Group 12 metal complexes of mixed thia/aza and thia/oxa/aza macrocyclic ligands

The coordination behaviour of the macrocyclic ligands N-(2-pyridylmethyl)-[12]aneNS(2)O (L-1) and N-(2-pyr-idylmethyl)-[12]aneNS(3) (L2) ([12]aneNS(2)O = 1-aza-4,10-dithia-7-oxacyclododecane, [12]aneNS(3) = 1-aza4,7,10-trithia-cyclododecane) was studied in complexation reactions with ZnCl2, CdI2 and HgCl2. The NMR and mass spectra suggest the formation of the ionic species [LMX](2)[MX4] [M = Zn, X = Cl, L = L-1 (1), L-2 (2); M = Cd, X = I, L = L-1 (3), L-2 (4); M = Hg, X = Cl, L = L-1 (5), L-2 (6)]. The X-ray diffraction studies confirmed the formation of the new species 3-6, with [LMX](+) cations and [MX4](2-)& nbsp;anions, while for the zinc(II) complex 1 the determined structure corresponds to the hydrolysis product of formula [(LZn)-Zn-1](2)[ZnCl3](2)[Zn2Cl6]center dot & nbsp;2H(2)O (1h), with [(LZn)-Zn-1(H2O)](2+) cations and [ZnCl3(H2O)](-) and [Zn2Cl6](2-)& nbsp;anions. In all complexes the metal ion is hexacoordinated in cations, while in anions the metal is tetrahedrally surrounded by halido ligands.