Metal Substitution and Solvomorphism in Alkylthiolate-Bridged Zn and HgZn Metal Clusters.

The impact of substituting Hg(II) for Zn(II) in a thiolate-bridged trinuclear cluster with parallels to a metallothionein metal cluster was investigated. A new solvomorph of [Zn(Zn)](ClO) () ( = -(2-pyridylmethyl)--(2-(ethylthiolato)-amine) and five solvomorphs of a new compound [Hg(Zn)](ClO) () were characterized by single-crystal X-ray crystallography. The interplay of hydrogen bonding and aromatic-packing interactions in producing lamellar, 2D lamellar, and columnar arrangements of complex cations in the crystalline state is discussed. Both variable temperature proton nuclear magnetic resonance and electrospray ion-mass spectrometry (ESI-MS) suggest that the complex ions of and are the predominant solution species at moderate concentrations. ESI-MS was also used to monitor differences in metal ion redistribution as was titrated with Hg(ClO) and [Hg(ClO)]. These studies document the facile replacement of Zn(II) by Hg(II) with the preservation of the overall structure in thiolate-rich clusters.