Synthesis, spectral, molecular structure, HOMO-LUMO and ... … · experimental values. In...

Available online at www.worldscientificnews.com

WSN 36 (2016) 27-46 EISSN 2392-2192

Synthesis, spectral, molecular structure, HOMO-LUMO and NLO analysis of some (E)-N’-(3,3-

dimethyl-2,6-diarylpiperidin-4-ylidene)-4-methoxybenzohydrazide

G. Sundaraselvan and S. Darlin Quine*

Department of Chemistry, Government Arts College, C. Mutlur, Chidambaram - 608102, India

*E-mail address: [email protected]

ABSTRACT

(E)-N’-(3,3-dimethyl-2,6-diarylpiperidin-4-ylidene)-4-methoxybenzohydrazide (DDMs) have

been synthesized and their IR and 1H spectra were recorded. The optimized geometric parameters

(bond lengths, bond angles and dihedral angles) were in good agreement with the corresponding

experimental values. In addition, HOMO-LUMO, MEP and atomic charges of carbon, nitrogen and

oxygen were calculated using B3LYP/6-311G(d,p) level theory. The polarizability and first order

hyperpolarizability of the title molecule were calculated and interpreted.

Keywords: piperidin-4-one; DFT; HOMO – LUMO energies; NLO

1. INTRODUCTION

The piperidone and its derivatives are a class of nitrogen containing heterocycles that

have received much attention because of their wide range of biological activities1-5

as well as

properties useful from the technological point of view 6,7

. Pipeeridin-4-ones were also used as

corrosion and oxidation inhibitors8. Regardless of this fact, studies regarding the investigation

World Scientific News 36 (2016) 27-46

-28-

of their molecular structure and their electronic structure by computational techniques are

lacking in the chemical literature 9-11

. Density functional theory (DFT) calculations are the

excellent alternative methods in the design of NLO molecules and it helps to predict

properties of the new materials, such as molecular dipole moments, polarizabilities, and

hyperpolarizabilities12

. The present work reports the results of a systematic study of the

geometrical and electronic structure, electrostatic potential surfaces and molecular

hyperpolarizability based on their density functional theory computations.

2. EXPERIMENTAL DETAILS

Synthesis of 3,3-Dimethyl-2,6-diarylpiperidin-4-ones ( 1-5)

Dry ammonium acetate (100 mmol), 3-methyl-2-butanone (100 mmol) and

appropriate substituted benzaldehyde (200 mmol) in ethanol were just heated to boil and

allowed to stand at room temperature overnight. The reaction mixture was diluted with ether

(100 mL) and treated with Conc. HCl (20 mL). The precipitated hydrochloride was washed

with ethanol–ether. The hydrochloride was suspended in acetone and neutralized with

aqueous ammonia. Dilution with water gave the free base which was recrystallized from

ethanol.

Synthesis of ethyl 4-methoxybezoate (6) and 4-methoxybezo hydrazide (7) Ethyl

4-methoxybezoate (6) and 4-methoxybezo hydrazide (7) were synthesized as per the

procedure described in literature 13

.

Synthesis of (E)-N’-(3,3-dimethyl-2,6-diarylpiperidin-4-ylidene)-4-methoxybenzohydrazide (8-12)

A mixture of 3,3-Dimethyl-2,6-diarylpiperidin-4-ones (1 mmol), 4-methoxybezo

hydrazide (1.5 mmol) in ethanol and a few drops of acetic acid was added and refluxed for 2–

4 h. On completion of the reaction time, a solid mass was formed, which was then cooled to

room temperature. The precipitate was filtered off and washed with ice-cooled water– ethanol

mixture. The crude product was recrystallized from ethanol. Synthetic routes of compounds

are given in scheme 1.

