the ChemicalSociety Dalton Transactions no 3 pp 519ndash525 1989

[5] S Sadiq-Ur-Rehman K Shahid S Ali M H Bhatti and MParvez ldquoOrganotin esterification of (E)-3-(3-fluoro-phenyl)-2-(4-chlorophenyl)-2-propenoic acid synthesis spectroscopiccharacterization and in vitro biological activities Crystal struc-ture of [Ph

3Sn(OC(O)C(4-ClC

6H4) =CH(3-FC

6H4))]rdquo Journal

of Organometallic Chemistry vol 690 no 5 pp 1396ndash14082005

[6] P J Heard Progress in Inorganic Chemistry vol 53 John Wileyamp Sons New York NY USA 2005 edited by D Karlin

[7] S H LThoonen B Deelman and G van Koten ldquoSynthetic as-pects of tetraorganotins and organotin(IV) halidesrdquo Journal ofOrganometallic Chemistry vol 689 no 13 pp 2145ndash2157 2004

[8] H Hussain V U Ahmad I R Green K Krohn J Hussain andA Badshah ldquoAntibacterial organotin(IV) compounds theirsynthesis and spectral characterizationrdquo Arkivoc vol 2007 no14 pp 289ndash299 2007

[9] S Y Dike J R Merchant and N Y Sapre ldquoA new and efficientgeneral method for the synthesis of 2-spirobenzopyrans firstsynthesis of cyclic analogues of precocene I and related com-poundrdquo Tetrahedron vol 47 no 26 pp 4775ndash4786 1991

[10] L E da Silva P T de Sousa Jr A C Joussef C Piovezan andANeves ldquoSynthesis structure and physicochemical properties ofzinc and copper complexes based on sulfonamides containing8-aminoquinoline ligandsrdquo Quımica Nova vol 31 no 5 pp1161ndash1164 2008

[11] J Anwer S Ali S Shahzadi M Shahid S K Sharma and KQanungo ldquoSynthesis characterization semi-empirical studyand biological activities of homobimetallic complexes of tranex-amic acid with organotin(IV)rdquo Journal of Coordination Chem-istry vol 66 no 7 pp 1142ndash1152 2013

[12] S Jabbar I Shahzadi R Rehman et al ldquoSynthesis character-ization semi-empirical study and biological activities of organ-otin(IV) complexes with cyclohexylcarbamodithioic acid asbiological active ligandrdquo Journal of Coordination Chemistry vol65 no 4 pp 572ndash590 2012

Bioinorganic Chemistry and Applications 7

[13] H N Khan S Ali S Shahzadi and M Helliwell ldquoSynthesisspectroscopy and antimicrobial activity of chloro-organotin(IV) complexes of S-donor ligand crystal structureof chloro-t-dibutyltin[4-methyl-1-piperidine]thiocarboxylaterdquoRussian Journal of Inorganic Chemistry vol 57 no 5 pp665ndash670 2012

[14] F A Shah A Ali S Shahzadi C Rizzoli and A Ahmad ldquoSyn-thesis spectral characterization and X-ray crystal struc-ture of biologically active organotin(IV) 3-[(31015840 51015840-dimethyl-phenylamido)]propanoatesrdquo Journal of Iranian Chemical Soci-ety vol 9 no 6 pp 923ndash932 2012

[15] MM Amin S Ali S Shahzadi S K Sharma and K QanungoldquoDi- and triorganotin(IV) complexes of 2-aminobenzoic acidwith and without triphenylphosphine synthesis spectroscopysemi-empirical study and antimicrobial activitiesrdquo Journal ofCoordination Chemistry vol 64 no 2 pp 337ndash350 2011

[16] E Khoo N K Goh G Eng D J Whalen andA Hzell ldquoSynthesis characterization and fungicidalactivity of triphenyl derivatives of sarcosine crystalstructures of [Ph

3Sn(OCOCH

2NH2CHB)

2]Cl and

[Ph3(OCOCH

2NH2CH3)2]NCSrdquo Applied Organometallic

Chemistry vol 9 no 8 pp 699ndash706 1995[17] DKovala-Demertzi P TauridouAMoukarika JMTsangaris

C P Raptopoulou and A Terzis ldquoSynthesis and characteriza-tion of tin(IV) and organotin(IV) 14-dimethylpiperazine-25-dione (cyclosarcosylsarcosine) adductsrdquo Journal of the ChemicalSociety Dalton Transactions no 1 pp 123ndash128 1995

[18] L Ronconi C Marzano U Russo S Sitran R Graziani and DFregona ldquoSynthesis characterization and in vitro cytotoxicityof new organotin(IV) derivatives of N-methylglycinerdquo Journalof Inorganic Biochemistry vol 91 no 2 pp 413ndash420 2002

