A new approach to study semi-coordination using two 2-methyl-5-nitroimidazole copper(ii) complexes of biological interest as a model system

Abstract

Two novel copper(II) complexes [Cu(2mni)₂(H₂O)₂](NO₃)₂·2H₂O (1) and [Cu(2mni)₂(NO₃)₂] (2), where 2mni is 2-methyl-5-nitroimidazole, were prepared and characterized in the solid state using single-crystal and powder X-ray diffraction analyses, EPR, electronic and vibrational spectroscopies (FTIR and Raman), and thermogravimetric methods. Both products present an elongated distorted octahedral geometry with axial Cu–O bond lengths of 2.606(14) and 2.593(15) Å, indicating semi-coordination. Density functional theory (DFT) calculations at the B3LYP/LANL2DZ theory level were used to study the electronic properties of 1 and 2. The Independent Gradient Model (IGM) was employed to determine the Intrinsic Bond Strength Index (IBSI) of the semi-coordination and to plot δ_g isosurfaces for the electronic sharing between the metal center and ligands. A moderate to weak antibacterial activity against Escherichia coli cultures was found for 1 with a 50% growth inhibition (GI₅₀) value of 0.25 mmol L⁻¹. To the best of our knowledge, this is the first time that the semi-coordination analysis using IGM was carried out for a copper(II) complex with axial elongation, finding a good correlation between the bond length and the IBSI, and the study was extended for a series of analogous complexes described in the literature.