A new Zn(II) complex of N'-(1-(thiophen-2-yl)ethylidene)isonicotinohydrazide: synthesis, spectral characterization, X-ray structure

  • Dame Gadiaga LSAO-MED, Gaston Berger University, Saint-Louis, Senegal and LCCOB Department of Chemistry, University Cheikh Anta DIOP, Dakar, Sénégal
  • Adama Sy LSAO-MED, Gaston Berger University, Saint-Louis, Senegal and LCCOB Department of Chemistry, University Cheikh Anta DIOP, Dakar, Sénégal
  • Andrea Daolio Department of Chemical Sciences, Life Science and Environmental Sustainability, University of Parma, Parco Area delleScienze 17/A, 43124 Parma, Italy
  • Ibrahima Elhadji Thiam LCCOB Department of Chemistry, University Cheikh Anta DIOP, Dakar, Sénégal
  • Paolo Pio Mazzeo Department of Chemical Sciences, Life Science and Environmental Sustainability, University of Parma, Parco Area delle Scienze 17/A, 43124 Parma, Italy and Biopharmanet-TEC, University of Parma, Parco Area Delle Scienze 27/A, Parma 43124, Italy
  • Alessia Bacchi Department of Chemical Sciences, Life Science and Environmental Sustainability, University of Parma, Parco Area delle Scienze 17/A, 43124 Parma, Italy and Biopharmanet-TEC, University of Parma, Parco Area Delle Scienze 27/A, Parma 43124, Italy
  • Mohamed Gaye LCCOB Department of Chemistry, University Cheikh Anta DIOP, Dakar, Sénégal
Keywords: Synthesis, X-ray crystal structure, isonicotinohydrazide, coordination complex

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.

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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

Published
2026-05-01
How to Cite
Gadiaga, D., Sy, A., Daolio, A., Thiam, I. E., Mazzeo, P. P., Bacchi , A., & Gaye, M. (2026). A new Zn(II) complex of N’-(1-(thiophen-2-yl)ethylidene)isonicotinohydrazide: synthesis, spectral characterization, X-ray structure . Earthline Journal of Chemical Sciences, 13(2), 187-198. https://doi.org/10.34198/ejcs.13226.14.187198