Bis(N,N-diethyldithiocarbamato-κ2S,S′)(3-hydroxypyridine-κN)zinc and bis[N-(2-hydroxyethyl)-N-methyldithiocarbamato-κ2S,S′](3-hydroxypyridine-κN)zinc: crystal structures and Hirshfeld surface analysis

Abstract

The common feature of the molecular structures of the title compounds, [Zn(C5H10NS2)2(C5H5NO)], (I), and [Zn(C4H8NOS2)2(C5H5NO)], (II), are NS4 donor sets derived from N-bound hydroxypyridyl ligands and asymmetrically chelating dithiocarbamate ligands. The resulting coordination geometries are highly distorted, being intermediate between square pyramidal and trigonal bipyramidal for both independent molecules comprising the asymmetric unit of (I), and significantly closer towards square pyramidal in (II). The key feature of the molecular packing in (I) is the formation of centrosymmetric, dimeric aggregates sustained by pairs of hydroxy-O—H...S(dithiocarbamate) hydrogen bonds. The aggregates are connected into a three-dimensional architecture by methylene-C—H...O(hydroxy) and methyl-C—H...π(chelate) interactions. With greater hydrogen-bonding potential, supramolecular chains along the c axis are formed in the crystal of (II), sustained by hydroxy-O—H...O(hydroxy) hydrogen bonds, with ethylhydroxy and pyridylhydroxy groups as the donors, along with ethylhydroxy-O—H...S(dithiocarbamate) hydrogen bonds. Chains are connected into layers in the ac plane by methylene-C—H...π(chelate) interactions and these stack along the b axis, with no directional interactions between them. An analysis of the Hirshfeld surfaces clearly distinguished the independent molecules of (I) and reveals the importance of the C—H...π(chelate) interactions in the packing of both (I) and (II)