POLYSULFONYLAMINES, CV - THE FIRST N,N-DISULFONYLATED SULFINIC AMIDES- SYNTHESIS AND CRYSTAL-STRUCTURES OF RS(O)-N(SO2ME)(2) (R = ME, CCL3)

The novel sulfinamides RS(O)-N(SO2Me)(2), where R = Me (1a) or CCl3, ( 1b), were obtained by treating the corresponding sulfinyl chlorides wi th Me3SiN(SO2Me)(2) or AgN-(SO2M)(2), respectively A presumedly ionic 1:1 adduct of 1b with 4-dimethylaminopyridine was isolated and analyti cally characterized. In the crystals of 1a (monoclinic, space group P2 (1)/n) and 1b (monoclinic, P2(1)/c), the molecules feature approximate ly planar NS3 moieties, unusually long S(O)-N bonds and, in the case o f 1b, an extremely long S(O)-C bond [for 1a and 1b, in order: sum of b ond angles at nitrogen 359.5 and 357.1 degrees, S(O)-N 178.2(2) and 17 3.6(2) pm, S(O)-C 178.8(2) and 194.1(2) pm]. In both molecular structu res, an attractive S(O)... O 1,4-interaction leads to a 7.30 discrepan cy in the S(O)-N-SO2 angles. The crystal packing of 1a displays a tape (double-chain) motif generated by two prominent intermolecular C-H .. . O interactions involving one MeSO2 group and the sulfinyl oxygen ato ms of two adjacent molecules, whereas in 1b the molecules are associat ed into parallel chains via a bonding Cl ... O(sulfonyl) interaction.