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)Å, 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.