| Abstract: | Polysulfonylamines. CLXIV. Crystal Structures of Metal Di(methanesulfonyl)amides. 13. Dithallium Tris(dimesylamido‐N)argentate: A Two‐Dimensional Coordination Polymer The complex salt Tl2Ag{N(SO2Me)2}3] (monoclinic, space group P21/n, Z′ = 1) was obtained by serendipity. Its layer structure displays two unprecedented characteristics, viz. one (MeSO2)2N— ion that strongly deviates from the C2‐symmetric standard conformation of this species and approximates to mirror symmetry, and a tris(dimesylamido)argentate anion featuring a trigonal‐planar AgN3 core with Ag—N bond lengths of 225.6(6), 226.0(6), 236.3(6) pm and N—Ag—N angles in accordance with VSEPR concepts 149.8(2) vs. 102.8(2) and 107.3(2)°]. The independent thallium ions are coordinated by the complex anions to form monolayer substructures, in which Tl(1) attains an O6 and Tl(2) an O5 environment; the monolayers are associated into bilayers via one independent set of Tl(2)—O bonds that concomitantly raise the coordination number for Tl(2) to six. Both TlO6 polyhedra may be viewed as extremely distorted octahedra reflecting the stereochemical activity of the 6s lone pair of electrons. The two‐dimensional Ag—N/Tl—O bonding system is reinforced by a three‐dimensional network of weak C—H···O hydrogen bonds. |
