The novel complexes [Zn(L)Cl] (1), [Cd(L)Cl] (2), [Hg(L)Cl] (3), {[Hg(L)Cl], NaOH, 2H(2)O} (3 center dot NaOH center dot 2H(2)O), and {[Hg-3(HL)(2)Cl-6]center dot 2H(2)O}(4) (L = -SCH2CH2NH2) were prepared and investigated by means of IR spectroscopy and single-crystal X-ray diffraction. The crystal structures of 1, 2, and 3, NaOH, 2H(2)O show chelating N, S-coordination of the cysteaminate ligand, bridging S, and terminally coordinating Cl. Apart from these common features, the coordination geometries and modes of intermolecular association are different. 1 forms a cyclic tetramer with a Zn4S4 ring, and 3, NaOH, 2H(2)O contains one-dimensional [Hg(L)Cl](n) chains with S-bridged Hg atoms. Zn and Hg atoms in 1 and 3, NaOH, 2H(2)O are tetracoordinate with a distorted tetrahedral M(CINS2) geometry (M = Zn, Hg). Each Cd atom of 2 binds to three S atoms and vice versa, such that layers of distorted Cd3S3 hexagons are formed. 2 is the first example for a compound exhibiting a group 12-group 16 layer structure, which can be described as an analogue of a graphite layer. Additionally, each Cd atom binds to a chlorine atom and a nitrogen atom from a cysteaminate ligand resulting in pentacoordination with a distorted trigonal bipyramidal Cd(CINS3) geometry. 4 contains two differently coordinate Hg atoms. One displays a distorted trans-octahedral Hg(Cl4S2) geometry, while the other is coordinated by four Cl atoms and one S atom and additionally forms a long Hg,,, Cl contact.