(E)-N’-(3,3-dimethyl-2,6-diphenylpiperidin-4-ylidene)-4-methoxybenzohydrazide (8)

Pale Yellow solid; Yield 65%., M.P: 191 °C, MF: C27H29N3O2; elemental analysis:

Calcd (%): C, 75.85; H, 6.84; N, 9.83; O, 7.48; found (%): C, 75.74; H, 6.86; N, 9.79; IR

(KBr, cm-1

): 3464 (N-H), 3068 (Ar-C-H), 2935 (AliC-H), 1647 (C=O); 1H-NMR (CDCl3)

7.26-8.01 (m, Ar-H), 2.14 (1H, N-H), 7.26 (1H, N-H), 3.01 (1H, H5ax,), 3.13 (1H, H5eq),

3.88 (1H, H2), 3.54 (1H, H6), 3.50 (3H, OCH3), 1.62 (3H, CH3); Mass (m/z): 426 (M+), 350,

265, 164, 107, 96, 77.

(E)-N’-(2,6-bis(4-fluorophenyl)-3,3-dimethyl-2,6-diphenylpiperidin-4-ylidene)-4-

methoxybenzohydrazide (9)

Yellow solid; Yield 63%., M.P: 204 °C, MF: C27H27F2N3O2; elemental analysis:

Calcd (%): C, 69.96; H, 5.87; F, 8.20; N, 9.07; O, 6.90; found (%): C, 69.665; H, 5.83; N,


-29-

9.03; IR (KBr, cm-1

): 3477 (N-H), 3064 (Ar-C-H), 2920 (AliC-H), 1674 (C=O); 1H-NMR

(CDCl3) 6.84-7.75 (m, Ar-H), 2.14 (1H, N-H), 7.28 (1H, N-H), 2.18 (1H, H5ax,), 2.54 (1H,

H5eq), 4.36 (1H, H2), 4.00 (1H, H6), 3.91 (3H, OCH3), 1.61 (3H, CH3); Mass (m/z): 462

(M+), 368, 328, 273, 150, 107.

(E)-N’-(2,6-bis(4-chlorophenyl)-3,3-dimethyl-2,6-diphenylpiperidin-4-ylidene)-4-


Pale Yellow solid; Yield 66%., M.P: 189 °C, MF: C27H27Cl2N3O2; elemental analysis:

Calcd (%): C, 65.32; H, 5.48; Cl, 14.28; N, 8.46; O, 6.45; found (%): C, 65.302; H, 5.45; N,

8.43; IR (KBr, cm-1

): 3427 (N-H), 3059 (Ar-C-H), 2927 (AliC-H), 1653 (C=O); 1H-NMR

(CDCl3) 7.47-8.18 (m, Ar-H), 1.97 (1H, N-H), 7.28 (1H, N-H), 2.37 (1H, H5ax,), 2.54 (1H,

H5eq), 3.19 (1H, H2), 4.78 (1H, H6), 3.68 (3H, OCH3), 1.66 (3H, CH3); Mass (m/z): 458

(M+), 444, 352, 324, 282, 135, 93.

(E)-N’-(3, 3-dimethyl-2,6-di-p-tolylpiperidin-4-ylidene)-4-methoxybenzohydrazide (11)



(KBr, cm-1


7.05-7.60 (m, Ar-H), 2.15 (1H, N-H), 6.75 (1H, N-H), 2.48 (1H, H5ax,), 2.66 (1H, H5eq),


349, 329, 293, 135.

(E)-I’-(2,6-bis(4-methoxyphenyl)-3,3-dimethyl-2,6-diphenylpiperidin-4-ylidene)-4-




(KBr, cm-1


6.75-7.32 (m, Ar-H), 2.17 (1H, N-H), 6.90 (1H, N-H), 2.70(1H, H5ax,), 3.06 (1H, H5eq),


456, 380, 352, 349, 164, 111.

Spectral measurements

The FT-IR spectrum of the synthesized DDMs was measured in the range 4000-500

cm-1

on a AVATAR-330 FT-IR spectrometer (Thermo Nicolet) using KBr (pellet form). 1H

NMR spectrum was recorded at 400 MHz on a BRUKER model using CDCl3 as solvent.

Tetramethylsilane (TMS) was used as internal reference for all NMR spectra, with chemical

shifts reported in δ units (parts per million) relative to the standard.

Computational studies

Structure optimizations of DDMs were performed at the Density Functional Theory

(DFT) level employing B3LYP/6-311G(d,p) functional as implemented in the Gaussain

03W14

. To investigate the reactive sites of the title molecules, the Mulliken and molecular

electrostatic potential were evaluated.


