European Journal of Chemistry 2022, 13(1), 91-98 | doi: | Get rights and content

Issue cover



Synthesis, crystal structure, Hirshfeld surface analysis, and DFT studies on (2,2’-bipyridine)chlorobis(N,N-bis(thiophen-2-ylmethyl)dithiocarbamato-S,S’)zinc(II) complex

Soundararajan Eswari (1) orcid , Subbiah Thirumaran (2,*) orcid

(1) Department of Chemistry, Faculty of Science, Annamalai University, Annamalainagar 608 002, India
(2) Department of Chemistry, Faculty of Science, Annamalai University, Annamalainagar 608 002, India
(*) Corresponding Author

Received: 15 Nov 2021 | Revised: 20 Dec 2021 | Accepted: 26 Dec 2021 | Published: 31 Mar 2022 | Issue Date: March 2022


Bis(N,N-bis(thiophen-2-ylmethyl)dithiocarbamato-S,S’)zinc(II) complex (1) and (2,2’-bipyridine)chlorobis(N,N-bis(thiophen-2-ylmethyl)dithiocarbamato-S,S’)zinc(II) complex (2) were synthesized. Complex 2 (final product) was structurally characterized by single crystal X-ray diffraction studies. Complex 2 (C21H18ClN3S4Zn) crystallized in triclinic crystal system with space group P-1 (no. 2), a = 8.7603(4) Å, b = 10.7488(6) Å, c = 13.0262(7) Å,    α = 103.965(2)°, β = 91.913(2)°, γ = 104.944(2)°, = 1144.07(10) Å3, Z = 2, T = 302(2) K, μ(MoKα) = 1.569 mm-1, Dcalc = 1.572 g/cm3, 14892 reflections measured (4.838° ≤ 2Θ ≤ 56.52°), 5570 unique (Rint = 0.0188, Rsigma = 0.0230) which were used in all calculations. The final R1 was 0.0810 (I > 2σ(I)) and wR2 was 0.2788 (all data). Complex 2 displays distorted square pyramidal coordination geometry. Crystal structure analysis of complex 2 shows that the crystal packing is mainly stabilized by C-H···π (chelate) and C-H···Cl interactions. Hirshfeld surface analysis was carried out to explore deeply into the nature and type of non-covalent interactions. The molecular and electronic structures of complexes 1 and 2 were also studied by DFT quantum chemical calculations.


Our editors have decided to support scientists to publish their manuscripts in European Journal of Chemistry without any financial constraints.

1- The article processing fee will not be charged from the articles containing the single-crystal structure characterization between November 15, 2022 and December 28, 2022 (Voucher code: SINGLE2022).

2. Young writers will not be charged for the article processing fee between November 15, 2022 and December 28, 2022 (Voucher code: YOUNG2022).

3. The article processing fee will not be charged from the articles containing a part of the PhD thesis between November 15, 2022 and December 28, 2022 (Voucher code: PhD2022).

4. The article processing fee will not be charged from authors who have at least one publication in the European Journal of Chemistry between November 15, 2022 and December 28, 2022 (Voucher code: (Voucher code: AUTHOR2022).


European Journal of Chemistry


Ligand; IR spectroscopy; Crystal structure; Zinc(II) dithiocarbamate; Density functional theory; Hirshfeld surface analysis

Full Text:

PDF    Open Access

DOI: 10.5155/eurjchem.13.1.91-98.2212

Links for Article

| | | | | |

| | | | | | |

| | | |

Related Articles

Article Metrics

icon graph This Abstract was viewed 255 times | icon graph PDF Article downloaded 60 times

Funding information

The American Chemical Society Petroleum Research Fund (PRF# 12345-AC1); the State of Delaware; the National Institute of General Medical Sciences (P20GM123456) from the National Institutes of Health (INBRE program); and a NSF EPSCoR grant IIA-1234567.


[1]. Maurya, V. K.; Singh, A. K.; Singh, R. P.; Yadav, S.; Kumar, K.; Prakash, P.; Prasad, L. B. Synthesis and Evaluation of Zn(II) Dithiocarbamate Complexes as Potential Antibacterial, Antibiofilm, and Antitumor Agents. J. Coord. Chem. 2019, 72 (19-21), 3338-3358.

[2]. Alam, M. N.; Mandal, S. K.; Debnath, S. C. Effect of Zinc Dithio-carbamates and Thiazole-Based Accelerators on the Vulcanization of Natural Rubber. Rubber Chem. Technol. 2012, 85 (1), 120-131.

[3]. Gallagher, W. P.; Vo, A. Dithiocarbamates: Reagents for the Removal of Transition Metals from Organic Reaction Media. Org. Process Res. Dev. 2015, 19 (10), 1369-1373.

