Molecular architecture and supramolecular association in the zinc-triad 1,1-dithiolates. Steric control as a design element in crystal engineering?

A survey of the fascinating structural chemistry of the zinc-triad 1,1-dithiolates is presented. A total of twelve distinct structural motifs are delineated ranging from monomeric, dimeric, tetrameric, linear polymeric, layer to 3-dimensional network architectures. Such diversity arises from the prevalent secondary bonding interactions, i.e. A⋯S, operating in the solid state. While the variation in structure suggests that the control of secondary interactions is difficult, a possible design tool for crystal engineering is identified, namely by moderating the steric profile of thiolate-bound organic substituents, at least for the systems described herein.