A new Zn(II) complex of N'-(1-(thiophen-2-yl)ethylidene)isonicotinohydrazide: synthesis, spectral characterization, X-ray structure
Abstract
The hydrazone ligand E-N'-(1-(thiophen-2-yl)ethylidene)isonicotinohydrazide (HL) was synthesized by a one-step condensation reaction and characterized by elemental analysis, infrared spectroscopy, and 1H and 13C NMR spectroscopies. The Zn(II) complex derived from ligand (HL) was synthesized and characterized by elemental analysis, conductivity measurements in DMF solutions, FT-IR and electronic spectroscopies, and single-crystal X‑ray diffraction. Elemental analysis showed that the Zn(II) complex is composed of a single metal, organic ligand, and chloride ions in a 1:1:2 molar ratio. This Zn(II) complex is a neutral electrolyte in solution in DMF. The mononuclear complex 1 crystallizes in the triclinic space group Pī with the following unit cell parameters: a = 5.831 (3) Å, b = 9.337 (4) Å, c = 13.738 (4) Å, V = 731.6 (5) Å3, Z = 2. The asymmetric unit of complex 1 contains one Zn(II) ion, one ligand molecule, and two coordinated chloride ions. In this complex, the ligand exists in its overall neutral bidentate form. The hydrazine group is deprotonated while the pyridine nitrogen atom is protonated. The ligand is coordinated to the Zn(II) through the carbonyl oxygen and the azomethine nitrogen. The metal cation is also coordinated with two chloride ions, resulting in a tetra-coordinated Zn(II). The environment around the cation Zn(II) is best described as a tetrahedral geometry. Numerous hydrogen bonds and an intramolecular chalcogen bond consolidate the structure into a three-dimensional network.
Downloads
References
Ngu, C. P., Sahu, R., Shah, K., Paliwal, D., Sah, A. K., & Prajapati, B. G. (2025). Recent development in synthesis and anticonvulsant activity of promising Schiff base derivatives. Journal of Heterocyclic Chemistry, 62(10), 1264–1284. https://doi.org/10.1002/jhet.700732
Bouznif, H., Justino, L. L. G., Costa, T., Soares, M. I. L., Ramos, M. L., Pinho e Melo, T. M. V. D., Zouari, N., & Fausto, R. (2025). A water-soluble Schiff base ligand and its Al(III) complex: optical properties, computational studies and photocatalytic performance. Inorganica Chimica Acta, 123014. https://doi.org/10.1016/j.ica.2025.123014
Singh, G., Kaur, K., Mohit, Kaur, A., Singh, M., Gill, B. S., Baliyan, D., & Dege, N. (2025). A dual-functional Schiff base probe for selective recognition of iridium ions and biological applications: Synthesis, characterization, and molecular docking insights. Journal of Molecular Structure, 1348, 143506. https://doi.org/10.1016/j.molstruc.2025.143506
Qaisar, A., Khan, H., Habib, U., Rasool, S., Mumtaz, A., Mahmud, T., & Basra, M. A. R. (2025). Design, synthesis and analysis of Schiff based derivatives of Sulfadoxine drug and their metal complexes. Results in Chemistry, 17, 102560. https://doi.org/10.1016/j.rechem.2025.102560
Burlov, A. S., Uraev, A. I., Garnovskii, D. A., Lyssenko, K. A., Vlasenko, V. G., Zubavichus, Y. V., Murzin, V. Y., Korshunova, E. V., Borodkin, G. S., Levchenkov, S. I., Vasilchenko, I. S., & Minkin, V. I. (2014). Synthesis, XAFS and X-ray structural studies of mono- and binuclear metal-chelates of N,O,O(N,O,S) tridentate Schiff base pyrazole derived ligands. Journal of Molecular Structure, 1064, 111–121. https://doi.org/10.1016/j.molstruc.2014.02.019
Ali, M., Jahan, K., Singh, J., Singh, R. K., Shoora, S. K., Feng, X., & Yue, Y. (2025). Use of cobalt(II) and chromium(III) metal-based Schiff base complexes for the preparation of potentiometric sensors to determine bromide at ultra-low concentrations. Sensors and Diagnostics, 4(11), 995–1005. https://doi.org/10.1039/d5sd00088b
