Polysulfonylamines. CXVI. Destructive complexation of the dimeric diorganyltin(IV) hydroxide [Me2Sn(A)(mu-OH)](2) (HA = benzene-1,2-disulfonimide): Formation and structures of the mononuclear complexes [Me2Sn(A)(2)(OPPh3)(2)] and [Me2Sn(phen)(2)](2 circle plus) center dot 2A(circle minus) center dot MeCN

Destructive complexation of the dimeric hydroxide [Me2Sn(A)(mu-OH)](2), whe re A(-) is deprotonated benzene-1,2-disulfonimide, with two equivalents of triphenylphosphine oxide or 1,10-phenanthroline in hot MeCN produced, along with Me2SnO and water, the novel coordination compounds [Me2Sn(A)(2)(OPPh3 )(2)] (3, triclinic, space group P (1) over bar) and [Me2Sn(phen)(2)](2+) . 2A(-) . MeCN (4, monoclinic, P2(1)/c). In the uncharged all-trans octahedr al complex 3, the heteroligands are unidentally O-bonded to the tin atom, w hich resides on a crystallographic centre of inversion [Sn-O(S) 227.4(2), S n-O(P) 219.6(2) pm, cis-angles in the range 87-93 degrees, anionic ligand p artially disordered over two equally populated sites for N, two S and non-c oordinating O atoms]. The cation occurring in the crystal of 4 has a severe ly distorted cis-octahedral C2N4 coordination geometry around tin and repre sents the first authenticated example of a dicationic tin(IV) dichelate [R2 Sn(L-L')(2)](2+) to adopt a cis-structure [C-Sn-C 108.44(11)degrees]. The f ive-membered chelate rings are nearly planar, with similar bite angles of t he bidentate ligands, but unsymmetric Sn-N bond lengths, each of the longer bonds being trans to a methyl group [ring 1: N-Sn-N 71.24(7)degrees, Sn-N 226.81(19) and 237.5(2)pm; ring 2: 71.63(7)degrees, 228.0(2) and 232.20(19) pm]. In both structures, the bicyclic and effectively Cs symmetric A(-) ion s have their five-membered rings distorted into an envelope conformation, w ith N atoms displaced by 28-43 pm from the corresponding C6S2 mean plane.