Synthesis and structure of the group 12 pyrimidinethiolate complexes ∞3[Zn(S-2-N2C4H3)2], ∞2[Cd(S-2-N2C4H3)2], [Hg(S-2-N2C4H3)2] and [Cd(S-2-N2C4H3)2(tmeda)]

The pyrimidinethiolate complexes (3)(infinity)[Zn(S-2-N2C4H3)(2)], (2)(infinity)[Cd(S-2-N2C4H3)(2)] and [Hg(S-2-N2C4H3)(2)] have been prepared by reaction Of MCl2 (M = Zn, Cd, Hg) with 2 equiv. of Me3SiS-2-N2C4H3 in organic solvents, whilst [Cd(S-2N(2)C(4)H(3))2(tmeda)] was obtained by recrystallisation of (2)(infinity)[Cd(S-2-N2C4H3)(2)] in TMEDA at 40 degrees C. The structures of the complexes were determined by single-crystal X-ray crystallography, which shows that the different metal atoms each have different coordination environments. The zinc atom in (3)(infinity)[Zn(S-2-N2C4H3)(2)] exhibits a tetrahedral coordination with one sulfur and three nitrogen atoms from pyrimidinethiolate ligands, whereas the cadmium atoms in (2)(infinity)[Cd(S-2-N2C4H3)(2)] and [Cd(S-2-N2C4H3)(2)(tmeda)] are six-coordinate with either three sulfur and three nitrogen atoms or two sulfur and four nitrogen atoms. In contrast, the mercury atoms in [Hg(S-2N(2)C(4)H(3))(2)] display a distorted square-planar coordination to a pair of chelating -S-2-N2C4H3 ligands with additional weak Hg-S interactions to adjacent molecules. While known cadmium and zinc pyrimidinethiolate complexes consist of one-dimensional chains, (3)(infinity)[Zn(S-2-N2C4H3)(2)] and (2)(infinity)[Cd(S-2N(2)C(4)H(3))(2)] form either three- or two-dimensional polymeric networks of metal atoms. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).