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 L ) 2 ](ClO 4 ) 2 ( 1 ) ( L = N -(2-pyridylmethyl)- N -(2-(ethylthiolato)-amine) and five solvomorphs of a new compound [Hg(Zn L ) 2 ](ClO 4 ) 2 ( 2 ) 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 1 and 2 are the predominant solution species at moderate concentrations. ESI-MS was also used to monitor differences in metal ion redistribution as 1 was titrated with Hg(ClO 4 ) 2 and [Hg L (ClO 4 )]. These studies document the facile replacement of Zn(II) by Hg(II) with the preservation of the overall structure in thiolate-rich clusters.

Synthesis of the unusual spirobicyclic pentanuclear complex [Zn((ZnL)2(µ‐OH))2](ClO4)4·CH3CN·7H2O (1) (LH = N‐(2‐pyridylmethyl)‐N‐(2‐(methylthio)ethyl)‐N‐(2‐thioethyl)‐amine is described. Compound 1 was thoroughly characterized by a combination of X‐ray crystallography, XPRD, IR, variable temperature 1H NMR and ESI‐MS. The peripheral zinc ions of 1 have distorted trigonal bipyramidal coordination geometry provided by the NN′SS′ donor set of one L and a µ2‐hydroxido bridge to another peripheral zinc ion. The central zinc atom has a distorted tetrahedral Zn(SR)4 coordination environment provided by four µ2‐thiolate bridges from L. In crystalline form, the complex ions of 1 are largely insulated from contact by an elaborate hydrogen bond network involving µ2‐hydroxido bridges, perchlorate ions and all the solvent molecules. Dissociation of 1 in CD3CN solution and recombination to form other multinuclear complexes was investigated by variable temperature 1H NMR.

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