Wang, X., Ma, M., Wu, J., Li, P., Li, M., Sang, W., Xu, S., Li, D., & Luo, R. (2025). High-density loading of bis Schiffs bases containing nitrogen, oxygen and sulphur active sites in UiO-66 for efficient and selective removal of heavy metals from water. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 718, 136970. https://doi.org/10.1016/j.colsurfa.2025.136970
Thennarasu, A. S., Mohammed, T. P., & Sankaralingam, M. (2022). Mononuclear copper(ii) Schiff base complexes as effective models for phenoxazinone synthase. New J. Chem., 46(45), 21684–21694. https://doi.org/10.1039/D2NJ03934F
Miroslaw, B. (2020). Homo- and hetero-oligonuclear complexes of platinum group metals (PGM) coordinated by imine Schiff base ligands. International Journal of Molecular Sciences, 21(10), 3493. https://doi.org/10.3390/ijms21103493
Sutradhar, D., Chowdhury, H., Banerjee, S., Saha, N. C., & Ghosh, B. K. (2019). Syntheses, crystal structures and luminescence behaviors of four neutral penta-/hexacoordinate cadmium(II) compounds containing a tridentate Schiff base: Variation in coordination numbers, nuclearities and dimensionalities by changing halides/pseudohalides. Inorganica Chimica Acta, 485, 86–97. https://doi.org/10.1016/j.ica.2018.10.002
Ngororabanga, J. M. V., Dembaremba, T. O., Mama, N., & Tshentu, Z. R. (2023). Azo-hydrazone tautomerism in a simple coumarin azo dye and its contribution to the naked-eye detection of Cu2+ and other potential applications. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 289, 122202. https://doi.org/10.1016/j.saa.2022.122202
Zengin, A., Serbest, K., Emirik, M., Özil, M., Menteşe, E., & Faiz, Ö. (2023). Binuclear Cu(II), Ni(II) and Zn(II) complexes of hydrazone Schiff bases: Synthesis, spectroscopy, DFT calculations, and SOD mimetic activity. Journal of Molecular Structure, 1278, 134926. https://doi.org/10.1016/j.molstruc.2023.134926
Tamboura, F. B., Haba, P. M., Gaye, M., Sall, A. S., Barry, A. H., & Jouini, T. (2004). Structural studies of bis-(2,6-diacetylpyridine-bis-(phenylhydrazone)) and X-ray structure of its Y(III), Pr(III), Sm(III) and Er(III) complex. Polyhedron, 23(7), 1191–1197. https://doi.org/10.1016/j.poly.2004.01.014
Kumar, D. S., & Alexander, V. (1999). Synthesis of lanthanide(III) complexes of chloro- and bromo substituted 18-membered tetraaza macrocycles. Polyhedron, 18(11), 1561–1568. https://doi.org/10.1016/S0277-5387(99)00016-9
Abouel-Enein, S. A., Emam, S. M., & Abdel-Satar, E. M. (2023). Bivalent metal chelates with pentadentate azo-Schiff base derived from nicotinic hydrazide: Preparation, structural elucidation, and pharmacological activity. Chemistry & Biodiversity, 20(6), e202201223. https://doi.org/10.1002/cbdv.202201223
Diouf, F., Fall, E. A., Tamboura, F. B., Gaye, M., Gruber, N., & Jouaiti, A. (2022). Synthesis, spectroscopic characterization, and crystal structures of Schiff bases derived from nicotinic hydrazide. IOSR Journal of Applied Chemistry, 15(1), 13-20. https://doi.org/10.9790/5736-1501021320
Mohammed, M. A., Fetoh, A., Ali, T. A., Youssef, M. M., El-Reash, Y. G. A., & Abu El-Reash, G. M. (2024). Co(II), Mn(II), and Fe(III) complexes of water-soluble hydrazone bearing 2-nicotinoylhydrazineylidene moiety: Preparation, characterization, cyclic voltammetry, computational and biological studies. Applied Organometallic Chemistry, 38(4), e7376. https://doi.org/10.1002/aoc.7376
