POLYSULFONYLAMINES .52. SYNTHESIS OF TRIORGANOTIN(IV)-DISULFONYLAMIDES - SOLID-STATE STRUCTURE OF PH3SNN(SO2ME)2, CHEX3SNN(SO2ME)2 AND PH3SNN(SO2ME)2.PH3SNOH.2MECN

By reacting R3SnCl with AgN(SO2R)2 and/or R3SnOH with HN(SO2R)2, the following compounds were obtained: R3SnN(SO2Me)2, where R = Et (3), (n)Bu, Ph (5) or (c)Hex (6); Me3SnN(SO2C6H4Cl-p)2; Me3SnZ and Me3SnZ . H2O (Z = anion of benzene-1,2-disulfonimide). With dimethyl sulfoxide, 3 gives the 1/2 complex Et3SnN(SO2Me)2 . 2DMSO. An improved method of preparation is described for the structurally known aqua complex [Me3Sn(OH2)2]+[(MeSO2)2N]-. From equimolar amounts of 5 and Ph3SnOH, a 1/1 adduct is obtained, which crystallizes from acetonitrile as a labile disolvate Ph3SnN(SO2Me)2 . Ph3SnOH . 2MeCN (12a); the latter readily loses one MeCN molecule to give the more stable monosolvate. The crystallographic data are for 5 (at -95-degree-C): orthorhombic, space group Pna2(1), a 1460.9(5), b 1086.3(4), c 1344.8(4) pm, V 2.1342 nm3, Z = 4; for 6 (at -100-degrees-C): triclinic, space group P1BAR, a 1004.6(2), b 1362.6(3), c 1964.2(4) pm, alpha 81.48(2), beta 75.35(2), gamma 70.98(2)-degrees, V 2.4529 nM3, Z = 4; for 12a (at -100-degrees-C): orthorhombic, space group P2(1)2(1)2(1), a 1001.8(2), b 1873.0(5), c 2237.8(4) pm, V 4.1989 nm3, Z = 4. The crystals of 5 and 6 consist of infinite chains built from R(3)Sn groups with trigonal-planar SnC3 skeletons and (alpha-O,omega-O)-bridging dimesylamide ligands, resulting in a slightly distorted trigonal-bipyramidal (C3O2) coordination of the tin atoms (one Sn in the repeat unit of 5, two independent Sn atoms in the repeat unit of 6). The tin-oxygen distances are in the range 226-235 pm. 6 appears to be the first example of a structurally characterized tricyclohexyltin compound in which (c)Hex3Sn groups with an essentially planar SnC3 geometry are incorportated into a polymeric chain. In the structure of 12a, Ph3Sn groups are connected into infinite chains by alternating mu-O(H) and (alpha-O,omega-O)-bonded dimesylamide groups; the two independent tin atoms adopt a distorted trigonal-bipyramidal (C3O2) coordination. The bond lengths Sn-O(H) and Sn-O(S) are 213.6 and 244.0 pm for Sn(1), 212.1 and 259.0 pm for Sn(2); the bond angle Sn(1)-O(H)-Sn(2) is 139.2-degrees. One MeCN molecule is hydrogen-bonded to the mu-O(H) group, the second lies in a lattice cavity between neighbouring chains.