Hexacoordinated complexes of bivalent zinc incorporating thioether binding

Abstract

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) ų, 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) ų, Z = 8, R = 5.65%, R_w = 5.42%.