-30-

Scheme 1. Synthetic routes of compounds (8-12).


-31-

Moreover, in order to show nonlinear optical (NLO) activity of studied molecules, the

dipole moment, linear polarizability and first order hyperpolarizability were obtained from

molecular polarizabilities based on theoretical calculations. Also, the HOMO-LUMO on

optimized structures is accomplished at B3LYP/6-311G(d,p) level computation. The

electronegativity (χ) were reported by Iczkowski et al.15

is performed as χ = (EHOMO +

ELUMO)/2. The global electrophilicity16

(ω) is also calculated following the expression ω =

(μ2/2η), where μ is the chemical potential (μ ≈ (EHOMO + ELUMO) / 2), and η is the chemical

hardness (ELUMO − EHOMO)/2)17

.

3. RESULTS AND DISCUSSION

Molecular geometry

The chair conformer of piperidine molecule is the most stable conformer18,19

.

Therefore, we neglected other conformations i.e. boat, envelope or twist boat because of their

high energy. Piperidine molecules show the equatorial disposition of N-H in chair conformer

as the most stable one 20

.

Fig. 1. Numbering Pattern of DDMs.

The optimized structural parameters such as bond lengths, bond and dihedral angles

of DDMs were determined at B3LYP level theory with 6-311G(d,p) basis set and are

presented in Table 1 in accordance with the atom numbering scheme of the molecule shown

in Fig. 1. To the best of our knowledge, no single crystal X-ray crystallographic data of

DDMs has yet been reported. However, the theoretical results obtained are almost

comparable with closely related molecules such as E)- N’-(3,3-Dimethyl-2,6-diphenylpiperidin-


-32-

4-ylidene)isonicotinohydrazide21

. The C2-N1 and C6-N1 bond nearly 1.464 Å by B3LYP,

which is coincide with literature value 1.463 Å21

.

(8)

(9)


-33-

(10)

(11)


-34-

(12)

Fig. 2. Optimized structures of DDMs.

Table 1. Selected bond lengths, bond angles and dihedral angles of DDMs.

Bond length (Å) XRDa 8 9 10 11 12

C2-N1 1.463 1.464 1.465 1.465 1.464 1.465

N1-H1 0.900 1.016 1.016 1.016 1.026 1.016

C6-N1 1.458 1.479 1.481 1.481 1.481 1.479

C2-C3 1.554 1.592 1.591 1.591 1.581 1.591

C3-C4 1.524 1.548 1.548 1.548 1.528 1.548

C4-C5 1.506 1.514 1.515 1.515 1.507 1.515

C5-C6 1.530 1.558 1.556 1.557 1.548 1.557

C3-C8 1.531 1.547 1.547 1.547 1.547 1.546

C3-C7 1.530 1.547 1.547 1.547 1.589 1.547

C4-N17 1.274 1.289 1.289 1.289 1.263 1.290

N17-N18 1.389 1.363 1.362 1.363 1.294 1.364


-35-

N18-H18 0.890 1.014 1.014 1.014 1.094 1.014

N18-C19 1.345 1.394 1.395 1.393 1.329 1.393

C19-O19 1.228 1.229 1.229 1.229 1.430 1.229

C24-025 - 1.420 1.421 1.421 1.421 1.420

Bond angle (°)

N1-C2-C3 109.55 112.01 111.86 111.94 112.02 111.98

N1-C6-C5 108.38 111.80 111.83 111.78 111.82 111.72

H1-N1-C2 108.00 110.58 110.25 110.40 110.48 110.56

H1-N1-C6 108.40 109.05 108.66 108.73 108.57 108.91

C2-C3-C4 105.43 106.59 106.60 106.72 106.61 106.71

C3-C4-C5 115.62 104.01 117.02 116.99 117.30 117.00

C4-C5-C6 109.92 113.95 114.09 114.15 114.09 114.05

C2-N1-C6 112.55 113.25 113.04 113.30 113.14 113.44

C3-C4-N17 127.81 128.85 128.82 128.84 128.92 128.82

C5-C4-N17 116.53 114.01 114.05 114.07 114.03 114.09

H18-N18-C19 110.21 111.00 110.84 110.97 111.40 111.04

N18-C19-O19 115.98 116.34 116.24 116.42 116.34 116.49

Dihedral (°)