[4]. Ajibade, P. A.; Mbese, J. Z.; Omondi, B. Group 12 Dithiocarbamate Complexes: Synthesis, Characterization, and X-Ray Crystal Structures of Zn(II) and Hg(II) Complexes and Their Use as Precursors for Metal Sulfide Nanoparticles. Inorg. nano-met. chem. 2017, 47 (2), 202-212.

[5]. Tiekink, E. Exploring the Topological Landscape Exhibited by Binary Zinc-Triad 1,1-Dithiolates. Crystals (Basel) 2018, 8 (7), 292.

[6]. Singh, V.; Kumar, V.; Gupta, A. N.; Drew, M. G. B.; Singh, N. Effect of Pyridyl Substituents Leading to the Formation of Green Luminescent Mercury(Ii) Coordination Polymers, Zinc(Ii) Dimers and a Monomer. New J Chem 2014, 38 (8), 3737.

[7]. Kumar, V.; Manar, K. K.; Gupta, A. N.; Singh, V.; Drew, M. G. B.; Singh, N. Impact of Ferrocenyl and Pyridyl Groups Attached to Dithiocarbamate Moieties on Crystal Structures and Luminescent Characteristics of Group 12 Metal Complexes. J. Organomet. Chem. 2016, 820, 62-69.

[8]. Gurumoorthy, G.; Thirumaran, S.; Ciattini, S. Unusual Octahedral Hg(II) Dithiocarbamate: Synthesis, Spectral and Structural Studies on Hg(II) Complexes with Pyrrole Based Dithiocarbamates and Their Utility for the Preparation of α- and β-HgS. Polyhedron 2016, 118, 143-153.

[9]. Eswari, S.; Selvaganapathi, P.; Thirumaran, S.; Ciattini, S. Effect of Solvent Used for Crystallization on Structure: Synthesis and Characterization of Bis(N,N-Di(4-Fluorobenzyl)Dithiocarbamato-S,S′) M(II) (M = Cd, Hg) and Usage as Precursor for CdS Nanophoto-catalyst. Polyhedron 2021, 206 (115330), 115330.

[10]. Tan, Y. S.; Sudlow, A. L.; Molloy, K. C.; Morishima, Y.; Fujisawa, K.; Jackson, W. J.; Henderson, W.; Halim, S. N. B. A.; Ng, S. W.; Tiekink, E. R. T. Supramolecular Isomerism in a Cadmium Bis(N-Hydroxyethyl, N-Isopropyldithiocarbamate) Compound: Physiochemical Characteri-zation of Ball (n = 2) and Chain (n = ∞) Forms of Cd[S2CN(IPr)CH2 CH2OH]2·solventn. Cryst. Growth Des. 2013, 13 (7), 3046-3056.

[11]. Onwudiwe, D. C.; Nthwane, Y. B.; Ekennia, A. C.; Hosten, E. Synthesis, Characterization and Antimicrobial Properties of Some Mixed Ligand Complexes of Zn(II) Dithiocarbamate with Different N-Donor Ligands. Inorganica Chim. Acta 2016, 447, 134-141.

[12]. Selvaganapathi, P.; Thirumaran, S.; Ciattini, S. Structural Variations in Zinc(II) Complexes with N,N-Di(4-Fluorobenzyl)Dithiocarbamate and Imines: New Precursor for Zinc Sulfide Nanoparticles. Polyhedron 2018, 149, 54-65.

[13]. Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. OLEX2: A Complete Structure Solution, Refinement and Analysis Program. J. Appl. Crystallogr. 2009, 42 (2), 339-341.

[14]. Sheldrick, G. M. SHELXT - Integrated Space-Group and Crystal-Structure Determination. Acta Crystallogr. A Found. Adv. 2015, 71 (Pt 1), 3-8.

[15]. Sheldrick, G. M. Crystal Structure Refinement with SHELXL. Acta Crystallogr. C Struct. Chem. 2015, 71 (Pt 1), 3-8.

[16]. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery J. A.; Vreven, J, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G.A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J. Cammi, R.; Pomelli, C. Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V.G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I. Martin, R. L.; Fox, D. J. Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez C.; Pople, J. A., Gaussian 03, Revision B.04, Gaussian, Inc., Pittsburgh PA, 2003.

[17]. Lee, C.; Yang, W.; Parr, R. G. Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron Density. Phys. Rev. B Condens. Matter 1988, 37 (2), 785-789.

[18]. Wolff, S. K.; Grimwood, D. J.; Mckinnon, J. J.; Turner, M. J.; Jayatilaka, D.; Spackman, M. A., Crystal Explorer Ver. 3.1, University of Western Australia, Perth, Australia, 2013.

