2-Ammoniumethanethiolate, -SCH2CH2NH3+, the first structurally characterized zwitterionic ammoniumthiolate, is the stable form of cysteamine (HL) in the solid state and in aqueous solution. Reactions of ZnCl2, Cd(Oac)2, and HgCl2 with cysteamine and NaOH in a 1:2:2 ratio, respectively, lead to the homoleptic complexes ML2. Their single-crystal X-ray structures demonstrate basic differences in the coordination chemistry of Zn-II, Cd-II, and Hg-II. While chelating N,S-coordination modes are found for all metal ions, Zn-II forms a mononuclear complex with a distorted tetrahedral Zn(N2S2) coordination mode, whereas Hg-II displays a dimer with Hg(N2S2) coordinated monomers being connected by two long (HgS)-S-... contacts. Solid-state Hg-199 NMR spectra of HgL2 and [Hg(HL)(2)]Cl-2 reveal a low-field shift of the signals with increasing coordination number. Strong and nearly symmetric Cd-S-Cd bridges in solid CdL2 lead to a chain structure, Cd-II displaying a distorted square pyramidal Cd(N2S3) coordination mode. The ab initio [MP2/LANL2DZ(d,f)] structures of isolated ML2 show a change from a distorted tetrahedral to bisphenoidal coordination mode in the sequence Zn-II-Cd-II-Hg-II. A natural bond orbital analysis showed a high ionic character for the M-S bonds and suggests that the S-M-S fragment is best described by a 3c4e bond. The strength of the (MN)-N-... interactions and the stability of ML2 toward decomposition to M and L-L decreases in the sequence Zn > Cd > Hg. A initio calculations further suggest that a tetrahedral S-M-S angle stabilizes Zn-II against substitution by Cd-II and Hg-II in a M(N2S2) environment. Such geometry is provided in zinc-finger proteins, as was found by a database survey.