N1-C2-C3-C4 57.28 46.62 47.24 47.20 47.62 46.72

N1-C6-C5-C4 -53.75 30.91 30.71 31.26 31.71 31.22

C8-C3-C4-N17 -71.68 -54.35 -55.40 -55.42 -55.41 -54.52

C7-C3C4-N17 67.09 68.22 67.16 67.18 67.16 68.13

N1-C2-C9-C10 86.41 34.35 33.31 33.74 34.35 35.10

N1-C2-C9-C10’ -138.95 -144.37 -145.04 -110.65 -144.38 -143.21

N1-C6-C13-C14 -32.70 -77.54 -85.67 -84.13 -77.54 -79.71

N1-C6-C13-C14’ 99.63 100.64 91.63 93.24 100.62 98.03

N17-N18-C19-C20 -16.25 -17.32 -16.19 -16.58 -17.40 -17.96

a- Values are taken from Ref. 21

Piperidine ring essentially adopts chair conformation, with all substituents equatorial as

evident from the torsional angles [N1–C2–C3–C4 ≈ -47.00 and 57.28 and N1–C6–C5–C4

≈ -30.91 and -53.75° by B3LYP and XRD, respectively. In the molecular optimized

structure, the hydrazone analogue is nearly planar with the dihedral angle


-36-

(N17-N18-C19-C20) around ~16.19° B3LYP and adopts an E configuration with respect to

the C4=N4 bond21

. Form the result we concluded that the E configuration is more stable than

the other possibilities.

Mulliken analysis

The calculation of Mulliken atomic charges plays an important role in the application of

quantum mechanical calculations to molecular systems. The Mulliken atomic charges for the

DDMs calculated at the B3LYP/6-31G(d,p) level in gas-phase are presented in Fig. 3 and Table

2. Results from Table 2 show that C7 has higher positive value than C8 in title compounds.

This difference is due to the from that C7 experiences –I effect from oxygen (N17) atom. The

Table 2 for DDMs shows that the high positive charge in molecule is [H1, C4, C12, C16,

H18, C19, C23]. The positive regions are related to nucleophilic reactivity. The negative

regions are located around the oxygen (O19, O27) and nitrogen (N1, N1 and N18) atoms

which are related to electrophilic reactivity22

. These data clearly show that DDMs are the

most reactive towards substitution reactions.

Table 2. Mulliken atomic charges of DDMs.

Atom 8 9 10 11 12

N1 -0.510 -0.509 -0.509 -0.511 -0.509

H1 0.240 0.240 0.240 0.242 0.239

C2 -0.012 -0.018 -0.019 -0.016 -0.018

C3 -0.251 -0.019 -0.018 -0.019 -0.018

C4 0.315 0.316 0.316 0.324 0.315

C5 -0.018 -0.254 -0.252 -0.261 -0.251

C6 0.038 0.033 0.033 0.040 0.033

C7 -0.327 -0.323 -0.323 -0.329 -0.323

C8 -0.314 -0.319 -0.319 -0.317 -0.319

C9 0.133 0.130 0.131 0.124 0.133

C12 0.386 0.353 0.310 0.327 0.351

R12 0.086 -0.297 -0.558 -0.381 -0.510

C13 0.132 0.083 0.082 0.066 0.088

C16 0.384 0.353 0.328 0.127 0.350

R16 0.086 -0.297 -0.558 -0.381 -0.518


-37-

N17 -0.327 -0.327 -0.329 -0.328 -0.329

N18 -0.413 -0.413 -0.412 -0.413 -0.412

H18 0.260 0.259 0.259 0.259 0.260

C19 0.553 0.552 0.551 0.553 0.553

O19 -0.514 -0.512 -0.514 -0.515 -0.515

C20 0.041 0.041 0.042 0.037 0.042

C23 0.360 0.360 0.359 0.359 0.359

O27 -0.514 -0.513 -0.514 -0.514 -0.514

C25 -0.081 -0.081 -0.081 -0.080 -0.080

R = H, F, O, C and O for 8, 9, 10, 11 and 12, respectivel.

