INDIAN J. CHEM., VOL. 17A, APRIL 1979

TABLE 1 - ANALYTICALDATA & MAGNETICMOMENTSOF COPPER(II) SEMICARBAZONECOMPLEXES

Complex Mol. formula Found (Calc.) (%) (.Lel!. (BM)

CuCu(OAAS) CuCllHllN,Oa 19·30

Cu(OATS) CuC12HlaN,Oa(19'55)18·70

Cu(OACAS) CuC12H1oClN503(18'75)17·60

Cu(OAXS) CUC13H15N50a(17-70)17·90

Cu(OAANS) CUC12H13N50.(18·00)17·90

(17,90)

C H N

40·00 3·40 21·00 1-30(40·61) (3·38) (21'54)45·50 4·10 21-10 1-13

(46,02) (3·83) (20·65);39·50 3:10 19·10 1·21(40·12) (2·79) (19'50)43·80 4'50 19·20 1-15

(44-19) (4'25) (19,83)39·95 3·91 19·60 1·15

(40'57) (3·67) (19'72\

. A. general method of preparation of the complexesIS given below: To a solution of the ligand, OAAS(2'6 g, 0·01 mol) in minimum amount 0'£ absoluteethanol (150 ml) Was added an aqueous solution ofcO'pper(!I) acetate monohydrate (1 g, 0·005 mol)and boiled for 15 min. On cooling a dirty greenproduct s~parated out, which was suction filtered,washed with hot water and aq. ethanol and driedin a vacuum desiccator over CaCI2• Copperffl)complexes of the other ligands were prepared in asimilar fashion.. ~he analytic~l ?ata of the complexes (Table 1)indicate Li] stoichiometry (metal: ligand) and hencethe semicarbazones act as tridentate dibasic ligands.

The infrared spectra (vmax in crrr") of the ligandsexhibited a strong band in the region 3480-3450.:rhi.s band is absent in the spectra of the complexes,indicating thereby deprotonation of oximino groupand formation of covalently bonded complexes.The. strong band at 9'95-970 in the ligands,attributable to vN-O, shifts to 1170-1140 in thecomplexes showing the coordination of metal ionto nitrogen of oxirnino groupsv". The strong bandaro,:nd 1610-1595 exhibited by the ligands isat tributeds to vC=N. In the complexes this bandundergoes a shift of 15 crrr+, and appears around1600-1580, thereby indicating the coordination ofsemicarbazide and oximino nitrogen atoms. Theband appearing around 1220 is attributed to enolicform of CONH2 group in semicarbazide moietyof the ligands. This band in the complexes appearsaround 1245. The shift of this band to higherfrequency region in the complexes indicates thecoordination through' oxygen atom of C-OHlo.The N -N band around 1040-1020 in the ligandsshifts to the higher frequency side in the com-plexestt. The magnitude of this positive shift(10-30 crrr+) indicates the monodentate Iinkage-s ofN -N residue as a shift of 50 cm-I is usuallyobserved in case of bidentate linking of N -N.

The electronic spectra .(reflectance spectra) of thecomplexes exhibit two bands, one centred at 16600~m-I and the other which is more intense is centeredat 25000 crrr-. The band at 25000 cm-I may beassigned to a symmetry-forbidden ligand-e-metalcharge transfer bandIO,13,l(, and the one at 16600crn? is assigned to the d-d transition correspondingto 2T2g+-2Eg; the band position is in agreement withthose generally observed for planar copper(II) com-plexes=. The room t emperature magnetic moments

416

..

(

of the complexes are in the range 1·15 to 1·30 B.M.(Table 1) which is markedly less than the spin onlyvalue of 1·73 B.M. expected for an 5 = t system.The low values of magnetic moments are probablydue to a dimeric structure-".

References1. PATEL, M. R. & MANKAD,B. N., Indian J. app], Chem.,

31 (1968). 32.2. PATEL, M. M., PATEL, M. R. & MANKAD,B. N., J. Indian

chem, Soc., Vol. LIII (1976), 454. .3. PATEL, M. M., PATEL, RATILAL P., PATEL, K. A. &

PATEL, N. L., Indian J. Chem., Vol. 11 (1973), 1177.4. PATEL, M. M. & PATEL, RATILAL P., J. Indian chem,

Soc., Vol. LI (1974), 770.5. GODYCKI, L. E. & RUNDLE, R. E., Acta Crystallogr.,

6 (1953),487.6. FRASSON, E., BARDI, R. & BEZZI, S., Acta Crysiallogr.,

12 (1959), 201.7. SCHLEMPER, E. 0., Inorg. Chem., 7 (1968), 1130.8. JARSKI, M. A., & LINGAFELTER, Acta Crystallogr., 17

