Synthesis and Structural Characterization of Picolinoyl (4-ethylthiosemicarbazide) and its New Heteroleptic Cu(II) Complex
Main Article Content
Abstract
The ligand picolinoyl(4-ethylthiosemicarbazide) HL was synthesized by the reaction of picolinohydrazide and ethyl isothiocyanate in absolute ethanol. The structure of HL was characterized by spectroscopic methods such as IR, 1H, and 13C NMR spectroscopy. One-pot reaction of CuCl2 and equimolar amounts of HL and o-phenanthroline in CH2Cl2/MeOH mixture with the presence of a supporting base like pyridine gave rise to a new heteroleptic cationic Cu(II) complex with the composition of [Cu(L)(o-phen)]+. Crystalline PF6– salt was obtained after workup with (n-Bu4N)(PF6) and single-crystal structure of the complex was determined. The spectroscopic data and X-ray crystallography demonstrated that the Cu(II) ion is five-coordinate with the coordination sphere consisted of (S, N1, Npyridine) and (N, N) donor sets belonging to the singly deprotonated ligand {L–} and o-phenanthroline, respectively.
Keywords:
Acyl thiosemicarbazides, heteroleptic complexes, Cu(II) complexes.
References
[1] A. Singh, M. K. Bharty, R. K. Dani, S. Singh, S. K. Kushawaha, N. K. Singh, Manganese(II) and Zinc(II) Complexes of 4-phenyl(2-methoxybenzoyl)-3-thiosemicarbazide: Synthesis, Spectral, Structural Characterization, Thermal Behavior and DFT Study, Polyhedron, Vol. 73, 2014, pp. 98-109, https://https://doi.org/10.1016/j.poly.2014.02.029.
[2] M. K. Bharty, R. K. Dani, N. K. Singh, R. J. Butcher, Polymeric, Dimeric and Monomeric Mn(II) Complexes Derived from [N′-(pyridine-4-carbonyl)-hydrazine]-carbodithioic Acid Methyl Ester and 1-isonicotinoyl-4-phenyl-3-thiosemicarbazide: Syntheses, Crystal Structure and Thermal Analysis, Polyhedron, Vol. 112, 2016, pp. 67-77,
https://https://doi.org/10.1016/j.poly.2016.03.050.
[3] J. S. Casas, E. E. Castellano, J. Ellena, M. S. G. Tasende, A. Sánchez, J. Sordo, A. Touceda, Molecular and Supramolecular Structures of 1-Phenyl-4-phenylacetyl-2-thiosemicarbazide (H2L) and its Complexes with Diphenyllead(IV) Chloride and Acetate, Z. Anorg. Allg. Chem, Vol. 631, 2005, pp. 2247-2252,
https://https://doi.org/10.1002/zaac.200570052.
[4] S. I. Orysyk, V. V. Bon, O. A. Zholob, V. I. Pekhnyo, V. V. Orysyk, Y. L. Zborovskii, M. V. Vovk, Rhodium(III), Palladium(II), and Platinum(II) Complexes with 2-(2-hydroxybenzoyl)-N-methylhydrazinecarbothioamide: Syntheses, Structures, and Spectral Characteristics, Russ, J. Coord. Chem, Vol. 40, 2014, pp. 160-170,
https://https://doi.org/10.1134/S1070328414030063.
[5] P. B. A. Bharti, N. K. Singh, M. K. Bharty, NNS Tridentate Thiosemicarbazide and 1,3,4-thiadiazole-2-amine Complexes of some Transition Metal Ions: Syntheses, Structure and Fluorescence Properties, J. Coord. Chem, Vol. 69, 2016, pp. 1258-1271, https://https://doi.org/10.1080/00958972.2016.1160074.
[6] W. S. Wu, W. D. Cheng, D. S. Wu, H. Zhang, Y. J. Gong, Y. Lu, Crystal Structure, Magnetic and Optical Properties of (2-picoloylcarbonyl) Thiosemicarbazonatocopper(II) ([Cu3L2(H2O)2]·2ClO4·3H2O, and L=[C7H8N4OS]2−), Inorg. Chem. Commun, Vol. 9, 2006, pp. 559-562,
https://https://doi.org/10.1016/j.inoche.2006.02.025.