Fig. 3. Mulliken charges of DDMs


-38-

Molecular electrostatic potential analysis

(8)

(9)


-39-

(10)

(11)


-40-

(12)

Fig. 4. MEP diagram of DDMs.

Molecular electrostatic potential (MEP) is a helpful descriptor used to visualize the

electrophilic or nucleophilic reactive sites of molecules22

, and to show the electrostatic

potential regions in terms of color grading. In MEP map (Fig. 4), different values of the

electrostatic potential are represented by different colors: red and blue represents the regions

of the most negative and positive electrostatic potential whereas green represents the region of

zero potential. Potential increases in the order of: red < orange < yellow < green < blue. The

positive regions are placed around all hydrogen atoms attached with the nitrogen, which are

related to nucleophilic reactivity 22

.

The negative regions are located around the oxygen and nitrogen atoms. As shown in Fig.

4, the negative potential sites are around the electronegative (oxygen and nitrogen) atoms and

the positive potential sites are hydrogen and carbon atoms, while the remaining species are

surrounded by orange, yellow and green. As we conclude from this our title molecules are

ready for both electrophilic and nucleophilic reactions.

Frontier molecular orbital analysis

The frontier molecular orbitals play an important role in the electric and optical

properties, as well as in chemical reactions, UV–Vis and fluorescence spectra23,24

. The

contour surfaces of the frontier molecular orbitals for each molecule drawn in Fig. 5. In the

DDMs, the electron cloud distribution in HOMO is piperidine ring and hydrazone unit, but

the contribution of molecular fragment to LUMO are mainly from the hydrazone unit. The

difference of the charge separation between the HOMO and LUMO of those structure play

important role in the internal charge transfer (ICT).


-41-

Furthermore, the difference on the values of ΔE of compounds 8-12 was observed, which

has different substituent at 12 & 16- sites of the phenyl core.

Table 3. Calculated energy values (eV) of DDMs in gas phase.

DFT/B3LYP/6-311G(d,p) 8 9 10 11 12

EHOMO -5.98 -6.07 -5.88 -5.94 -5.80

ELUOMO -0.88 -0.98 -0.83 -0.86 -0.80

ELUMO-HOMO 5.10 5.09 5.05 5.08 5.00

EHOMO-1 -6.04 -6.19 -5.96 -6.00 -5.89

ELUOMO+1 -0.28 -0.52 -0.22 -0.13 -0.15

E(LUMO+1)- (HOMO-1) 5.76 5.67 5.74 5.87 5.73

Electrinegativity(χ) -3.43 -3.53 -3.35 -3.41 -3.30

Hardness(η) 2.55 2.55 2.52 2.55 2.50

Electrophilicity index(ψ) 2.31 2.44 2.23 2.28 2.18

Softness(s) 145.23 145.24 146.67 145.40 148.15

For a system lower value of ΔE makes it more reactive or less stable and also has a

direct influence on the electron density difference for the stabilizing ICT process. In this

sense, it seems that the selection of a methoxy containing substituent has a beneficial effect

among the designed candidate. As a result, the trend of ΔE gap of inspected compounds

becomes 12 > 10 > 11 > 9 > 8.

We can observe from this Table 3, the introduction of different substituent at 12 & 16-

sites of the phenyl core significantly change the ΔE value.

Chemical hardness is related with the stability and reactivity of a chemical system, it

measures the resistance to change in the electron distribution or charge transfer. In this sense,

chemical hardness corresponds to the gap between the HOMO and LUMO. The larger the

HOMO–LUMO energy gap, the harder and more stable/less reactive the molecule. The

higher value of ΔE represents more hardness or less softness of a compound, thus compound

8 referred as hard molecule when compared to 9-1225

.

Another global reactivity descriptor electrophilicity index (ψ) describes the electron

accepting ability of the systems quite similar to hardness and chemical potential. High values

of electrophilicity index increases electron accepting abilities of the molecules. Thus, electron

accepting abilities of compounds 8-12 are arranged in following order: 9 > 8 > 10 > 11 > 12.


-42-

Fig. 5. Molecular orbitals and energies for the HOMO and LUMO in gas phase.