(1964), 109.9. STERK, H. & ZIEGLER\ E., Monatsch Chem., 97 (1966),

1131.10. SYAMAL,A. & KALE, K. S., Indian J. Chem., 16A (1978),

46.11. AGGARWAL,R. C. & NARANG, K. K., Indian J. Chem.,

9 (1971), 1413.12. BHAIBANTI, A., DALLVALLE, F., PELLINGHELL, M. A.,

Inorg. Chem., 7 (1968), 1430.13. DUBICKI~ L. & MA.RTIN, R. L., Inorg. Chem., 5 (1966),

2203.14. GREGSON, A. K., MARTINI, R. L. & MITRA, S., Proc.

ray. soe., A320 (1971), 473.15. SACCONI, L. & CIAMPOLINI, M., J. chem, Soc., (1964),

276.

Studies on Some Adducts of Copper(II)Tartrate

D. C. DAS & s. PA.NI*Post-Graduate Department-of Chemistry

Sarnbalpur University, ]yoti Vihar, Burla 768017

Received 11 May 1978; revised 14 August 1978;accepted 5 October 1978

Compounds of the type CuTM(X)a-4H.O [where M =Ni(II) , Cu(II), Co(II), Zn(II); T = tartrate ion; X =OH-, F-] have been prepared and characterized on thebasis of analytical, magnetic susceptibility and IRspectral data. The solubility data of copper(II)-tartrate' in MCt. and MBr2 solutions also corroboratethe formation of the above type of complexes in solution.

COPPER (II) tartrate, a sparingly soluble com-pound, behaves as a monobasic acid and is

known to form soluble complex salts with bothstronc and weak bases>". The results indicatethat the strength of the base is not a factor incomplex formation. The present note describesthe preparation and physicochemical studies onthe adducts of CuT with some other sparin~lysoluble compounds of the type M(OH)2' MF2 andMOH(C6H50) (M = Ni, Co, Cu and Zn).

All the chemicals used were of AR (BDH) quality.The infrared spectra Were recorded in KBr on aPerkin-Elmer 257 infrared spectrophotometer.Magnetic measurements were carried out using aGuoy balance. For pH and conductivity measure-ments, Cambridge portable pH meter and Phillipsconductivity bridge with a dip-type cell wereemployed. The starting material CuT Was pre-pared by the method reported earlier>. The hydro-xides, hydroxy phenate and the fluorides of themetals Were prepared by adding respectively sodiumhydroxide, sodium phenate and sodium fluoride tosoluble salts of the metals.

All the compounds of the type CuTM(X)2.4H20were prepared by refluxing an aqueous suspensionof CuT and MX2 (X = OH-, F-) for 4-5 hr. Itwas filtered and evaporated to dryness. Tartrateand metal contents of the crystalline solids obtainedwere analyzed following the procedure reportedearlier='. The analytical results are shown inTable 1. The analytical results show the formationof 1: 1 adducts in all the cases. Solubility studysupports such type of adduct formation in solution.Solubilities of CuTCu(OH)2.4H20,CuTCo(OH)2.4H20,CuTNi(OH)2.4H20 and CuTZn(OH)2.4H20 in waterat 30° are 5'5xl0-3; 1·01 X 10-2, 1'68xl0-2 and5·75 x l 0-2 moles/litre respectively. The solubilityof CuT in sodium chloride of different concentra-tions at 31° is nearly the same as that in pure water.The solubilities in MX2 (X = Cl', Br-) solutions atthe same temperature are appreciably higher indicat-ing the formation of complex CuT(MX2)n.

kCu'T(s) +nMX2 ~ CuT(MX2)nIt can be shown that,log [CuT(MX2)n] = log k+n log [MX2].

The values of n and log k were evaluated by themethod reported earlier". The results indicate theformation of 1: 1 adducts in solution and the orderof solubilities is MF2>MCl2>MBr2. The molarconductance values (154-212 ohrrr ' em- mole-I) ofCuTM(OH)2.4H20 indicate that the compoundsdissociate in solution. The dissociation may bedue to liberation of a proton which is supported byPH measurements.

50 ml of O'OIM solution of CuTM(OH)2.4H20 andthe same volume of water were separately titratedagainst 0·087 sodium hydroxide solution and thepH of the solution was measured at 30° after eachaddition. The pH titration curves indicate thecompounds to be reacting with base. The averagenumber (n) of ionisable hydrogens attached to themolecule Was calculated from the horizontal distancebetween the two curves and n values Were plottedagainst the corresponding pH values. From the.

