The synthesis and structural properties of a chloridobis{N-[(4-methoxyphenyl)imino]pyrrolidine-1-carboxamide}zinc(II) (acetonitrile)trichloridozincate coordination complex

Abstract

The title complex, [ZnCl(C12H15N3O2)2][ZnCl3(CH3CN)], was synthesized and its structure was fully characterized through single-crystal X-ray diffraction analysis. The complex crystallizes in the orthorhombic system, space group Pbca (61), with a central zinc atom coordinating one chlorine atom and two pyrrolidinyl-4-methoxyphenyl azoformamide ligands in a bidentate manner, utilizing both the nitrogen and oxygen atoms in a 1,3-heterodiene (N=N - C=O) motif for coordinative bonding, yielding an overall positively (+1) charged complex. The complex is accompanied by a [(CH3CN)ZnCl3]- counter-ion. The crystal data show that the harder oxygen atoms in the heterodiene zinc chelate form bonding interactions with distances of 2.002 (3) and 2.012 (3) Å, while nitrogen atoms are coordinated by the central zinc cation with bond lengths of 2.207 (3) and 2.211 (3) Å. To gain further insight into the intermolecular interactions within the crystal, Hirshfeld surface analysis was performed, along with the calculation of two-dimensional fingerprint plots. This analysis revealed that H⋯H (39.9%), Cl⋯H/H⋯Cl (28.2%) and C⋯H/H⋯C (7.2%) interactions are dominant. This unique crystal structure sheds light on arrangement and bonding interactions with azoformamide ligands, and their unique qualities over similar semicarbazone and azothioformamide structures.