-43-

Non-linear optical activity

NLO is important property providing key for areas such as telecommunications, signal

processing and optical interactions26,27

. A large variety of NLO switches exhibiting large

changes in the first order hyperpolarizability (β), the molecular second-order NLO response.

In this context, the design of NLO switches, that is, molecules computed for their first

hyperpolarizability by alternate their substitution at 12 and 16- sites in phenyl core. The total

static dipolemoment (μ), the Mean polarizabilty (α) , Anisotropy of the polarisabiltiy (Δα)

and the first order hyperpolarizability (β0) using the x, y, z components are calculated using

the following equations.

μ = (μx2 + μy

2 + μz

2)

1/2

√ [( )

( )

( )

(

)]

( ) ( )

(

)

Table 4. Non-linear optical properties of DDMs calculated using B3LYP method using

6-311G(d,p) basis set.

NLO behavior 8 9 10 11 12

Dipole moment (μ) D 3.94 3.54 5.17 3.83 5.28

Mean polarizabilty (α) x10-23

esu 2.70 3.00 2.80 2.90 2.90

Anisotropy of the

Polarisabiltiy (Δα) x10-24

esu 6.66 4.50 7.91 7.09 9.53

First order polarizabilty (β0) x10-30

esu 1.29 2.01 2.06 1.23 2.41

As the results mentioned previously10,28,29

, hydrazones may have significance nonlinear

optical property. In this sense a series of new molecules possessing nonlinear optical property

are designed which includes S, F, OH, CH3 and OCH3 groups at 12 & 16- sites of the phenyl

core. According to Table 4, all values of each mentioned molecules are greater than their

urea30

values. Therefore, NLO properties of our compounds are better than urea.


-44-

Results from Table 4, the general ranking of NLO properties should be as follows: 12 >

10 > 8 > 11 > 9. With results in hand, molecule 5 is the best candidate for NLO properties. To

sum up, it can be concluded that the presence of an electron donating group (methoxy) in the

para position at the phenyl ring contributes to decrease the dipole moments, mean

polarisability and first order hyperpolarizability of the DDMs probably because of an

inductive competition between the methoxy and the electronic density available in the

molecule.

When it is compared with similar compounds in the literature, the β0 value tittle

compounds are high than that of 3t-pentyl-2r,6c-diphenylpiperidin-4-one semicarbazone

(β0 = 0.65 x10-30

esu)28

and 3t-pentyl-2r,6c-diphenylpiperidin-4-one thiosemicarbazone (β0 =

1.28 x10-30

esu)29

. The above results show that DDMs can be best material for NLO

applications

4. CONCLUSIONS

Results from in hand, piperidone ring adopts chair conformation with equatorial

orientation of substituent at C2, C3, C6 and hyzrazone analogue adopts an E configuration

with respect to C4=N17. In addition, Mulliken charge and MEP analysis predicts the most

reactive parts in the molecule. The result of molecular orbital composition analysis revealed

for DDMs, that the ΔE gap could be lowered upon modifying the 12 & 16- sites of the phenyl

core. Among this, compound 12 is the best candidate for the stabilizing ICT process. Another

conclusion of the paper is the calculated first hyperpolarizability is comparable with reported

values of similar derivatives and the 12 is a strong candidate for future studies of nonlinear

optics.

References

[1] C. Ramalingam, Y.T. Park, S. Kabilan, Eur. J. Med. Chem., 41 (2006) 683.

[2] S. Balasubraanian, G. Aridoss, P. Parthiban, Biol. Pharm. Bull., 29 (2006) 125.

[3] S. Murugesan, S. Perumal, S. Selvaraj, Chem. Pharm. Bull., (Tokyo) 54 (2006) 795.

[4] M.X. Li, C.L. Chen, C.S. Ling, J. Zhou, B.S. Ji, Y.J. Wu, J.Y. Niu, Bioorg. Med. Chem.

Lett., 19 (2009) 2704.

[5] Sethukumar, C. Udhaya Kumar, R. Agilandeshwari, B. Arul Prakasam, J. Mol. Struct.,

1047 (2013) 237.

[6] J. Jayabharathi, V. Thanikachalam, M. Padamavathy, N. Srinivasan, Spectrochim.