[19] W L F Armarego and C L L Chai Purification of LaboratoryChemicals Elsevier Burlington Vt USA 6th edition 2000

[20] W D Honnick and J J Zuckerman ldquoDiorganotin halide car-boxylates thiocarboxylates and halide haloacetatesrdquo Journal ofOrganometallic Chemistry vol 178 no 1 pp 133ndash155 1979

[21] E R T Tiekink ldquoStructural chemistry of organotin carboxyl-ates a review of the crystallographic literaturerdquo Applied Organ-ometallic Chemistry vol 5 no 1 pp 1ndash23 1991

[22] M Nath R Jairath G Eng X Song and A Kumar ldquoSynthesisspectral characterization and biological studies of some organ-otin(IV) complexes of l-proline trans-hydroxy-l-proline and l-glutaminerdquo SpectrochimicaActaA vol 62 no 4-5 pp 1179ndash11872005

[23] B S Hammes M T Kieber-Emmons J A Letizia et al ldquoSyn-thesis and characterization of several zinc(II) complexes con-taining the bulky heteroscorpionate ligand bis(5-tert-butyl-3-methylpyrazol-2-yl)acetate relevance to the resting states ofthe zinc(II) enzymes thermolysin and carboxypeptidase ArdquoInorganica Chimica Acta vol 346 pp 227ndash238 2003

[24] R Singh and N K Kaushik ldquoSpectral and thermal studies withanti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta A vol 71 no 2 pp669ndash675 2008

[25] H L Singh and J B Singh ldquoSynthesis and characterization ofnew lead(II) and organotin(IV) complexes of schiff basesderived fromhistidine andmethioninerdquo International Journal ofInorganic Chemistry vol 2012 Article ID 568797 7 pages 2012

[26] A Saxena J P Tandon K C Molloy and J J ZuckermanldquoTin(IV) complexes of tridentate schiff bases having ONS

donor systemsrdquo Inorganica Chimica Acta vol 63 no C pp 71ndash74 1982

[27] A K Saxena H B Singh and J P Tandon ldquoSynthesis andcharacterization of tin(IV) complexes of azinesrdquo SynthesisReactivity Inorganic and Metal-Organic Chemistry vol 10 pp117ndash136 1980

[28] H O Kalinowski S Berger and S Brown 13C NMR Spectro-skopie Thieme Stuttgart Germany 1984

[29] S Ali F Ahmad M Mazhar A Munir and M T MasoodldquoSynthesis and spectral studies of di- and triorganotin(IV) com-plexes with 2-(6-methoxynaphthyl)propionic acid (naproxen)rdquoSynthesis and Reactivity in Inorganic and Metal-Organic Chem-istry vol 32 no 2 pp 357ndash372 2002

[30] J Holecek M Nadvornık K Handlır and A Lycka ldquo13C and119Sn NMR spectra of Di-n-butyltin(IV) compoundsrdquo Journalof Organometallic Chemistry vol 315 no 3 pp 299ndash308 1986

[31] DHWilliams and I Fleming SpectroscopicMethods inOrganicChemistry McGraw-Hill London UK 4th edition 1987

[32] S S Konstantinovic B C Radovanovic S P Sovilj and SStanojevic ldquoAntimicrobial activity of some isatin-3-thiosemi-carbazone complexesrdquo Journal of the Serbian Chemical Societyvol 73 no 1 pp 7ndash13 2008

[33] R V Singh P Chaudhary S Chauhan and M Swami ldquoMicro-wave-assisted synthesis characterization and biological activi-ties of organotin (IV) complexes with some thio schiff basesrdquoSpectrochimica Acta A vol 72 no 2 pp 260ndash268 2009

[34] W Rehman M K Baloch A Badshah and S Ali ldquoSynthesischaracterization and biological study of diorganotin(IV) com-plexes ofmonomethyl phthalaterdquo SpectrochimicaActaA vol 65no 3-4 pp 689ndash694 2006

[35] K K Chaturvedi and M Goyal ldquoAntibacterial studies of7-(120572-substituted sulphonamido)methyl- and 7-(120572-substitutedsulphonamido)phenyl-8-hydroxyquinolinesrdquo Journal of theIndian Chemical Society vol 61 no 2 pp 175ndash176 1984

[36] H L Singh B Khungar U D Tripaathi and A K VarshneyldquoSpectral and antimicrobial studies of organotin(IV) complexesof bidentate schiff bases having nitrogen and sulphur donorsystemsrdquo Main Group Metal Chemistry vol 24 no 1 pp 5ndash122001

