N-(sulfinylimine)chlorocarbonylsulfane, ClCOSNSO (I), was prepd. by treating ClCOSCl with Hg(NSO)2. The crystal structure of I was detd. by x-ray diffraction of crystals grown at low temp. using a miniature zone-melting procedure. I exhibits only 1 form with Cs 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 to the S:O double bond. Skeletal parameters were given. These exptl. parameters compare satisfactorily with those obtained by ab initio HF and DFT calcns. The best agreement was found with the B3PW91/6-31+G* calcn. These quantum-chem. methods were also used to predict the vibrational spectra, providing good agreement with the exptl. Raman spectra measured from a liq. sample. Anal. of the vibrational spectra provides a sound basis for the detn. of the conformation and configuration of R-N:S:O compds. Raman excitation profiles were detd. at 514-413 nm. Most of the modes are predominantly enhanced via the p -> p* transition at 296 nm, but addnl. intensity is derived from low-electronic transitions at .apprx.450 and 430 nm which are too weak to be detectable in the UV/VIS absorption spectra.