ISSN:
0044-2313
Keywords:
Sulfoximide
;
Sulfoximidium Salts
;
Structure
;
Hydrogenbonding
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Sulfoximide and Sulfoximidium Salts - Structures and Hydrogen BondingIn 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)2S(O)NH2+Hal- ((2), Hal-=Cl-; (4), Hal-=Br-) reacts with metal halides to yield (CH3)2S(O)NH2+MHalyn- with the complex anions ((5), MHalyn-=SbCl4-; (6), MHalyn-=SbCl52-; (7), MHalyn-=SbCl6-; (8), MHalyn-=SbBr52-; (9), MHalyn-=AlCl4-). 2 crystallizes from ethanol (96%) as [(CH3)2S(O)NH2+Cl-]2 · H2O (3). The structures of 3 (monoclinic; space group P21/c; a = 917.0, b = 1344.7, c = 1080.8 pm and β = 103.8°; 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 β = 153.8°; Z = 8) are determined by X-ray analysis. In 6 Sb is coordinated in a distorted octahedra by 6 Cl in three short (mean 245,5 pm; SbCl3) and three long distances (291 to 299 pm; Cl-). Two of the chloride ions connect the Sb atoms to infinite Sb … Cl … Sb chains. Except for 7 and 9 there are bridges between the NH2 groups and the halide ions. The NH valence vibrations are discussed in view of hydrogen bonding.
Notes:
Im festen Dimethylsulfoximid (1) (orthorhombisch; Raumgruppe Pbca; a = 577,8, b = 931,2 und c = 1645,6 pm) sind zwischen den Imidgruppen N—H … N-Brückenbindungen ausgebildet. Die mit HHal darstellbaren Salze (CH3)2S(O)NH2+Hal- ((2), Hal-=Cl-; (4), Hal-=Br-) reagieren mit MHalx zu (CH3)2S(O)NH2+MHalyn- ((5), MHalyn-=SbCl4-; (6), MHalyn-=SbCl52-; (7), MHalyn-=SbCl6-; (8), MHalyn-=SbBr52-; (9), MHalyn-=AlCl4-). 2 kristallisiert aus 96% Ethanol als [(CH3)2S(O)NH2+Cl-]2 · H2O (3). Die Strukturen von 3 (monoklin; Raumgruppe P21/c; a = 917,0, b = 1344,7, c = 1080,8 pm und β = 103,8°; Z = 10), 4 (orthorhombisch; Raumgruppe Pbcn; a = 1028,9, b = 1132,6, c = 1074,1 pm; Z = 8) und 6 (monoklin; Raumgruppe C2/c; a = 2041,1, b = 1101,4, c = 3365.6 pm und β = 153,8°; Z = 8) wurden bestimmt. In 6 ist Sb verzerrt oktaedrisch von 6 Cl in drei kurzen (im Mittel 245,5 pm; SbCl3) und drei langen Abständen (291 bis 299 pm; Cl-) umgeben. Zwei der lang gebundenen Cl-Ionen verknüpfen die Sb-Atome zu unendlichen Sb … Cl … Sb-Ketten. Die NH2-Gruppen der Kationen bilden außer in 7 und in 9 H—Brückenbindungen zu den Halogenidionen. Die NH-Valenzschwingungen werden im Hinblick auf die Wasserstoffbrückenbindungen diskutiert.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19976230727
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