Preethi, V., Vijukumar, V. G., AnilaRaj, S., & Vidya, V. G. (2024). Synthesis, characterization, DFT studies and evaluation of the potential anti-tumour activity of nicotinic hydrazide based Schiff base using in vitro and molecular docking techniques. Heliyon, 10(9), e29689. https://doi.org/10.1016/j.heliyon.2024.e29689
Vijayan, J. G. (2017). Synthesis, characterization, magnetic, thermal and redox properties of oxovanadium(IV) complex of heterocyclic acid hydrazone. European Journal of Chemistry, 8(4), 328–332. https://doi.org/10.5155/eurjchem.8.4.328-332.1571
Masoud, D. M., Azzam, R., Hussein, H. S., Mekawey, A. A. I., & Abdel-Aziz, H. A. (2020). Synthesis of some novel substituted nicotines and evaluation of their antimicrobial activity. Egyptian Journal of Chemistry, 63(3), 791–803. https://doi.org/10.21608/ejchem.2019.13805.1853
Meenatchi, V., Cheng, L., & Han, S. S. (2023). Twisted intramolecular charge transfer, nonlinear optical, antibacterial activity, and DFT analysis of ultrasound processed (E)-N′-(4-isopropylbenzylidene)nicotinohydrazide. Journal of Molecular Liquids, 376, 121489. https://doi.org/10.1016/j.molliq.2023.121489
Christopher Leslee, D. B., Shanmugam, L., Venkatesan, N., Madheswaran, B., Ravula, V., Karuppannan, S., & Kuppannan, S. B. (2025). A coumarin–nicotinic hydrazone probe for chromofluorogenic detection of toxic cyanide ions and its application in molecular logic gate and real water samples analysis. Photochemical & Photobiological Sciences, 24(4), 543–554. https://doi.org/10.1007/s43630-025-00704-z
Li, H., Xu, G.-C., Zhang, L., Guo, J.-X., & Jia, D.-Z. (2013). Structural diversity and properties of four complexes with 4-acyl pyrazolone derivative. Polyhedron, 55, 209–215. https://doi.org/10.1016/j.poly.2013.03.024
Mohammed, M. A., Fetoh, A., Ali, T. A., Youssef, M. M., El-Reash, Y. G. A., & Abu El-Reash, G. M. (2024). Co(II), Mn(II), and Fe(III) complexes of water-soluble hydrazone bearing 2-nicotinoylhydrazineylidene moiety: Preparation, characterization, cyclic voltammetry, computational and biological studies. Applied Organometallic Chemistry, 38(4), e7376. https://doi.org/10.1002/aoc.7376
Gunasekaran, J., Muthuselvan, S., Annadurai, D., Leslee, D. B. C., Venkatesan, N., Murthy, S., Ramasamy, B., Alves, L. G., Martins, A. M., & Kuppannan, S. B. (2024). Novel half-sandwich ruthenium(II) nicotinic hydrazone complexes: An efficient class of catalyst for the N-alkylation of amines with benzyl alcohol via transfer hydrogen mechanism and effective antibacterial agents. Journal of Molecular Structure, 1309, 138179. https://doi.org/10.1016/j.molstruc.2024.138179
Aydoğdu, Ö., Öztürkkan, F. E., Hökelek, T., Uğurlu, G., & Necefoğlu, H. (2025). Syntheses, crystal structures, and DFT calculations of N’-(Pyridin-2-ylmethylene)nicotinohydrazide dihydrate and its copper complex. Journal of the Iranian Chemical Society, 22(4), 683–697. https://doi.org/10.1007/s13738-025-03177-0
Mohammed, M. A., Fetoh, A., Ali, T. A., Youssef, M. M., El-Reash, Y. G. A., & Abu El-Reash, G. M. (2024). Co(II), Mn(II), and Fe(III) complexes of water-soluble hydrazone bearing 2-nicotinoylhydrazineylidene moiety: Preparation, characterization, cyclic voltammetry, computational and biological studies. Applied Organometallic Chemistry, 38(4), e7376. https://doi.org/10.1002/aoc.7376
Çakmak, R., Başaran, E., Sahin, K., Şentürk, M., & Durdağı, S. (2024). Synthesis of novel hydrazide–hydrazone compounds and in vitro and in silico investigation of their biological activities against AChE, BChE, and hCA I and II. ACS Omega, 9(18), 20030–20041. https://doi.org/10.1021/acsomega.3c10182