Acta, Part A 81 (2011) 380.

[7] J. Jayabharathi, V. Thanikachalam, M. Padamavathy, M. Venkatesh Perumal, J.

Fluoresc., 22 (2012) 269.

[8] L. Ravikumar, G. Rathika, R. Punitha, Int. J. Eng. Res. Tech., 2 (2013) 3137.

[9] S. Subashchandrabose, H. Saleem, Y. Erdogdu, G. Rajarajan, V. Thanikachalam,

Spectrochim. Acta, Part A 82 (2011) 260.


-45-

[10] Dhandapani, S. Manivarman, S. Subaschandrabose, H. Saleem, J. Mol. Struct., 1058

(2014) 41.

[11] G. Velraj, S. Soundharam, C. Sridevi, J. Mol. Struct., 1060 (2014) 156.

[12] M. Arockia doss, S. Savithiri, G. Rajarajan, V. Thanikachalam, C. Anbuselvan,

Spectrochimica Acta Part A 151 (2015) 773.

[13] G. Thiyagarajan, P. Anjana, P. Nithya, P. Ashutosh, Int. J. Org. Chem., 1 (2011) 71.

[14] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,

G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato, X.

Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M. Hada, M.

Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y.Honda, O. Kitao,

H. Nakai, T. Vreven, J.A. Montgomery, Jr., J.E. Peralta, F. Ogliaro, M. Bearpark, J.J.

Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J. Normand, K.

Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.

M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R.

Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W.

Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador, J.J.

Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas, J.B. Foresman, J.V. Ortiz, J.

Cioslowski, D.J. Fox, Gaussian 03, Revision C.02, Gaussian Inc., Wallinford, CT,

2004.

[15] R. P. Iczkowski, J.L. Margrave, J. Am. Chem. Soc., 83 (1961) 3547.

[16] R.G. Parr, L. Szentpaly, S. Liu, J. Am. Chem. Soc., 121 (1999) 1922.

[17] R.G. Parr, R. G. Pearson, J. Am. Chem. Soc., 105 (1983) 7512.

[18] Manimekalai, S. Sivakumar, Magn. Reson. Chem., 49 (2011) 830.

[19] J. Jayabharathi, A. Thangamani, S. Balamurugan, A. Thiruvalluvar, Acta Cryst., E 64,

(2008) o1181.

[20] K. Ravichandran, S. Sethuvasan, K. Thirunavukarasu, S. Ponnuswamy, M.N.

Ponnuswamy, Acta Cryst., E 68 (2012) o2453.

[21] C. Sankar, K. Pandiarajan, A. Thiruvalluvar, P. Gayathri, Acta Cryst. (2010). E66,

o2841.

[22] F.J. Luque, J.M. Lopez, M. Orozco, Theor. Chem. Acc., 103 (2000) 343.

[23] Fleming, I. Frontier Orbitals and Organic Chemical Reactions. Wiley, London, 1976.

[24] F. Kandemirli, S. Sagdinc, Corros. Sci., 49 (2007) 2118.

[25] Z. Demircioğlu, C. Albayrak Kaştaş, O. Büyükgüngör, J. Mol. Struct., 1091 (2015)

183.

[26] K. Gokula Krishnan, R. Sivakumar, V. Thanikachalam, H. Saleem, M. Arockia doss,


[27] S. Savithiri, M. Arockia Doss, G. Rajarajan, V. Thanikachalam, J. Mol. Struct., 1105

(2016) 225.


-46-

[28] M. Arockia doss, S. Savithiri, G. Rajarajan, V. Thanikachalam, H. Saleem,


[29] S. Savithiri, M. Arockia Doss, G. Rajarajan, V. Thanikachalam, S. Bharanidharan, H.

Saleem, Spectrochimica Acta Part A. 2015, 136, 782.

[30] Z.M. Jin, B. Zhao, W. Zhou, Z.H. Jin, J. Powder Diff. 12 (1997) 47.

( Received 02 January 2016; accepted 13 January 2016 )

Synthesis, spectral, molecular structure, HOMO-LUMO and ... … · experimental values. In...

Documents

Transcript of Synthesis, spectral, molecular structure, HOMO-LUMO and ... … · experimental values. In...