[7] E. E. Mohamed, A. T. AbedelKarim, Y. H. Elmalik, A. E. Mohamed, M. S. Aljahdali, Characterization and Biological Activity Studies on some Transition Metal Complexes of Thiosemicarbazide Derived from 2-picolinic Acid Hydrazide, Eur. J. Chem, Vol. 5, 2014, pp. 252-259, https://10.5155/eurjchem.5.2.252-259.990.
[8] G. J. Kubas, B. Monzyk, A. L. Crumbliss, Tetrakis(Acetonitrile)Copper(I) Hexafluorophosphate, in Inorganic Syntheses, D. F. Shriver (Ed.), 1979, pp. 90-92.
[9] Bruker, APEX2, Bruker AXS Inc., Madison, Wisconsin, USA, 2014.
[10] O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard, H. Puschmann, OLEX2: a Complete Structure Solution, Refinement and Analysis Program, J. Appl, Crystallogr, Vol. 42, 2009, pp. 339-341,
https://https://doi.org/doi:10.1107/S0021889808042726.
[11] S. D. G. Dhumwad, K. B. Goudar, Synthesis and Structural Characterization of Biologically Active Metal Complexes of N1-(N-morpholinoacetyl)-N4-Phenyl Thiosemicarbazide and 3,4-Methylenedioxybenzaldehyde Thiosemicarbazone with Oxovanadium(lV) Chromiumtlll), Manganese(II), Iron(III), Cobalt(II), Nickel(II), Copper(II), Cadmium(II), Uranium(VI), Thorium(IV) and Silicon(IV), Indian J. Chem., Sect A, Vol. 33A, 1994, pp. 320-324,
http://nopr.niscair.res.in/handle/123456789/40655.
[12] K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, Part A, Theory and Applications in Inorganic Chemistry, 6th ed., Wiley, 2009.
[13] X. Shen, D. Wu, X. Huang, Q. Liu, Z. Huang, B. Kang, Copper Complexes Derived from 1-(2-Carboxybenzoyl) Thiose Micarbazide (H3L): Syntheses, Characterization and Crystal Structure of [Cu3L2(Py)6](HIm)(H2O)2, Polyhedron, Vol. 16, 1997, pp. 1477-1482, https://https://doi.org/10.1016/S0277-5387(96)00441-X.
[14] M. L. Liu, J. M. Dou, D. C. Li, D. Q. Wang, J. Z. Cui, Synthesis, Structural Characterization and Thermal Properties of Three Copper(II) Complexes Based on Aryl Hydrazide Ligands, Transit, Met. Chem, Vol. 37, 2012, pp. 117-124, https://https://doi.org/10.1007/s11243-011-9565-0.
[15] P. T. Thuy, L. C. Dinh, N. G. Huy, P. T. N. Oanh, P. C. Thang, Synthesis and Structural Characterization of N-methylanthraniloyl- (4-ethylthiosemicarbazide) and its Cu(II) Trinuclear Complex, Vietnam J. Chem, Vol. 59, 2021, pp. 290-295, https://https://doi.org/10.1002/vjch.202000129.
[2] M. K. Bharty, R. K. Dani, N. K. Singh, R. J. Butcher, Polymeric, Dimeric and Monomeric Mn(II) Complexes Derived from [N′-(pyridine-4-carbonyl)-hydrazine]-carbodithioic Acid Methyl Ester and 1-isonicotinoyl-4-phenyl-3-thiosemicarbazide: Syntheses, Crystal Structure and Thermal Analysis, Polyhedron, Vol. 112, 2016, pp. 67-77,
https://https://doi.org/10.1016/j.poly.2016.03.050.
[3] J. S. Casas, E. E. Castellano, J. Ellena, M. S. G. Tasende, A. Sánchez, J. Sordo, A. Touceda, Molecular and Supramolecular Structures of 1-Phenyl-4-phenylacetyl-2-thiosemicarbazide (H2L) and its Complexes with Diphenyllead(IV) Chloride and Acetate, Z. Anorg. Allg. Chem, Vol. 631, 2005, pp. 2247-2252,
https://https://doi.org/10.1002/zaac.200570052.
