Structure of inorganic–organic hybrid polymer assembled by mercury(II) iodide and sulfur-rich compound

The metal complex, [Hg₂I₄(PEDT)]_∞ (1), PEDT=4,5-(phenyl-ethylenedithio)-1,3-dithiole-2-thione, has been synthesized and characterized by single crystal X-ray diffraction. It is found to be an unusual organic–inorganic hybrid structure. The inorganic layer is composed of chains of Hg with bridging I, in one case doubly bridged and in the other singly, interconnected by further bridging I to complete the two dimensional connectivity. The organic layers contain pairs of centrosymmetrically related, and therefore head to tail, face to face molecules. Each molecule of such a pair participates in the formation of short SS contacts with a molecule of a centrosymmetrically related neighboring molecule pair thus creating chains of molecules. The connectivity within the organic layer is completed by C–Hπ contacts between the chains. Connectivity between the organic and inorganic layers is achieved by participation of the thione S in the coordination of one type of Hg.