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]aneNS2O (L1) and N-(2-pyridylmethyl)-[12]aneNS3 (L2) ([12]aneNS2O = 1-aza-4,10-dithia-7-oxacyclododecane, [12]aneNS3 = 1-aza-4,7,10-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 = L1 (1), L2 (2); M = Cd, X = I, L = L1 (3), L2 (4); M = Hg, X = Cl, L = L1 (5), L2 (6)]. The X-ray diffraction studies confirmed the formation of the new species 3–6, with [LMX]+ cations and [MX4]2− anions, while for the zinc(II) complex 1 the determined structure corresponds to the hydrolysis product of formula [L1Zn]2[ZnCl3]2[Zn2Cl6]·2H2O (1h), with [L1Zn(H2O)]2+ cations and [ZnCl3(H2O)]− and [Zn2Cl6]2− anions. In all complexes the metal ion is hexacoordinated in cations, while in anions the metal is tetrahedrally surrounded by halido ligands.