Equilibrium and structural studies on Co(II), Ni(II), Cu(II) and Zn(II) complexes with N-(2-benzimidazolyl)methyliminodiacetic acid: crystal structures of Ni(II) and Cu(II) complexes

Combined pH-metric, UV–Vis, 1H NMR and EPR spectral investigations on the complex formation of M(II) ions (M=Co, Ni, Cu and Zn) with N-(2-benzimidazolyl)methyliminodiacetic acid (H2bzimida, hereafter H2L) in aqueous solution at a fixed ionic strength, I=10−1 mol dm−3, at 25 ± 1 °C indicate the formation of M(L), M(H−1L)− and M2(H−1L)+ complexes. Proton–ligand and metal–ligand constants and the complex formation equilibria have been elucidated. Solid complexes, [M(L)(H2O)2] · nH2O (n=1 for M = Co and Zn, n=2 for M = Ni) and {Cu (μ-L) · 4H2O}n, have been isolated and characterized by elemental analysis, spectral, conductance and magnetic measurements and thermal studies. Structures of [Ni(L)(H2O)2] · 2H2O and {Cu(μ-L) · 4H2O}n have been determined by single crystal X-ray diffraction. The nickel(II) complex exists in a distorted octahedral environment in which the metal ion is coordinated by the two carboxylate O atoms, the amino-N atom of the iminodiacetate moiety and the pyridine type N-atom of the benzimidazole moiety. Two aqua O atoms function as fifth and sixth donor atoms. The copper(II) complex is made up of interpenetrating polymeric chains of antiferromagnetically coupled Cu(II) ions linked by carboxylato bridges in syn–anti (apical–equatorial) bonding mode and stabilized via interchain hydrogen bonds and π–π stacking interactions.