Synthesis and crystal structure of Os4S11SeCl8

Abstract

A new quaternary osmium compound, Os 4 S 11 SeCl 8 , has been synthesized and its crystal structure has been determined by X-ray powder diffraction. The crystal structure of Os 4 S 11 SeCl 8 (Pbcn-d 6 , oP48, Z = 2, a = 8.8845(2), b = 11.8108(3), c = 10.9621(3) Å; 713 reflections measured, 34 parameters refined, R I = 0.0230, R p = 0.0302, R wp = 0.0413, χ 2 = 2.87) represents a new structure type of inorganic compounds. Binuclear clusters with a partly disordered arrangement of S 2 and S-Se ligands are interconnected via double Cl-bridges to form 1D-polymers [Os 2 Cl 4 (µ-S 2)(µ-S(S,Se)) 2 ] n .

Reactivity of Binary and Ternary Sulfur Halides towards Transition‐Metal Compounds

“…At transition‐metal compounds in higher oxidation states, the formation of a variety of metal halide sulfide clusters was observed . The composition of the furnished clusters strongly depends on the reaction conditions and the ratios of starting compounds, as for instance reported for the reaction of [OsO 4 ] ( 5 ) towards S 2 Cl 2 . Additional sulfur or selenium in the reaction mixture seems to be a suitable tool to induce the formation of bridging polysulfide ligands or mixed polychalcogene entities in the clusters …”