POLYSULFONYL AMINES .41. A SILVER(I) HYDRATE WITH AN UNUSUAL COMPOSITION - CHARACTERIZATION OF TETRAKIS(DIMESYLAMIDO)AQUATETRASILVER(I) [AG4(N(SO2CH3)2)4(H2O)] BY X-RAY-DIFFRACTION AND THERMAL-ANALYSIS

The title compound is obtained by crystallizing AgN(SO2CH3)2 from wate r at room temperature. Crystallographic data (at -95-degrees-C): Tricl inic space group P1BAR, a = 864.6(4), b = 1211.2(5), c = 1 399.1(5) pm , alpha = 90.97(3), beta = 90.90(3), gamma = 98.25(4)-degrees, V = 1.4 496 nm3, Z = 2, D(x) = 2.608 Mg m-3. The four independent silver atoms and the water molecule form zigzag chains Ag(1)-Ag(2)-(mu-H2O)-Ag(3) ... Ag(4) ... Ag(1') with distances Ag(1)-Ag(2) 309.7, Ag(2)-O(w) 241. 8, O(w)-Ag(3) 241.4, Ag(3) ... Ag(4) 342.9, Ag(4) ... Ag(1') 361.4 pm. The catenated silver atoms are further connected by the dimesylamide anions acting as tridentate bridging (alpha-O, N, omega-O)-ligands. Th e resulting strands are interconnected into layers through one O(S)-Ag ' contact (247 pm) and one hydrogen bond O(w)-H(1) ... O'(S) per repea ting unit. Between the layers, a weak O(S) ... Ag'' interaction (271 p m) and a hydrogen bond O(w)-H(2) ... O''(S) per repeating unit are obs erved. The silver atoms Ag(1) to Ag(4) display the coordination number s 5 [NO3Ag(2), distorted trigonal bipyramid], 5 [NO2O(w)Ag(1), distort ed trigonal bipyramid], 5 [O4O(w), trigonal bipyramid], and 2 + 1 (N2, linear; plus a secondary Ag ... O contact). The dehydration of the ti tle compound and a solid-solid phase transformation in anhydrous AgN(S O2CH3)2 were quantitatively investigated by thermoconductometry and ti me- and temperature-resolved X-ray diffractometry (TXRD).