Molecular structure of methyl-2-nitrophenyl sulphide. An electron-diff raction study

Abstract

The molecular structure of methyl-2-nitrophenyl sulphide has been determined in the gas phase by electron diffraction. The following values were obtained for bond lengths (r_g/Å): S—C(aryl), 1.774 ± 0.006; S—C(methyl), 1.809 ± 0.006; N—C, 1.468 ± 0.006; (CC)_mean, 1.400 ± 0.003; (ON)_mean, 1.227 ± 0.003; (C—H)_mean, 1.107 ± 0.006; and bond angles (°): C(methyl)—S—C(aryl), 104.6 ± 0.7; S—CC(N), 117.6 ± 0.7; (S)CC—N, 124.8 ± 0.7; C—NO, 117.9 ± 0.8 and 117.3 ± 0.8; NO⋯S 92.6 ± 0.5; O⋯S—C(aryl) 76.1 ± 0.4. The S⋯O non-bonded distance (r_a= 2.769 ± 0.009 Å) is markedly shorter than the sum of van der Waals radii of the two atoms (3.25 Å), but longer than the corresponding S⋯O distance in 2-nitrobenzenesulphenyl chloride (2.414 Å), indicating the decisive influence of the “counter-atom” on the intramolecular sulphur–oxygen non-bonded interactions. The O⋯S—C(methyl) arrangement is nearly linear; the C(methyl) atom and NO₂ group are coplanar or nearly coplanar with the benzene ring.