Iliev, I., Kontrec, D., Detcheva, R., Georgieva, M., Balacheva, A., Galić, N., & Pajpanova, T. (2019). Cancer cell growth inhibition by aroylhydrazone derivatives. Biotechnology & Biotechnological Equipment, 33(1), 756–763. https://doi.org/10.1080/13102818.2019.1608302
Seck, G. A., Guèye, M. N., Tamboura, F. B., Thiam, I. E., Diouf, O., Sall, A. S., & Gaye, M. (2024). Synthesis and characterization of binuclear complexes of metals transition of N’1,N’4-bis(1-(pyridin-2-yl)ethylidene)succinohydrazide. International Research Journal of Pure and Applied Chemistry, 25(5), 111–122. https://doi.org/10.9734/irjpac/2024/v25i5879
Gueye, M. N., Dieng, M., Lo, D., Thiam, I. E., Barry, A. H., Gaye, M., Sall, A. S., & Retailleau, P. (2017). Synthesis, physical studies and crystal structure determination of Y(III) and Er(III) complexes of 1-(pyridin-2-yl)-2-(pyridine-2-ylmethylene)hydrazine. European Journal of Chemistry, 8(2), 137–143. https://doi.org/10.5155/eurjchem.8.2.137-143.1557
Ndiaye-Gueye, M., Diop, A., Gaye, P. A., Thiam, I. E., Tamboura, F. B., & Gaye, M. (2021). Syntheses, characterization, and X-ray crystal structure of binuclear lanthanide complexes assembled with Schiff base and acetate. Earthline Journal of Chemical Sciences, 7(1), 81–95. https://doi.org/10.34198/ejcs.7122.8195
Diop, A., Sarr, M., Diop, M., Thiam, I. E., Barry, A. H., Coles, S., Orton, J., & Gaye, M. (2019). Metal transition complexes of tridentate Schiff base ligands derived from 2-hydrazinopyridine: synthesis, spectroscopic characterization and X-ray structures. Transition Metal Chemistry, 44(5), 415–423. https://doi.org/10.1007/s11243-019-00317-3
APEX4, Bruker AXS Inc., Madison, Wisconsin, USA, 2021.
Sheldrick, G. M. (2015). SHELXT – Integrated space-group and crystal-structure determination. Acta Crystallographica Section A, 71(1), 3–8. https://doi.org/10.1107/S2053273314026370
Sheldrick, G. M. (2015). Crystal structure refinement with SHELXL. Acta Crystallographica Section C, 71(1), 3–8. https://doi.org/10.1107/S2053229614024218
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K., & Puschmann, H. (2009). OLEX2: a complete structure solution, refinement and analysis program. Journal of Applied Crystallography, 42(2), 339–341. https://doi.org/10.1107/S0021889808042726
Spek, A. L. (2009). Structure validation in chemical crystallography. Acta Crystallographica Section D, 65, 148-155. https://doi.org/10.1107/S090744490804362X
Farrugia, L. J. (2012). WinGX and ORTEP for Windows: an update. Journal of Applied Crystallography, 45(4), 849–854. https://doi.org/10.1107/S0021889812029111
Faye, N., Gaye, A. A., Fall, A., Ndoye, C., Diop, M., Excoffier, G., & Gaye, M. (2022). Syntheses, antioxidant activity and crystal structures of 1-nicotinoyl-4-phenylthiosemicarbazide and its derivative N-phenyl-5-(pyridin-3-yl)-1,3,4-oxadiazol-2-amine. Modern Chemistry, 10(4), 113–120. https://doi.org/10.11648/j.mc.20221004.12
Gadiaga, D., Sy, A., Ndoye, C., Traoré, B., Excoffier, G., Diouf, O., & Gaye, M. (2023). New Fe(III) trichlorido complex of a bidentate N’-(thiophen-2-ylmethylene)isonicotinohydrazide ligand: Synthesis, X-ray structure, spectral characterization, and electrochemistry study. International Research Journal of Pure and Applied Chemistry, 24(2), 49–60. https://doi.org/10.9734/irjpac/2023/v24i2809
Casellato, U., Guerriero, P., Tamburini, S., Vigato, P. A., & Benelli, C. (1993). Mononuclear, homo- and heteropolynuclear complexes with acyclic compartmental Schiff bases. Inorganica Chimica Acta, 207(1), 39–58. https://doi.org/10.1016/S0020-1693(00)91454-3
Aruna, V. A. J., & Alexander, V. (1996). Synthesis of lanthanide(III) complexes of a 20-membered hexaaza macrocycle. J. Chem. Soc., Dalton Trans., (9), 1867–1873. https://doi.org/10.1039/DT9960001867