[37] T R Fritsche P F McDermott T R Shryock and R DWalkerldquoAgar dilution and disk diffusion susceptibility testing ofCampylobacter spprdquo Journal of Clinical Microbiology vol 45no 8 pp 2758ndash2759 2007

[38] M Jabeen S Ali S Shahzadi et al ldquoHomobimetallic complexesof ligand having O and S donor sites with same and differentdi- and trialkylaryltin(IV) moiety their synthesis spectralcharacterization and biological activitiesrdquo Journal of IranianChemical Society vol 9 no 3 pp 307ndash320 2012

[39] S Shahzadi K Shahid S Ali and M Bakhtiar ldquoCharacteri-zation and antimicrobial activity of organotin(IV) complexes of2-[(2101584061015840-diethylphenylamido)]benzoates and 3-[(2101584061015840-diethyl-phenylamido)]propanoatesrdquo Turkish Journal of Chemistry vol32 no 3 pp 333ndash353 2008

[40] MAshfaqM I KhanMK Baloch andAMalik ldquoBiologicallypotent organotin(IV) complexes of 2-maleimidoacetic acidrdquoJournal of Organometallic Chemistry vol 689 no 1 pp 238ndash245 2004

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Bioinorganic Chemistry and Applications 7

[13] H N Khan S Ali S Shahzadi and M Helliwell ldquoSynthesisspectroscopy and antimicrobial activity of chloro-organotin(IV) complexes of S-donor ligand crystal structureof chloro-t-dibutyltin[4-methyl-1-piperidine]thiocarboxylaterdquoRussian Journal of Inorganic Chemistry vol 57 no 5 pp665ndash670 2012

[14] F A Shah A Ali S Shahzadi C Rizzoli and A Ahmad ldquoSyn-thesis spectral characterization and X-ray crystal struc-ture of biologically active organotin(IV) 3-[(31015840 51015840-dimethyl-phenylamido)]propanoatesrdquo Journal of Iranian Chemical Soci-ety vol 9 no 6 pp 923ndash932 2012

[15] MM Amin S Ali S Shahzadi S K Sharma and K QanungoldquoDi- and triorganotin(IV) complexes of 2-aminobenzoic acidwith and without triphenylphosphine synthesis spectroscopysemi-empirical study and antimicrobial activitiesrdquo Journal ofCoordination Chemistry vol 64 no 2 pp 337ndash350 2011

[16] E Khoo N K Goh G Eng D J Whalen andA Hzell ldquoSynthesis characterization and fungicidalactivity of triphenyl derivatives of sarcosine crystalstructures of [Ph

3Sn(OCOCH

2NH2CHB)

2]Cl and

[Ph3(OCOCH

2NH2CH3)2]NCSrdquo Applied Organometallic

Chemistry vol 9 no 8 pp 699ndash706 1995[17] DKovala-Demertzi P TauridouAMoukarika JMTsangaris

C P Raptopoulou and A Terzis ldquoSynthesis and characteriza-tion of tin(IV) and organotin(IV) 14-dimethylpiperazine-25-dione (cyclosarcosylsarcosine) adductsrdquo Journal of the ChemicalSociety Dalton Transactions no 1 pp 123ndash128 1995

[18] L Ronconi C Marzano U Russo S Sitran R Graziani and DFregona ldquoSynthesis characterization and in vitro cytotoxicityof new organotin(IV) derivatives of N-methylglycinerdquo Journalof Inorganic Biochemistry vol 91 no 2 pp 413ndash420 2002

[19] W L F Armarego and C L L Chai Purification of LaboratoryChemicals Elsevier Burlington Vt USA 6th edition 2000

[20] W D Honnick and J J Zuckerman ldquoDiorganotin halide car-boxylates thiocarboxylates and halide haloacetatesrdquo Journal ofOrganometallic Chemistry vol 178 no 1 pp 133ndash155 1979

[21] E R T Tiekink ldquoStructural chemistry of organotin carboxyl-ates a review of the crystallographic literaturerdquo Applied Organ-ometallic Chemistry vol 5 no 1 pp 1ndash23 1991

[22] M Nath R Jairath G Eng X Song and A Kumar ldquoSynthesisspectral characterization and biological studies of some organ-otin(IV) complexes of l-proline trans-hydroxy-l-proline and l-glutaminerdquo SpectrochimicaActaA vol 62 no 4-5 pp 1179ndash11872005

[23] B S Hammes M T Kieber-Emmons J A Letizia et al ldquoSyn-thesis and characterization of several zinc(II) complexes con-taining the bulky heteroscorpionate ligand bis(5-tert-butyl-3-methylpyrazol-2-yl)acetate relevance to the resting states ofthe zinc(II) enzymes thermolysin and carboxypeptidase ArdquoInorganica Chimica Acta vol 346 pp 227ndash238 2003

