Polysulfonylamine, CV. Die ersten N,N-disulfonylierten Sulfinsäureamide: Synthese und Kristallstrukturen von RS(O)-N(SO2Me)2 (R = Me, CCl3) / Polysulfonylamines, C V. The First N,N -Disulfonylated Sulfinic Amides: Synthesis and Crystal Stru ctures of RS(O)-N(SO2Me)2 (R = Me, CCl3)

Abstract

Abstract The novel sulfinamides RS(O) -N(SO2Me)2, where R = Me (1a) or CCl3 (1b), were obtained by treating the corresponding sulfinyl chlorides with Me3SiN(SO2Me)2 or AgN-(SO2Me)2, respectively. A presumedly ionic 1:1 adduct of 1b with 4-dimethylaminopyridine was isolated and analytically characterized. In the crystals of 1a (monoclinic, space group P21/c) and 1b (monoclinic, P21/c) , the molecules feature approximately planar NS3 moieties, unusually long S(O) -N bonds and, in the case of 1b, an extremely long S(O) -C bond [for la and 1b, in order: sum of bond angles at nitrogen 359.5 and 357.1°, S(O) -N 178.2(2) and 173.6(2) pm, S(O) -C 178.8(2) and 194.1(2) pm]. In both molecular structures, an attractive S(O) ··· O 1,4-interaction leads to a 7.3° discrepancy 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 atoms of two adjacent molecules, whereas in 1b the molecules are associated into parallel chains via a bonding Cl ⋯ O(sulfonyl) interaction.