Electron-diffraction investigation of the molecular structure of methyl chlorosulphate

Abstract

An electron-diffraction structure analysis has yielded the following bond lengths (r_a) and bond angles of the title compound: SO 1.419(3), S–O 1.562(4), and S–Cl 2.023(4)Å; Cl–S–O 102.8(14), O–SO 108.7(8), Cl–SO 106.4(6), OSO 122.2(15), and S–O–C 114.4(11)°. A gauche form characterized by a rotation angle of 74° around the S–O bond (0° corresponds to a form in which the O–C bond eclipses the S–Cl bond) prevails in the vapour phase. The sulphur bond configuration is consistent with other simple sulphone structures. Both valence-shell electron-pair repulsions and non-bonded interactions are thought to be responsible for the observed geometrical variations.