INTRAMOLECULAR SULPHUR(II)-OXYGEN INTERACTION IN SULPHIDES AND DISULPHIDES WITH 2-METHOXYCARBONYLPHENYL AND 2-NITROPHENYL GROUPS: AN X-RAY STUDY

Article abstract of DOI:10.1016/0022-2860(84)85031-0

The molecular structures of methyl 2-(methylthio)benzoate, dimethyl 2,2'-dithiodibenzoate, dimethyl 2,2'-thiodibenzoate, methyl 2-(2-nitrophenylthio)benzoate, 2,2'-dinitrodiphenyl sulphide and methyl 2-(2-nitrophenylthio)phenylacetate exhibiting S(II)...O(carbonyl) or S(II)...O-(nitro) close contact have been investigated by X-ray diffraction.Planar (ArSMe), equatorial (Ar2S2) and skew (Ar2S) conformations are explained by steric and conjugative effects and sulphur(II)-oxygen interaction.Linear and nonlinear X-S...O close contacts resulting from favourable ''bond direction'' and unfavourable ''lone-pair direction'' approaches (2.619-2.722 and 2.900-3.402 Angstroem, respectively) are discussed in detail.Possible aryl ring positions, the geometry of rings with S...O contact and the nature of counter-atom (X=C, S) are considered as decisive factors.The results are consistent with different neighbouring group effects found earlier for o-CO2Me, o-CH2CO2Me and o-NO2 groups.Data support the mutual dependence of S-S and S...O distances in compounds with a linear S-S...O arrangement.Other bond lengths, e.g.C=O, N=O and S(II)-C_ar are not affected significantly by sulphur-oxygen interaction.