Mono urotropine adducts of some binary zinc xanthates and dithiocarbamates: solid-state molecular structures and supramolecular self-assembly

Abstract

Abstract The molecular structures of [Zn(S2COR)2(hmta)], R=Et (I) and iPr (II), and [Zn(S2CNRR′)2(hmta)], R=R′=Et (III) and R=iPr, R′=CH2CH2OH (IV), feature chelating 1,1-dithiolate ligands and monodentate hmta molecules; hmta=hexamethylenetetramine. The resulting NS4 donor sets are highly distorted, with tendencies towards square pyramidal. Systematic differences in the structures are related to the greater chelating ability of the dithiocarbamate ligands leading to, e.g., elongated Zn–N bond lengths in III and IV. In the molecular packing, an unusual C–H···π(chelate ring) interaction is noted in III, which is correlated with the close to symmetric Zn–S bond lengths formed by the relevant dithiocarbamate ligand and resultant greater metalloaromatic character of the resulting ZnS2C chelate ring, and to the greater distortion of the coordination geometry compared with literature precedents. A three-dimensional architecture found for IV is sustained by hydroxyl-O-H···O, S and N hydrogen bonding.