The crystal structure of N-sulfinylimine fluorocarbonylsulfane, FC(O)SNSO, was detd. by X-ray diffraction anal. from crystals obtained at 271 K using a miniature zone melting procedure. The mol. exhibits only one form with Cs symmetry: the C:O double bond syn with respect to the S-N single bond, C-S single bond anti to the N:S double bond and S-N single bond syn with respect to the S:O double bond. Theor. calcns. using different levels of approxns. were carried out. They reproduce both exptl. parameters and vibrational data very well. The extension of the pre-resonance Raman effect is assocd. with the planarity of the mol. Overtone and combination bands are obsd. in these spectra.