POLYSULFONYLAMINES .43. TRIMETHYLGERMANIUM(IV) AND TRIMETHYLLEAD(IV) DIMESYLAMIDE - SYNTHESIS AND SOLID-STATE STRUCTURES

The new compounds Me3GeN(SO2Me)2 (3) and Me3PbN(SO2Me)2 (4) were prepared from the corresponding chlorides Me3ECl and AgN(SO2Me)2 in MeCN solution. The crystallographic data at -95-degrees-C are for 3: triclinic, space group P1BAR. a 771.7(2), b 1204.1(4), c 1388.4(5) pm, alpha 66.75(3), beta 84.12(3), gamma 74.15(2)-degrees, V 1.1401 nm3. Z = 4; for 4: monoclinic, space group P2(1)/c, a 751.1(3), b 1065.5(4), c 1493.9(5) pm, beta 100.99(3)-degrees, V 1.1738 nm3, Z = 4. The crystal structure of 3 consists of two crystallographically independent, monomeric molecules with tetrahedral Ge atoms and trigonal-planar N atoms (average angle values: C-Ge-C 112.7, C-Ge-N 106.0, Ge-N-S 121.1, S-N-S 117.3-degrees). The most striking features of the molecular structure are the extremely long Ge-N bond distances of 198.2(2) and 198.5(2) pm, which are equal to the uncorrected sum of the covalent single bond radii. In the crystal structure of 4, Me3PbN(SO2Me)2 units are linked by an intermolecular Pb-O interaction (265.3(6) pm) to form infinite parallel chains. The Pb atom has a distorted trigonal-bipyramidal arrangement (N-Pb-O 169.3: average values: C-Pb-C 119.2, C-Pb-N 95.5, C-Pb-0 84.8-degrees), in which the N atom is trigonal-planar (S-N-S 119.2, mean Pb-N-S 119.8-degrees). The Pb-N distance is 248.4(6) pm, i.e. 30 pm longer than the sum of the covalent radii, suggesting a mainly ionic bond character. In both structures secondary intramolecular 1,4-interactions with Ge...O distances of 295.8 and Pb...O of 328 pm, respectively, are observed.