Structural and spectroscopic characterization of ClC(O)SNSO. A theoretical and experimental study

Abstract

N-(Sulfinylimine)chlorocarbonylsulfane, ClC(O)SNSO, was prepared by the reaction of ClC(O)SCl with Hg(NSO)₂. The crystal structure of ClC(O)SNSO was determined by X-ray diffraction analysis from crystals obtained at low temperature using a miniature zone melting procedure. The molecule exhibits only one form with C_s symmetry: the C=O double bond syn with respect to the S–N single bond, the C–S single bond anti to the N=S double bond and the S–N single bond syn with respect to the S=O double bond. The following skeletal parameters were determined (distances in Å, angles in degrees, errors between parentheses expressed as sigma): Cl–C=1.771(2), C=O=1.184(3), C–S=1.750(2), S–N=1.666(2), N=S=1.534(2), S=O=1.455(2), ClCO=122.9(2), ClCS=107.1(1), OCS=130.0(2), CSN=97.4(1), SNS=122.3(1). NSO=118.0(1), OCSN=-1.9, ClCSN=178.0, CSNS=-178.0, SNSO=-1.2. These experimental parameters compare satisfactorily with those obtained by abinitio and DFT calculations. The best agreement was found with the B3PW91/6–31+G* calculation. These quantum chemical methods were also employed to predict the vibrational spectra providing a good agreement with the experimental Raman spectra measured from the liquid sample. It is shown that the analysis of the vibrational spectra provides a sound basis for the determination of the conformation and configuration of R–N=S=O compounds. Raman excitation profiles were determined in the range from 514 to 413 nm. Most of the modes are predominantly enhanced via the π→π* transition at 296 nm but additional intensity is derived from low-electronic transitions at ca. 450 and 430 nm which are too weak to be detectable in the UV/VIS absorption spectra.

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