Polysulfonylamines .77. Synthesis of new triorganoelement(IV) di(fluorosulfonyl)amides R(3)EN(SO2F)(2) (E=Si, Ge, Sn, Pb) and crystal structures of Me(3)PbN(SO2F)(2) and CsN(SO2F)(2)

The following compounds were prepared for the first time and/or by new procedures [Z=N(SO2F)(2)]: Me(3)SiZ by transamination of HZ with (Me(3)Si)(2)NH; Ph(3)SiZ (1b), Ph(3)SnZ (3f), Me(3)PbZ (4a) and Ph(3)PbZ (4b) by metathesis of the corresponding R(3)ECl with AgZ or AgZ . C6H6; Me(3)GeZ (2), Me(3)SnZ, 4a and 4b by acidolysis of R(4)E with HZ; degrees Hex(3)SnZ (3e) by neutralization of degrees Hex(3)SnOH with HZ. Compounds 1b, 2, 3e, 3f, 4a and 4b have not been reported previously. The crystal structures of 4a (triclinic, space group P (1) over bar) and of Cs(+)Z(-) (8; monoclinic, space group P2(1)/n) were determined by low-temperature X-ray diffraction. The asymmetric unit of 4a consists of an ion pair Me(3)Pb(+)Z(-), connected by a lead-nitrogen bond and a weak lead-oxygen interaction (Pb-N 260.3, Pb ... O 337.5 pm). The pairs are linked by a lead-oxygen interaction (Pb-O' 261,5 pm) to form parallel chains and further by five independent C-H ... O hydrogen bonds (H ... O 250-275 pm) to form a three-dimensional network. In the crystal of 8, the anion is surrounded by seven cations, displaying eleven Cs-X bonding interactions (1x Cs-N 321.1 pm, 6x Cs-O in the range 308.5-323.6 pm, 2x Cs-F337.3 and 338.0 pm, 1x Cs-F 369.5 pm and 1x Cs-O 375.3 pm). The irregular coordination polyhedron of the cation is best described by a coordination number of 9 + 2. The conformation of Z(-) in both structures does not deviate appreciably from the pseudo C-2-symmetry that is observed for the same anion in onium salts.