POLYSULFONYLAMINES .35. SYNTHESIS, X-RAY STRUCTURAL-ANALYSIS AND HIGH-RESOLUTION SOLID-STATE NMR-SPECTRA OF IONIC ORGANOTIN(IV) DIMESYLAMIDES [ME3SN(NH3)2][N(SO2ME)2] AND [ME2SN(DMSO)4][N(SO2ME)2]2

[Me3Sn(NH3)2][N(SO2Me)2](4) was prepared by treating Me3SnN(SO2Me)2 (1) With liquid ammonia; single crystals suitable for X-ray diffraction were grown from a solution in liquid ammonia by slow evaporation of the solvent at -42-degrees-C. [Me2Sn(DMSO)4][N(SO2Me)2]2 (5) was obtained from dimethyl sulfoxide and Me2Sn[N(SO2Me)2]2 or 1 in refluxing CCl4, the co-product in the latter case being SnMe4. The crystallographic data at -95-degrees-C are for 4: monoclinic, space group P2(1)/c, a 650.3(2), b 1464.7(3), c 1479.6(4) pm, beta 94.63(2), U 1.4046 nm3, Z = 4; for 5: triclinic, space group P1BAR, a 818.3(2), b 986.6(2), c 1119.9(3) pm, alpha 79.10(2), beta 77.51(2), gamma 77.58(2)-degrees, U 0.8524 nM3, Z = 1. The structure refinement of 4 was based on 3092 reflections with F > 4sigma(F) to give R = 0.018. For 5, refinement using 3579 reflections with F > 4sigma(F) yielded R = 0.021. The crystals of both compounds consist of discrete (MeSO2)2N- anions and Me3Sn(NH3)2+ or Me2Sn(DMSO)42+ cations, respectively. The structures of the anions are similar to those observed in other ionic dimesylamides. In the cation of 4, the tin atom has an axially distorted trigonal-bipyramidal environment with apical NH3 molecules (Sn-N 232.8 and 238.3, Sn-C 211.7-212.4 pm, N-Sn-N 179.2, C-Sn-C 118.1-122.1, N-Sn-C 88.0-91.3-degrees). The tin atom in the centrosymmetric cation of 5 displays trans-octahedral geometry with four DMSO molecules bonded through their oxygen atoms (Sn-C 211.4, Sn-O 219.9 and 221.4 pm, (O-Sn-O)cis 88.9 and 91.1, O-Sn-C 86.8-93.2-degrees). The oxygen centres of the sulfoxide ligands are sp2-hybridized with Sn-O-S 121.8 and 123.1-degrees, S-O 154.4 and 155.4 pm. 5 is the first example of a structurally characterized tin(IV)-sulfoxide complex in which four sulfoxide ligands are coordinated to a single tin centre. C-13, N-15 and Sn-119 CP/MAS NMR spectra of solid 4 and 5 agree very well with the X-ray diffraction results. In both cases, the isotropic Sn-119 chemical shifts and their tensorial properties support the nearest-neighbours-environment as shown by crystallography. The slight inequivalences of the NH3 and DMSO ligands, respectively, are mirrored in the N-15 and C-13 CP/MAS spectra of 4 and 5. The Sn-119 CP/MAS spectrum of 4 is complicated by the simultaneous presence of scalar and quadrupolar coupling of two inequivalent N-14 nuclei with Sn-119.