/

..

NOTES

TABLE 1 - ANALYTICAL,AND MAGNETICMOMENT DATA OPCuTMX2 COMPOUNDS

Found (calc.), % lLeff(BM)

Cu M T

CuTCu(OHh·4H2O 32'28 38·42 3·98

CuTCo(OHh·4H2O(33-34) (38'81)16'78 15·75 6·7

(16'80) (15-60)CuTNi(OHh.4H2O 16·08 14-95 5-4

(16'90) (15'60)CuTZn(OHh.4H2O 16'30 17·05 2'02

(16'60) (17'07)CuTCu(F)2.4H2O 32'67 38·31 4'2

(33'00) (38'43)CuTCo(F)2.4H2O 16'03 15'03 7·1

(16'69) (15-40)CuTNi(Fh.4H2O 16'20 14-80 6'1

(16'60) (15-40)CuTZn(F)2.4H2O 2'08CuTCu(OH) (OC6 27'50 32'12Hs).4H2O (27-80) (32·38)

CuTCo(OH) (OC6 14·18 13'13Hs).4H2O (14'06) (13'02)

CuTNi(OH) (OC6 14,86 12·07Hs,I.4H2O / (14·05) (12'98)

CuTZn(OH) (OC6 13-5 14·34Hs)·4H.O (13'85) (14'24)

TABLE 2 - ACID DISSOCIATIONCONSTANTSOF CuTM(OHh.4H.O AT 30°

Bjerrum's Schroder's methodhalf-n-method

Compound log h1 log h2log h1 log h.

CuTCO(OH) •.4H.O 6·47 2'81 6·49 3'50CuTNi(OH)2.4H.O 6'5 4'2 6'65 4'05CuTCu(OH) •.4H.O 5'9 5'28CuTZn(OHJ..4H.O 3·76

curves log kl and log k2 Were_evaluated by Bjerrum'shalf-ii-method with subsequent correction by themethod employed by Schrader", The values areshown in Table 2.

Very close values of log kl and log k2 forCuTCu(OH)2.4H20 indicates that both the reactionsare taking place simultaneously whereas very lowvalue of log k2 compared to log kl for CuTZn(OH)2'4H20 indicates predominance of monobasic acidbehaviour.

In the IR spectrum] of sodium potassium tar-trate, a strong and a medium intensity bands areobserved at 1615 and 1460 respectively. These areprobably due to symmetric and antisymmetricvibration of the carboxylate group. In tartaricacid, sharp bands at 1750 and 1097 have beenassigned to the carboxylic acid group and v C-O ofsecondary alcoholic group". In the present com-pounds a strong and sharp band is observed at1600-1625, but no band is observed around 1460arid 1750. This indicates the probable coordinationof both the carboxylate groups. In lactate ion,the secondary alcoholic group has an in-plane O-Hbending absorption at 1275 which is shifted to1390 on chelation with zinc". The bands in the

+Band positions in cm-".

417

,INDIAN J. CHEM., VOL. 17A, APRIL 1979

range 1370-1400 in these compounds might be dueto chelation of alcoholic group. Instead of singleband at 1097, as reported for tartaric acid, splitbands around 1116-1145 and .1050-1080 are observedwhich means that one of the 1.wo secondary alco-holic groups is coordinated. The positions of allthese bands compare well with those of NaCuT(OH)lwith an additional band of medium intensity pre-sent in the range 925-950. This may be attributed l>

to the presence of bridging OH group".However, room temperature [1.eff values of the

complexes (Table 1) reflect the magnetic momentsof the individual metal ions constituting the com-plex and' absence of any interaction.

Grateful thanks are due to the UGC, New Delhifor the award of a Teacher Fellowship to one of theauthors (D.C.D.).

References1. PATEL, R. C., SATPATHY, K. C. & PANI, S., J. Indian

chem, Soc., 50 (1973), 439. '2. SAHOO,S. C., MrsHRA, S., DAs, D. C. & PANI, S., J. Indian

chem, Soc., 54 (1977), 774.3. DAS, A. K., DAS, D. C. & PANI, S., J. Lndian+chem, Soc.

(communicated).4. VOGEL, A. I., A textbook of quantitative inorganic analysis

(Longmans Green, London), 1969, 389; 470; 533.5. CHOUDHARY,B. N. & PANI, S., J. Indian chem, Soc., 33

(1956),34.6. SCHRODER,N. H., Acta chem, scand., 20 (1966), 1401.7. KIRSCHNER, S. & KIESLING, R., J. Am. chem, Soc., 82

(1960), 4174.8. GOULDEN, J. D. S., Specirochim, Acta, 16 (1960), 715.9. FERRARO,J. R. & WALKER, W, R., Inorg. Chem., 4 (1965),

1382.