[24] R Singh and N K Kaushik ldquoSpectral and thermal studies withanti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta A vol 71 no 2 pp669ndash675 2008

[25] H L Singh and J B Singh ldquoSynthesis and characterization ofnew lead(II) and organotin(IV) complexes of schiff basesderived fromhistidine andmethioninerdquo International Journal ofInorganic Chemistry vol 2012 Article ID 568797 7 pages 2012

[26] A Saxena J P Tandon K C Molloy and J J ZuckermanldquoTin(IV) complexes of tridentate schiff bases having ONS

donor systemsrdquo Inorganica Chimica Acta vol 63 no C pp 71ndash74 1982

[27] A K Saxena H B Singh and J P Tandon ldquoSynthesis andcharacterization of tin(IV) complexes of azinesrdquo SynthesisReactivity Inorganic and Metal-Organic Chemistry vol 10 pp117ndash136 1980

[28] H O Kalinowski S Berger and S Brown 13C NMR Spectro-skopie Thieme Stuttgart Germany 1984

[29] S Ali F Ahmad M Mazhar A Munir and M T MasoodldquoSynthesis and spectral studies of di- and triorganotin(IV) com-plexes with 2-(6-methoxynaphthyl)propionic acid (naproxen)rdquoSynthesis and Reactivity in Inorganic and Metal-Organic Chem-istry vol 32 no 2 pp 357ndash372 2002

[30] J Holecek M Nadvornık K Handlır and A Lycka ldquo13C and119Sn NMR spectra of Di-n-butyltin(IV) compoundsrdquo Journalof Organometallic Chemistry vol 315 no 3 pp 299ndash308 1986

[31] DHWilliams and I Fleming SpectroscopicMethods inOrganicChemistry McGraw-Hill London UK 4th edition 1987

[32] S S Konstantinovic B C Radovanovic S P Sovilj and SStanojevic ldquoAntimicrobial activity of some isatin-3-thiosemi-carbazone complexesrdquo Journal of the Serbian Chemical Societyvol 73 no 1 pp 7ndash13 2008

[33] R V Singh P Chaudhary S Chauhan and M Swami ldquoMicro-wave-assisted synthesis characterization and biological activi-ties of organotin (IV) complexes with some thio schiff basesrdquoSpectrochimica Acta A vol 72 no 2 pp 260ndash268 2009

[34] W Rehman M K Baloch A Badshah and S Ali ldquoSynthesischaracterization and biological study of diorganotin(IV) com-plexes ofmonomethyl phthalaterdquo SpectrochimicaActaA vol 65no 3-4 pp 689ndash694 2006

[35] K K Chaturvedi and M Goyal ldquoAntibacterial studies of7-(120572-substituted sulphonamido)methyl- and 7-(120572-substitutedsulphonamido)phenyl-8-hydroxyquinolinesrdquo Journal of theIndian Chemical Society vol 61 no 2 pp 175ndash176 1984

[36] H L Singh B Khungar U D Tripaathi and A K VarshneyldquoSpectral and antimicrobial studies of organotin(IV) complexesof bidentate schiff bases having nitrogen and sulphur donorsystemsrdquo Main Group Metal Chemistry vol 24 no 1 pp 5ndash122001

[37] T R Fritsche P F McDermott T R Shryock and R DWalkerldquoAgar dilution and disk diffusion susceptibility testing ofCampylobacter spprdquo Journal of Clinical Microbiology vol 45no 8 pp 2758ndash2759 2007

[38] M Jabeen S Ali S Shahzadi et al ldquoHomobimetallic complexesof ligand having O and S donor sites with same and differentdi- and trialkylaryltin(IV) moiety their synthesis spectralcharacterization and biological activitiesrdquo Journal of IranianChemical Society vol 9 no 3 pp 307ndash320 2012

[39] S Shahzadi K Shahid S Ali and M Bakhtiar ldquoCharacteri-zation and antimicrobial activity of organotin(IV) complexes of2-[(2101584061015840-diethylphenylamido)]benzoates and 3-[(2101584061015840-diethyl-phenylamido)]propanoatesrdquo Turkish Journal of Chemistry vol32 no 3 pp 333ndash353 2008

[40] MAshfaqM I KhanMK Baloch andAMalik ldquoBiologicallypotent organotin(IV) complexes of 2-maleimidoacetic acidrdquoJournal of Organometallic Chemistry vol 689 no 1 pp 238ndash245 2004

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of