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: [ZnX2(Im)2] (X = Cl (1a), Br (1b), I (1c)) and [ZnX2(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.