[4] S. I. Orysyk, V. V. Bon, O. A. Zholob, V. I. Pekhnyo, V. V. Orysyk, Y. L. Zborovskii, M. V. Vovk, Rhodium(III), Palladium(II), and Platinum(II) Complexes with 2-(2-hydroxybenzoyl)-N-methylhydrazinecarbothioamide: Syntheses, Structures, and Spectral Characteristics, Russ, J. Coord. Chem, Vol. 40, 2014, pp. 160-170,
https://https://doi.org/10.1134/S1070328414030063.
[5] P. B. A. Bharti, N. K. Singh, M. K. Bharty, NNS Tridentate Thiosemicarbazide and 1,3,4-thiadiazole-2-amine Complexes of some Transition Metal Ions: Syntheses, Structure and Fluorescence Properties, J. Coord. Chem, Vol. 69, 2016, pp. 1258-1271, https://https://doi.org/10.1080/00958972.2016.1160074.
[6] W. S. Wu, W. D. Cheng, D. S. Wu, H. Zhang, Y. J. Gong, Y. Lu, Crystal Structure, Magnetic and Optical Properties of (2-picoloylcarbonyl) Thiosemicarbazonatocopper(II) ([Cu3L2(H2O)2]·2ClO4·3H2O, and L=[C7H8N4OS]2−), Inorg. Chem. Commun, Vol. 9, 2006, pp. 559-562,
https://https://doi.org/10.1016/j.inoche.2006.02.025.
[7] E. E. Mohamed, A. T. AbedelKarim, Y. H. Elmalik, A. E. Mohamed, M. S. Aljahdali, Characterization and Biological Activity Studies on some Transition Metal Complexes of Thiosemicarbazide Derived from 2-picolinic Acid Hydrazide, Eur. J. Chem, Vol. 5, 2014, pp. 252-259, https://10.5155/eurjchem.5.2.252-259.990.
[8] G. J. Kubas, B. Monzyk, A. L. Crumbliss, Tetrakis(Acetonitrile)Copper(I) Hexafluorophosphate, in Inorganic Syntheses, D. F. Shriver (Ed.), 1979, pp. 90-92.
[9] Bruker, APEX2, Bruker AXS Inc., Madison, Wisconsin, USA, 2014.
[10] O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard, H. Puschmann, OLEX2: a Complete Structure Solution, Refinement and Analysis Program, J. Appl, Crystallogr, Vol. 42, 2009, pp. 339-341,
https://https://doi.org/doi:10.1107/S0021889808042726.
[11] S. D. G. Dhumwad, K. B. Goudar, Synthesis and Structural Characterization of Biologically Active Metal Complexes of N1-(N-morpholinoacetyl)-N4-Phenyl Thiosemicarbazide and 3,4-Methylenedioxybenzaldehyde Thiosemicarbazone with Oxovanadium(lV) Chromiumtlll), Manganese(II), Iron(III), Cobalt(II), Nickel(II), Copper(II), Cadmium(II), Uranium(VI), Thorium(IV) and Silicon(IV), Indian J. Chem., Sect A, Vol. 33A, 1994, pp. 320-324,
http://nopr.niscair.res.in/handle/123456789/40655.
[12] K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, Part A, Theory and Applications in Inorganic Chemistry, 6th ed., Wiley, 2009.
[13] X. Shen, D. Wu, X. Huang, Q. Liu, Z. Huang, B. Kang, Copper Complexes Derived from 1-(2-Carboxybenzoyl) Thiose Micarbazide (H3L): Syntheses, Characterization and Crystal Structure of [Cu3L2(Py)6](HIm)(H2O)2, Polyhedron, Vol. 16, 1997, pp. 1477-1482, https://https://doi.org/10.1016/S0277-5387(96)00441-X.
[14] M. L. Liu, J. M. Dou, D. C. Li, D. Q. Wang, J. Z. Cui, Synthesis, Structural Characterization and Thermal Properties of Three Copper(II) Complexes Based on Aryl Hydrazide Ligands, Transit, Met. Chem, Vol. 37, 2012, pp. 117-124, https://https://doi.org/10.1007/s11243-011-9565-0.
[15] P. T. Thuy, L. C. Dinh, N. G. Huy, P. T. N. Oanh, P. C. Thang, Synthesis and Structural Characterization of N-methylanthraniloyl- (4-ethylthiosemicarbazide) and its Cu(II) Trinuclear Complex, Vietnam J. Chem, Vol. 59, 2021, pp. 290-295, https://https://doi.org/10.1002/vjch.202000129.