SULFOXIMIDE AND SULFOXIMIDIUM SALTS - STR UCTURES AND HYDROGEN-BONDING

In the solid state dimethylsulfoximide (1) (orthorhombic; space group Pbca; a=577.8, b=931.2 and c=1645.6 pm) makes intermolecular N-H ... N hydrogen bonds. The hydrogen halide salts (CH3)(2)S(O)NH(2)(+)Hal(-) ((2), Hal(-)=Cl-; (4), Hal(-)=Br-) reacts with metal halides to yield (CH3)(2)S(O)NH(2)(+)MHal(y)(n-) with the complex anions ((5), MHal(y)( n-)=SbCl4-; (6), MHal(y)(n-)=SbCl52-; (7), MHal(y)(n-)=SbCl6-; (8), MH al(y)(n-)=SbBr52-; (9), MHal(y)(n-)=AlCl4-), 2 crystallizes from ethan ol (96%) as [(CH3)(2)S(O)NH2+Cl-](2) . H2O (3). The structures of 3 (m onoclinic; space group P2(1)/c; a=917.0, b=1344.7, c=1080.8 pm and bet a=103.8 degrees; Z=10), 4 (orthorhombic; space group Pbcn; a=1028.9, b =1132.6, c=1074.1 pm; Z=8) and 6 (monoclinic; space group C2/c; a=2041 .1, b=1101.4, c=3365.6 pm and beta=153.8 degrees; Z=8) are determined by X-ray analysis. In 6 Sb is coordinated in a distorted octahedra by 6 CI in three short (mean 245,5 pm; SbCl3) and three long distances (2 91 to 299 pm; Cl-). Two of the chloride ions connect the Sb atoms to i nfinite Sb . Cl . Sb chains. Except for 7 and 9 there are bridges betw een the NH2 groups and the halide ions. The NH valence vibrations are discussed in view of hydrogen bonding.