ISSN:
1600-5740
Source:
Crystallography Journals Online : IUCR Backfile Archive 1948-2001
Topics:
Chemistry and Pharmacology
,
Geosciences
,
Physics
Notes:
The crystal and molecular structures of four novel β-ketosulfones, phenyl benzoyl(phenylhydrazono)methyl sulfone (I), phenyl benzoyl(4-nitrophenylhydrazono)methyl sulfone (II), (benzoyl)(phenyl)(phenylazo)methyl phenyl sulfone (III) and (benzoyl)(phenyl)(3-chlorophenylazo)methyl 4-tolyl sulfone (IV), have been investigated using X-ray analysis and density functional theory supplemented by ab initio Hartree–Fock calculations. The conformations of (I) and (II) are stabilized by strong intramolecular resonance-assisted hydrogen bonds formed between the sulfonyl and the α-hydrazono moieties. The following increase of a positive charge on the S atoms is compensated via π-conjugation and stereoelectronic back-donation from the nearby β-carbonyl group. Compounds (III) and (IV) adopt a strongly distorted propeller shape with pivotal tetrahedral C1 atoms. Distortion mostly follows from the approximate coplanarity of the α-azophenyl and α-phenyl moieties opposite each other. The main stereoelectronic interactions involve the donation of electron density from the α-azo N2 towards the sulfonyl S and the β-carbonyl C2 atoms.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1107/S0108768100013197