[19]. Spackman, M. A.; McKinnon, J. J.; Jayatilaka, D. Electrostatic Potentials Mapped on Hirshfeld Surfaces Provide Direct Insight into Intermolecular Interactions in Crystals. CrystEngComm 2008, 10 (4), 377-388.

[20]. Sathiyaraj, E.; Srinivasan, T.; Thirumaran, S.; Velmurugan, D. Synthesis and Spectroscopic Characterization of Ni(II) Complexes Involving Functionalised Dithiocarbamates and Triphenylphosphine: Anagostic Interaction in (N-Cyclopropyl-N-(4-Fluorobenzyl)Dithiocarbamato-S,S′) (Thiocyanato-N)(Triphenylphosphine)Nickel(II). J. Mol. Struct. 2015, 1102, 203-209.

[21]. Sattigeri, V. J.; Soni, A.; Singhal, S.; Khan, S.; Pandya, M.; Bhateja, P.; Mathur, T.; Rattan, A.; Khanna, J. M.; Mehta, A. Synthesis and Antimicrobial Activity of Novel Thiazolidinones. ARKIVOC 2005, 2005 (2), 46-59.

[22]. Lai, C. S.; Tiekink, E. R. T. Crystallographic Report: Chloro(N,N-Diethyl dithiocarbamato)(4, 7-Dimethyl-1, 10-Phenanthroline) Mercury(II) Hemi-Chloroform Solvate. Appl. Organomet. Chem. 2003, 17 (2), 141-142.

[23]. Tiekink, E. R. T.; Wardell, J. L.; Wardell, S. M. S. V. Hydrogen-Bonding Interactions in the Crystal Structure of Bis(N-Propyl-N-(2-Hydroxy ethyl)Dithiocarbamato-S,S′)Nickel(II): Ni[S2CN(NPr)(CH2CH2OH)]2. J. Chem. Crystallogr. 2007, 37 (7), 439-443.

[24]. Alverdi, V.; Giovagnini, L.; Marzano, C.; Seraglia, R.; Bettio, F.; Sitran, S.; Graziani, R.; Fregona, D. Characterization Studies and Cytotoxicity Assays of Pt(II) and Pd(II) Dithiocarbamate Complexes by Means of FT-IR, NMR Spectroscopy and Mass Spectrometry. J. Inorg. Biochem. 2004, 98 (6), 1117-1128.

[25]. Sathiyaraj, E.; Thirumaran, S.; Selvanayagam, S.; Sridhar, B.; Ciattini, S. C H⋯Ni and C H⋯π(Chelate) Interactions in Nickel(II) Complexes Involving Functionalized Dithiocarbamates and Triphenylphosphine. J. Mol. Struct. 2018, 1159, 156-166.

[26]. Tiekink, E. R. T. The Remarkable Propensity for the Formation of C-H⋯π(Chelate Ring) Interactions in the Crystals of the First-Row Transition Metal Dithiocarbamates and the Supramolecular Architectures They Sustain. CrystEngComm 2020, 22 (43), 7308-7333.

[27]. Mangasuli, S. N.; Hosamani, K. M.; Managutti, P. B. Synthesis of Novel Coumarin Derivatives Bearing Dithiocarbamate Moiety: An Approach to Microwave, Molecular Docking, Hirshfeld Surface Analysis, DFT Studies and Potent Anti-Microbial Agents. J. Mol. Struct. 2019, 1195, 58-72.

[28]. Mehmood, T.; Bhosale, R. S.; Reddy, J. P. Bis(2-Methylpyridinium) Tetrachloridocuprate(II): Synthesis, Structure and Hirshfeld Surface Analysis. Acta Crystallogr. E Crystallogr. Commun. 2021, 77 (7), 726-729.

[29]. Lakshmanan, P.; Thirumaran, S.; Ciattini, S. Synthesis, Spectral and Structural Studies on NiS2PN and NiS2P2 Chromophores and Use of Ni(II) Dithiocarbamate to Synthesize Nickel Sulfide and Nickel Oxide for Photodegradation of Dyes. J. Mol. Struct. 2020, 1220 (128704), 128704.

[30]. Prabhuswamy, A.; Mohammed, Y. H. E.; Al-Ostoot, F. H.; Venkatesh, G. D.; Anandalwar, S. M.; Khanum, S. A.; Krishnappagowda, L. N. Synthesis, Crystal Structure Elucidation, Hirshfeld Surface Analysis, 3D Energy Frameworks and DFT Studies of 2-(4-Fluorophenoxy) Acetic Acid. Eur. J. Chem. 2021, 12 (3), 304-313.

[31]. Krishnan, K. G.; Thanikachalam, V. Synthesis, Spectral, Crystallo-graphic, and Computational Investigation of a Novel Molecular Hybrid 3-(1-((Benzoyloxy)Imino)Ethyl)-2H-Chromen-2-Ones. Eur. J. Chem. 2021, 12 (2), 133-146.