Ran, J.-W., Zhang, S.-Y., Hu, B., Xu, B., & Li, Y. (2008). Trinuclear and mononuclear nickel(II) complexes incorporating tridentate 2-[(pyridine-2-ylimine)methyl]phenol ligand: Syntheses, crystal structures and magnetic properties. Inorganic Chemistry Communications, 11(12), 1474–1477. https://doi.org/10.1016/j.inoche.2008.10.013
Charef, N., Arrar, L., Ourari, A., Zalloum, R. M., & Mubarak, M. S. (2009). Synthesis and chelating properties of polystyrene supported Schiff base (N,N′-disalicylidenepropylenetriamine) resin toward some divalent metal ions. Journal of Macromolecular Science, Part A, 47(2), 177–184. https://doi.org/10.1080/10601320903458796
Cardoso, S. H., Assis, J. V. de, Almeida, M. V. de, Lourenço, M. C. S., Vicente, F. R. C., & Souza, M. V. N. de. (2009). Synthesis and antitubercular activity of isoniazid condensed with carbohydrate derivatives. Química Nova, 32, 1557–1560. https://doi.org/10.1590/S0100-40422009000600038
Geary, W. J. (1971). The use of conductivity measurements in organic solvents for the characterisation of coordination compounds. Coordination Chemistry Reviews, 7(1), 81–122. https://doi.org/10.1016/S0010-8545(00)80009-0
Egekenze, R. N., Gultneh, Y., & Butcher, R. (2018). Mn(III) and Mn(II) complexes of tridentate Schiff base ligands; synthesis, characterization, structure, electrochemistry and catalytic activity. Inorganica Chimica Acta, 478, 232–242. https://doi.org/10.1016/j.ica.2018.01.027
Sedighipoor, M., Kianfar, A. H., Sabzalian, M. R., & Abyar, F. (2018). Synthesis and characterization of new unsymmetrical Schiff base Zn (II) and Co (II) complexes and study of their interactions with bovin serum albumin and DNA by spectroscopic techniques. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 198, 38–50. https://doi.org/10.1016/j.saa.2018.02.050
Orie, K. J., Ike, C. D., & Nzeneri, J. U. (2021). Synthesis and characterization of metal complexes with 4-methyl-N-(p-methylphenylsulphonyl)-N-(pyridin-2-yl)benzene sulphonamide. Modern Chemistry, 9(3), 46–51. https://doi.org/10.11648/j.mc.20210903.11
Singh, Y. P., Patel, R. N., Singh, Y., Choquesillo-Lazarte, D., & Butcher, R. J. (2017). Classical hydrogen bonding and stacking of chelate rings in new copper(II) complexes. Dalton Trans., 46(9), 2803–2820. https://doi.org/10.1039/C6DT04661D
Ling, N., Wang, X., Zeng, D., Zhang, Y.-W., Fang, X., & Yang, H.-X. (2020). Synthesis, characterization and biological assay of three new benzotriazole-based Zn(II) complexes. Journal of Molecular Structure, 1206, 127641. https://doi.org/10.1016/j.molstruc.2019.127641
Dehghanpour, S., & Mahmoudi, A. (2007). Synthesis and characterization of Cobalt(II), Nickel(II), and Zinc(II) Complexes with N,N′‐bis(2‐nitrocinnamaldehyde)‐1,2‐diiminoethane ligand. Crystal structure of Zn(nca2en)Br2. Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 37(1), 35–40. https://doi.org/10.1080/15533170601172427
Taghizadeh, L., Montazerozohori, M., Masoudiasl, A., Joohari, S., & White, J. M. (2017). New tetrahedral zinc halide Schiff base complexes: Synthesis, crystal structure, theoretical, 3D Hirshfeld surface analyses, antimicrobial and thermal studies. Materials Science and Engineering: C, 77, 229–244. https://doi.org/10.1016/j.msec.2017.03.150
Groom, C. R., Bruno, I. J., Lightfoot, M. P., & Ward, S. C. (2016). The Cambridge Structural Database. Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials, 72(2), 171–179. https://doi.org/10.1107/S2052520616003954

This work is licensed under a Creative Commons Attribution 4.0 International License.
