Computational study on molecular structure, vibrational and electronic properties of a novel Schiff base: Benzyl2-(4-(bis(2-chloroethyl)benzylidene) hydrazinecarbodithioate

Bhuvanendra Singh, Rajeev Singh, Bhoop Singh, Dilip Kumar


The present study reports a novel Schiff base ‘Benzyl2-(4-(bis(2 chloroethyl)amino)benzylidene)hydrazinecarbodithioate’ and its characterization by infra red (IR), nuclear magnetic resonance (NMR), mass spectral methods with its density functional theory (DFT) quantum chemical studies. Tautomerism in this molecule was investigated theoretically by semi-empirical methods. The molecular geometry was calculated by DFT methods using split-valence triple-zeta 6311-G(2d,2p) Pople style basis set. The vibrational frequencies were calculated by DFT method at the same basis set level. The molecular parameters such as highest occupied molecular orbital energy, lowest unoccupied molecular orbital energy, frontier molecular orbital energy gap and dipole moment were calculated by DFT methods using 6311-G(2d,2p) basis set. Molecular electrostatic surface potential and electron localization function plots were also presented. The reactive sites in the molecule studied theoretically with electronic structure in sight.


DFT; electron localization function; HOMO-LUMO; MESP; quantum chemical calculations.

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Becke, A.D. & Edgecombe, K.E. (1990). A simple

measure of electron localization in atomic and molecular

systems. The Journal of Chemical Physics, 92(9):5397.

Blaudeau, J.-P., McGrath, M.P., Curtiss, L. A. &

Radom L. (1997). Extension of Gaussian-2 (G2) theory

to molecules containing third-row atoms K and Ca. The

Journal of Chemical Physics, 107(13):5016–5021.

Cheah, P.-S., Ling, K.-H., Crouse, K.A. & Rosli, R.

(2007). Characterization of the S-benzyldithiocarbazate

effects on cell proliferation and oncogene expression

in human breast cancer cells. Medical and Biological

Sciences, 1(2):1257.

Coates, J. (2006) Encyclopedia of Analytical Chemistry

R. A. Meyers, ed., Chichester, UK: John Wiley & Sons,


Davis, W. & Larionov, L.F. (1964). Progress in

chemotherapy of cancer. Bulletin of the World Health

Organization, 30:327–341.

Dill, J.D. & Pople, J.A. (1975). Self-consistent

molecular orbital methods. XV. Extended Gaussian-type

basis sets for lithium, beryllium, and boron. The Journal

of Chemical Physics, 62(7):2921.

Francl, M.M., Pietro, W.J., Hehre, W.J., Binkley, J.S.,

Gordon, M.S. et al. (1982). Self-consistent molecular

orbital methods. XXIII. A polarization-type basis set for

second-row elements. The Journal of Chemical Physics,

(7): 3654–3665.

Fu, Y., Zhou, S., Liu, Y., Yang, Y., Sun, X. et al. (2014).

The cytotoxicity of benzaldehyde nitrogen mustard-

-pyridine carboxylic acid hydrazone being involved

in topoisomerase IIα inhibition. BioMed Research

International, 2014: 527042. doi: 10.1155527030/2014/.

Fukui, K., Yonezawa, T. & Shingu, H. (1952). A

molecular orbital theory of reactivity in aromatic

hydrocarbons. The Journal of Chemical Physics,


Gunasekaran, S., Kumaresan, S., Balaji, R.A., Anand,

G., Seshadri, S. (2008). Vibrational spectra and normal

coordinate analysis on structure of chlorambucil and

thioguanine. Pramana, 71(6):1291–1300.

Halgren, T.A. (1996). Merck molecular force field. I.

Basis, form, scope, parameterization, and performance

of MMFF94. Journal of Computational Chemistry, 17(5–


Hanwell, M.D., Curtis, D.E., Lonie, D.C.,

Vandermeersch, T., Zurek, E. et al., (2012). Avogadro:

An advanced semantic chemical editor, visualization, and

analysis platform. Journal of Cheminformatics, 4:1–17.

Krishnan, R., Binkley, J.S., Seeger, R. & Pople, J.A.

(1980). Self-consistent molecular orbital methods. XX.

A basis set for correlated wave functions. The Journal of

Chemical Physics, 72(1):650–654.

Mayer, R. (1967). Organosulfur chemistry. In M.

J. Janssen, ed. Organosulfur chemistry. New York:

Interscience, New York, p. 17.

McLean, A.D. & Chandler, G.S. (1980). Contracted

Gaussian basis sets for molecular calculations. I. Second

row atoms, Z= 11--18. The Journal of Chemical Physics,


Mendoza-Huizar, L.H. & Rios-Reyes, C.H. (2011).

Chemical reactivity of Atrazine employing the Fukui

function. Journal of the Mexican Chemical Society,


Modi, J.D., Sabnis, S.S. & Deliwala, C. V. (1970). Potential

anticancer agents. III. Schiff bases from benzaldehyde

nitrogen mustards and aminophenylthiazoles. Journal of

Medicinal Chemistry, 13(5):935–941.

Neese, F. (2012). The ORCA program system. Wiley

Interdisciplinary Reviews: Computational Molecular

Science, 2(1):73–78.

Okulik, N. & Jubert, A.H. (2005). Theoretical analysis

of the reactive sites of non-steroidal anti-inflammatory

drugs. Internet Electronic Journal of Molecular Design,


Pavan, F.R., Maia, P.I.D.S., Leite, S.R.A., Deflon,

V.M., Batista, A.A. et al., (2010). Thiosemicarbazones,

semicarbazones, dithiocarbazates and hydrazide/

hydrazones: anti-Mycobacterium tuberculosis activity and

cytotoxicity. European journal of medicinal chemistry,


Pearson, R.G. (1986). Absolute electronegativity

and hardness correlated with molecular orbital theory.

Proceedings of the National Academy of Sciences of the

United States of America, 83(22):8440–8441.

Pearson, R.G. (2005). Chemical hardness and density

functional theory. Journal of Chemical Sciences,


Popp, F.D. & Kirsch, W. (1961). Synthesis of Potential

Anticancer Agents. V. Schiff Bases and Related

Compounds 12-. The Journal of Organic Chemistry,


Rao, C.N.R., Venkataraghavan, R. & Kasturi,

T.R. (1964). Contribution to the infrared spectra

of organosulphur compounds. Canadian Journal of

Chemistry, 42(1):36–42.

Savin, P.-D.A., Nesper, R., Wengert, S. & Fassler,

T.F. (1997). ELF: The Electron Localization Function.

Angewandte Chemie International Edition in English,


Savin, A. Silvi, B. & Colonna, F. (1996). Topological

analysis of the electron localization function applied

to delocalized bonds. Canadian Journal of Chemistry,


Scrocco, E. & Tomasi, J. (1978). Advances in Quantum

Chemistry Volume 11, Elsevier.

Sundara Raj, S.S., Yamin B.M., Yussof, Y. A., Tarafder,

M. T. H., Fun, H. et al. ,(2000). trans – cis S -Benzyl

dithiocarbazate. Acta Crystallographica Section C Crystal

Structure Communications, 56(10):1236–1237.

Stewart, J.J.P. Stewart Computational Chemistry,

Version 15.145L web:

Tarafder, M.T.H., Kasbollah, A., Saravanan, N., Crouse,

K.A., Ali AM et al., (2002). S-methyldithiocarbazate and

its Schiff bases: evaluation of bondings and biological

properties. Journal of biochemistry, molecular biology,

and biophysics, 6(2):85–91.


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