The RhX_n(X=S,Se,Te) Coordination polyhedra in crystal structures

摘要

The Voronoi-dirichlet polyhedra (VDP) and the method of intersecting spheres were applied to crystal-chemical analysis of all known compounds whose structures contain rhodium atoms surrounded by chalcogen atoms.The influence of the rhodium valence state and the nature of the chalcogen on the main features of Rh stereochemistry are siscussed.Rhodium atoms exhibit coordination numbers of 6,5,or 4 with respect to S,Se,or Te atoms;in addition to the bonds with chalcogens,rhodium can form 1 to 4 bonds with metal atoms.The VDPvolume for Rh(III),Rh(2.67),and Rh(II) atoms in selenides andtellurides very weakly depends on the valence state,whereas in the caseof sulfides,the volume increases rather regularly with a decrease in themetal oxidation number from Rh(III) to Rh(I).