Preparation and crystal and molecular structure of a polymeric bis(sulphinylnitrilo)sulphur complex of silver(I): [Ag4{S(NSO)2}9][AsF6]4·SO2

Abstract

The title compound was isolated from the reaction of AgAsF6 with S(NSO)2 in liquid SO2. It crystallises in the rhombohedral space group R3c, with a=b= 18.249(5), c= 35.95(2)A, and Z= 6. The structure was refined to R= 0.070 for 1 653 unique observed diffractometer data. There are two crystallographically independent silver atoms. One lies on a three-fold axis and is octahedrally co-ordinated by the terminal oxygens of six S(NSO)2 ligands; the other occupies a general position and is unsymmetrically co-ordinated by the nitrogen atoms of three S(NSO)2 ligands. The ligands bridge the silver atoms to form a polymeric cationic network; the AsF6– anions and SO2 solvent molecule occupy holes in this network without themselves acting as ligands.