Hexacoordinated complexes of bivalent zinc incorporating thioether binding

The reaction of zinc(II) acetate dihydrate with dithiaalkyl-substituted triazene 1-oxides, [RN(O)NNHC6H4S]2(CH2)2 (H2RL; RMe, Ph) has afforded light-yellow Zn(MeL) and light-green Zn(PhL).½CH2Cl2, the first hexacoordinated of zinc bonded by acyclic ligands incorporating thioether sites. Spectral features ff the complexes are briefly noted. Both the complexes have been structurally characterized revealing distorted octahedral binding of the metal ion in ZnO2N2S2 coordination spheres; the ZnO, ZnN and ZnS distances lie in the ranges 2.056(7)−2.105(8), 2.005(8)−2.029(8) and 2.649(4)−2.720(3) Å, respectively. Crystal data: Zn(MeL): monoclinic, space group P21/c, a = 26.529(9), b = 7.974(3), c=19.396(8) Å, β = 110.57(3)°, V=3842(3) Å3, Z = 8, R = 5.40%, Rw = 5.73%; Zn(PhL).½CH2Cl2; orthorhombic, space group Pbcb, a = 9.540(3), b = 19.449(6), c = 29.534(8) Å, V=5480(3) Å3, Z = 8, R = 5.65%, Rw = 5.42%