POLYSULFONYL AMINES .42. AN AQUASILVER(I) COMPLEX WITH AN AG(MU-H2O)2AG STRUCTURAL UNIT - CHARACTERIZATION OF 1,1,3,3-TETRAOXO-1,3,2-BENZODITHIAZOLIDO)SILVER(I) BY X-RAY-DIFFRACTOMETRY AND THERMAL-ANALYSIS

The title compound C6H4(SO2)2NAg.H2O, where C6H4(SO2)2N- is the anion of 1,2-benzenedisulfonimide, crystallizes in the monoclinic space grou p C2/m with (at -95-degrees-C) a = 1 129,7(3), b = 1196.1(3), c = 810. 7(2) pm, beta = 124.25(2)-degrees, V = 0.9055 nm3, Z = 4, D(x) = 2.524 Mg m-3. The crystal packing consists of Ag(mu-H2O)2Ag{mu-C6H4(SO2)2N }2!n bands with crystallographic mirror symmetry, associated into laye rs by H-bonds with O(W) ... O(S) 289.7 pm. The Ag(mu-H2O)2Ag moiety fo rms a planar four-membered ring with Ag-O(W)-Ag 97.3-degrees O(W)-Ag-O (W) 82.7-degrees, and Ag ... Ag 372.1 pm. In the Ag{C6H4(SO2)2N}2Ag' u nit, the anions act as tridentate (N, 1-O, 3-O)-ligands: One is N-bond ed to Ag and O,O-chelated to Ag', the other N-bonded to Ag' and O,O-ch elated to Ag. The silver atoms are (O4N)-pentacoordinate, with nitroge n in the apical position of a distorted square pyramid Ag-N 223.6, Ag -O(W) 247.8, Ag-O(S) 259.4 pm!. The thermochemical behaviour of the hy drate was investigated by thermal analysis and calorimetry. Water is o nly released at temperatures above 220-degrees-C. The dehydration enth alpy at 298 K is +13.9 kJ mol-1.