Synthesis, Structure, and Biologic Activity of Some Copper, Nickel, Cobalt, and Zinc Complexes with 2-Formylpyridine N 4-Allylthiosemicarbazone

Vasilii Graur; Yurii Chumakov; Olga Garbuz; Christelle Hureau; Victor Tsapkov; Aurelian Gulea

doi:10.1155/2022/2705332

Synthesis, Structure, and Biologic Activity of Some Copper, Nickel, Cobalt, and Zinc Complexes with 2-Formylpyridine N ⁴-Allylthiosemicarbazone

Bioinorg Chem Appl. 2022 May 25:2022:2705332. doi: 10.1155/2022/2705332. eCollection 2022.

Authors

Vasilii Graur¹, Yurii Chumakov², Olga Garbuz¹, Christelle Hureau³, Victor Tsapkov¹, Aurelian Gulea¹

Affiliations

¹ Laboratory of Advanced Materials in Biofarmaceutics and Technics, Moldova State University, 60 Mateevici Street, MD 2009, Chisinau, Moldova.
² Institute of Applied Physics, 5 Academiei Street, MD 2028, Chisinau, Moldova.
³ Laboratoire de Chimie de Coordination, 205 Route de Narbonne 31077 Toulouse Cedex 04, Toulouse, France.

Abstract

A series of zinc(II) ([Zn(H₂O)(L)Cl] (1)), copper (II) ([Cu(L)Cl] (2), [Cu(L)Br] (3), [Cu₂(L)₂(CH₃COO)₂]·4H₂O (4)), nickel(II) ([Ni(HL)₂]Cl₂·H₂O (5)), and cobalt(III) ([Co(L)₂]Cl (6)) complexes were obtained with 2-formylpyridine N ⁴-allylthiosemicarbazone (HL). In addition another two thiosemicarbazones (3-formylpyridine N ⁴-allylthiosemicarbazone (HL ^a) and 4-formylpyridine N ⁴-allylthiosemicarbazone (HL ^b)) have been obtained. The synthesized thiosemicarbazones have been studied using ¹H and ¹³C NMR spectroscopy, IR spectroscopy, and X-ray diffraction analysis. The composition and structure of complexes were studied using elemental analysis, IR and UV-Vis spectroscopies, molar conductivity, and magnetic susceptibility measurements. Single crystal X-ray diffraction analysis elucidated the structure of thiosemicarbazones HL, HL ^a, and HL ^b, as well as complexes 4 and 5. The antiproliferative properties of these compounds toward a series of cancer cell lines (HL-60, HeLa, BxPC-3, RD) and a normal cell line (MDCK) have been investigated. The nickel complex shows high selectivity (SI > 1000) toward HL-60 cell line and is the least toxic. The zinc complex shows the highest selectivity toward RD cell line (SI = 640). The copper complexes (2-4) are the most active molecular inhibitors of proliferation of cancer cells, but exhibit not such a high selectivity and are significantly more toxic. Zinc and copper complexes manifest high antibacterial activity. It was found that calculated at B3LYP level of theory different reactivity descriptors of studied compounds strongly correlate with their biological activity.