[32]. Yu, X.; Wang, N.; He, H.; Wang, L. Theoretical Investigations of the Structures and Electronic Spectra of Zn(II) and Ni(II) Complexes with Cyclohexylamine-N-Dithiocarbamate. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2014, 122, 283-287.

[33]. Adole, V. A.; Jagdale, B. S.; Pawar, T. B.; Sawant, A. B. Experimental and Theoretical Exploration on Single Crystal, Structural, and Quantum Chemical Parameters of (E)‐7‐(Arylidene)‐1,2,6, 7‐tetrahydro‐8 H ‐indeno[5,4‐ b ]Furan‐8‐one Derivatives: A Comparative Study. J. Chin. Chem. Soc. 2020, 67 (10), 1763-1777.

[34]. Domingo, L. R.; Ríos-Gutiérrez, M.; Pérez, P. A Molecular Electron Density Theory Study of the Participation of Tetrazines in Aza-Diels-Alder Reactions. RSC Adv. 2020, 10 (26), 15394-15405.

Supporting information

The Supplementary Material for this article can be found online at: Supplementary files

How to cite

Eswari, S.; Thirumaran, S. Eur. J. Chem. 2022, 13(1), 91-98. doi:10.5155/eurjchem.13.1.91-98.2212
Eswari, S.; Thirumaran, S. Synthesis, crystal structure, Hirshfeld surface analysis, and DFT studies on (2,2’-bipyridine)chlorobis(N,N-bis(thiophen-2-ylmethyl)dithiocarbamato-S,S’)zinc(II) complex. Eur. J. Chem. 2022, 13(1), 91-98. doi:10.5155/eurjchem.13.1.91-98.2212
Eswari, S., & Thirumaran, S. (2022). Synthesis, crystal structure, Hirshfeld surface analysis, and DFT studies on (2,2’-bipyridine)chlorobis(N,N-bis(thiophen-2-ylmethyl)dithiocarbamato-S,S’)zinc(II) complex. European Journal of Chemistry, 13(1), 91-98. doi:10.5155/eurjchem.13.1.91-98.2212
Eswari, Soundararajan, & Subbiah Thirumaran. "Synthesis, crystal structure, Hirshfeld surface analysis, and DFT studies on (2,2’-bipyridine)chlorobis(N,N-bis(thiophen-2-ylmethyl)dithiocarbamato-S,S’)zinc(II) complex." European Journal of Chemistry [Online], 13.1 (2022): 91-98. Web. 3 Dec. 2022
Eswari, Soundararajan, AND Thirumaran, Subbiah. "Synthesis, crystal structure, Hirshfeld surface analysis, and DFT studies on (2,2’-bipyridine)chlorobis(N,N-bis(thiophen-2-ylmethyl)dithiocarbamato-S,S’)zinc(II) complex" European Journal of Chemistry [Online], Volume 13 Number 1 (31 March 2022)

The other citation formats (EndNote | Reference Manager | ProCite | BibTeX | RefWorks) for this article can be found online at: How to cite item

DOI Link:

CrossRef | Scilit | GrowKudos | Researchgate | Publons | ScienceGate | Scite | Lens | OUCI

WorldCat Paperbuzz | LibKey Citeas | Dimensions | Semanticscholar | Plumx | Kopernio | Zotero | Mendeley

ZoteroSave to Zotero MendeleySave to Mendeley

European Journal of Chemistry 2022, 13(1), 91-98 | doi: | Get rights and content


  • There are currently no refbacks.

Copyright (c) 2022 Authors

Creative Commons License
This work is published and licensed by Atlanta Publishing House LLC, Atlanta, GA, USA. The full terms of this license are available at and incorporate the Creative Commons Attribution-Non Commercial (CC BY NC) (International, v4.0) License ( By accessing the work, you hereby accept the Terms. This is an open access article distributed under the terms and conditions of the CC BY NC License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited without any further permission from Atlanta Publishing House LLC (European Journal of Chemistry). No use, distribution or reproduction is permitted which does not comply with these terms. Permissions for commercial use of this work beyond the scope of the License ( are administered by Atlanta Publishing House LLC (European Journal of Chemistry).

© Copyright 2010 - 2022  Atlanta Publishing House LLC All Right Reserved.

The opinions expressed in all articles published in European Journal of Chemistry are those of the specific author(s), and do not necessarily reflect the views of Atlanta Publishing House LLC, or European Journal of Chemistry, or any of its employees.

Copyright 2010-2022 Atlanta Publishing House LLC. All rights reserved. This site is owned and operated by Atlanta Publishing House LLC whose registered office is 2850 Smith Ridge Trce Peachtree Cor GA 30071-2636, USA. Registered in USA.