Anil Complexes of Uranyl Acetate

SUSHIL K. MISRA* & FARIDA S. SIDDIQUIChemistry Department, Luckno w University

Lucknow 226007

Received 27 March 1978; revised 9 November 1978;accepted 16 November 1978

Anil complexes of uranium(VI) of the type UO.(CHsCOO)(SB) (where SB represents the anions of theSchiff bases derived from salicylaldehyde and aryla-mines) have been synthesized in almost quantitativeyields by the reaction of uranyl acetate with the Schiffbase (HSB) in I: I molar ratio. Conductance, electronand IR spectral studies have been carried out to charac-terize the complexes. The complexes are assignedoctahedral structures in which acetate group actsas a btdentate ligand.

SEVERAL Schiff base complexes of dioxouranium(VI) have been reported-+, However, uranyl

complexes of Schiff bases derived from sali-cylaldehyde and substituted anilines have not beenreported. Synthesis and' physicochemical studiesof some -new complexes of uranyl acetate withligands of type (I) have been described in this note.

Uranyl acetate, amines and salicylaldehyde (allBDH reagents) as well as the solvents (BDH andE.Merck reagents) were used without further puri-fication.

418

(

fj RA-C=N~~O-H '\3

WhereR:: 0-, rrr; p- CH3j0-, m-, p-OCH3m,p-N02p-CI

(l)

The ligands were prepared by condensing salicyl-aldehyde with different aromatic am~nes. I~ atypical experiment, equimolar eth'l;nohc .solutIOnsof salicylaldehyde and the aromatic amine w~rerefluxed for an hour. On cooling a crystallineproduct separated which was filtered and recrystal-lized from the same solvent.

The complexes were prepared by the direct inter-action of uranyl acetate (1 mmole) and the base(1 mmole) using methanol as the solvent and reflux-ing for 1-2 hr. The product was dried and filteredin vacuo.

Carbon, hydrogen and nitrogen in the complexeswere determined by semimicro methods and ura-nium was estimated as oxinate (Table 1).

_ Using the bidentate Schiff bases HSB, complexes'of the type U02(CH3COO)(SB) were obt ain ed.These complexes are soluble in common orga~lcsolvents and are stable in the solid and solutionstates. Molecular weights were measured by thecryoscopic method and the results show that thecomplexes are monomers. The co~p~ex~s are nor~-electrolytes in absolute methanol indicating coordi-nated nature of the acetate group. In DMF alsothe complexes behave as non-electrolytes indicatingthat the acetate ion is not replaced even by thestrongly coordinating DMF molecule",

The molar magnetic susceptibilities (Xm) of thecomplexes determined (Gouy method) at roomtemperature (30 ± 1°) show them to be diamagne-tic.

The hydrogen-bonded v O-H vibration p~esentat 2800 cm-1 in the ligands is not observed m the

TABLE 1 - ANALYTICALDATA AND MELTING POINTS OFTHE COMPLEXES

Complex Found (Calc.), %

C H N U m.p.

U02(CHsCO.) 35'68 2·70 2·62 44'00 195(CUH12ON-o) (35'62) (2,78) (2'59) (44'15)

192 (d)U02(CHsCO.) 35,70 2,82 2·64 44·32(C14H12ON-m) (35'62) (2'78) (2'59) (44-15)

UO.(CHsCO.) 35'55 2'69 2'50 44'22 210(C14H12ON-p) (35'62) (2'78) (2'59) (44'15)

UO.(CHsCO.) 34·65 2·80 2'59 42·94 168 (d)(C14H12U2N-o) . (34'59) (2'70) (2'52) (42-88)

196 (d)UO.(CH3CO.) 34·48 2'75 2'60 42'80(C14H12O.N-m) (34'59) (2'70) (2'52) (42-88)

UO.(CHSC02) 34-62 2·64 2·55 42'82 160(C14H12C'2N-P) (34'59) (2'70) (2'52) (42-88)

168 (d)UO.(CH3C02) 31'58 2·04 5·00 41·77(C13H.OsN-m) (31'63) (2'10) (4'92) (41'82)

U02(CHsCO.) 31·70 2·01 4·86 41'80 150(C13H.OsN-P) (31'63) (2'10) (4'92) (41'82)

UO.(CHSC02) 32·08 2'19 2,43 42'62 135 (d)(C1sH.OCl-P) (32'14) (2'14) (2'50) (42'50)

-,\