Zn(II) halide coordination compounds with imidazole and 2-methylimidazole. Structural and computational characterization of intermolecular interactions and disorder

Novel zinc(II) coordination compounds with imidazole (Im) and 2-methylimidazole (2-MeIm) were prepared and characterized: [ZnX(2)(Im)(2)] (X = Cl (1a), Br (1b), I (1c)) and [ZnX(2)(2-MeIm)(2)] (X = Cl (2a), Br (2b), I (2c)). Coordination compounds 1a–c were prepared mechanochemically by neat grinding while 2a–c were prepared by solution synthesis. The complexes were characterized by FT-IR and NMR spectroscopy and by powder X-ray diffraction. Crystal and molecular structures were determined by the single crystal X-ray diffraction. The characteristic of all structures is a distorted tetrahedral coordination of zinc consisting of two halide atoms and two nitrogen atoms from the imidazole (or 2-methylimidazole) ligand. Molecules in 1a–c are interconnected by hydrogen bonds into 3D structures. Structures of 1b and 1c were found to have similar unit cells and similar crystal packing and hydrogen bonding. Introduction of the 2-methylimidazole substituent introduced disorder in the crystal structures of 2a–c. Because of the very small size of the crystals data were collected by synchrotron radiation. For the disordered 2a,2b and 2c fixed geometry was used in refining of the structures. Crystal structures of 2a–c are characterized by chains of molecules connected by hydrogen bonds of the type N–H⋅⋅⋅X, with weak π⋅⋅⋅π and van der Waals interactions between the chains. The QTAIM, RDG and NCI computational analysis of 1a and 2a–c confirmed the presence of weak attractive intermolecular interactions that can be attributed to weak N–H⋅⋅⋅X and van der Waals interactions.