The first X-ray crystal structure of a mercury(II) complex with an SP(N)(3)-based ligand: Synthesis and crystal structure of SP(NC5H10)(3) and [Hg{SP(NC5H10)(3)}Cl-2](2)

摘要

The synthesis, spectral characteristics (IR and NMR), elemental analysis and X-ray crystal structure of phosphorothioic triamide SP(NC5H10)(3) (1) and its dinuclear mercury(II) complex [Hg-2(-Cl)(2)(Cl)(2){SP(NC5H10)(3)}(2)] (2) were investigated. A survey using the Cambridge Structural Database (CSD, version 5.38, May 2017) shows structures of coordination compounds of Au, Ag, Cd, Cu, Li, Mo, Ni, Pd, Te, Ti, Zn, and Zr with sulfur-donor SP(N)(3)-based ligands; the complex 2 is the first example of a mercury complex with the SP(N)(3)-based ligand studied by X-ray crystallography. Valence bond calculation was performed for the Hg-S bond in 2 and compared with the Hg-O bond in the only structure with a Cl2Hg-OP(N)(3) structural motive in the CSD. The calculation confirms a more covalent nature of the Hg-S bond with respect to the Hg-O bond made by the EP(N)(3)-based ligands (E=S, O). The supramolecular structures based on C-HS=P contacts in 1 and C-HS?P and C-HCl-Hg assemblies in 2 are discussed.