Supramolecular Assemblies in Pyridine- and Pyrazole-Based Coordination Compounds of Co(II) and Ni(II): Characterization, Hirshfeld Analysis and Theoretical Studies

Abstract

Two new Ni(II) and Co(II) coordination compounds,viz., [Ni(H2O)5(DMAP)](IPhth)·2H2O (1) and [Co(Hdmpz)4(H2O)2]Cl2 (2) (where DMAP = 4-dimethylaminopyridine, IPhth = Isophthalate, Hdmpz = 3,5-dimethylpyrazole),were synthesized and characterized using elemental analysis, TGA, spectroscopic (FTIR and electronic) and single-crystal X-ray diffraction techniques. Compound 1 crystallizes as a co-crystal hydrate of Ni(II), whereas compound 2 is a mononuclear compound of Co(II). The crystal structure analysis of compound 1 reveals the presence of various non-covalent interactions such as anion‒π, π‒π, C‒H∙∙∙π, C‒H∙∙∙C, etc., which stabilize the layered assembly of the compound. In compound 2, enclathration of counter chloride ions within the supramolecular trimeric host cavity plays a crucial role in the stabilization of the compound. The non-covalent interactions observed in the crystal structures were further studied theoretically, focusing on the cooperative π-stacking interactions between the DMAP and IPhth counter-ions in 1. To identify the non-covalent interactions of the compounds, Hirshfeld surfaces and their associated two-dimensional fingerprint regions were analyzed. Theoretical calculations confirm that H-bonding interactions combined with the π-stacking contacts are crucial synthons for the solid-state stability of compound 1.

Combining Copper and Zinc into a Biosensor for Anti-Chemoresistance and Achieving Osteosarcoma Therapeutic Efficacy

“…Furthermore, the anti-tumour activity of tetrahedral copper derivatives (average IC50 of 18.91 μM at 72 h) is better than that of zinc derivatives (average IC50 of 57.25 μM at 72 h) [147]. Another benzimidazole example, 4-butyloxy-2,6-bis(1-methyl-2-benzimidazolyl) pyridine, was also synthesised with CuZn to form six-coordinated tridentate complexes with distorted octahedral configurations [148]. Their anti-tumour activity findings are that copper (II) derivatives (IC50 = 26.09 μM) outperform zinc (II) derivatives (IC50 = 46.13 μM), followed by cisplatin (IC50 = 43.99 μM) [149].…”

Combining Copper and Zinc into a Biosensor for Anti-Chemoresistance and Achieving Osteosarcoma Therapeutic Efficacy

“…Furthermore, the anti-tumour activity of tetrahedral copper derivatives (average IC 50 of 18.91 μM at 72 h) is better than that of zinc derivatives (average IC 50 of 57.25 μM at 72 h) [ 149 ]. Another benzimidazole example, 4-butyloxy-2,6-bis(1-methyl-2-benzimidazolyl) pyridine, was also synthesised with CuZn to form six-coordinated tridentate complexes with distorted octahedral configurations [ 150 ]. Their anti-tumour activity findings are that copper(II) derivatives (IC 50 = 26.09 μM) outperform zinc(II) derivatives (IC 50 = 46.13 μM), followed by cisplatin (IC 50 = 43.99 μM) [ 151 ].…”