Polysulfonylamine LII. Darstellung neuer Triorganozinn(IV)-disulfonylamide. Festkoerperstrukturen von Ph3SnN(SO2Me)2, cHex3SnN(SO2Me)2 und Ph3SnN(SO2Me)2*Ph3SnOH*2MeCN

Article abstract of DOI:10.1016/0022-328X(94)80003-0

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), ⁿBu, Ph (5) or ^cHex (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 ⁺<(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 deg C): orthorhombic, space group Pna2₁, a 1460.9(5), b 1086.3(4), c 1344.8(4) pm, V 2.1342 nm³, Z = 4; for 6 (at -100 deg C): triclinic, space group P<*>, a 1004.6(2), b 1362.6(3), c 1964.2(4) pm, α 81.48(2), β 75.35(2), γ 70.98(2) deg, V 2.4529 nm³, Z = 4; for 12a (at -95 deg C): orthorhombic, space group P2₁2₁2₁, 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 R3Sn groups with trigonal-planar SnC3 skeletons and (α-O, ω-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 ^cHex3Sn groups with an essentially planar SnC3 geometry are incorporated into a polymeric chain.In the structure of 12a, Ph3Sn groups are connected into infinite chains by alternating μ-O(H) and (α-O,ω-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 deg.One MeCN molecule is hydrogen-bonded to the μ-O(H) group, the second lies in a lattice cavity between neighbouring chains. Key words: Tin; Sulfonyl; Amide; Crystal structure