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The addition of CF 3 SCl (2) to the fluorinated nitriles R f CN[R f  = CF 3  (3), NSF 2  (4), NSOF 2  (5)] leads to N-perfluoromethanesulphenyl-formylimidoylchlorides CF 3 S-N = C(Cl)R ƒ  (6, 11, 12). From the reactions of SCl 2  (1) with (3) and (5), which yielded the N-sulphenyl-chlorides ClS-N = C(Cl)-R ƒ (7, 13), it proved possible also to isolate the oxidation product [CF 3 CCl 2 NSCl 2  (8)] and an oligomer of the nitrile [(NCNSOF 2 ) 3  (14)]. Dechlorination of 7 with Hg gives the corresponding di-and tri-sulphides (CF 3 C(Cl) = N-) 2 S x ; (9, 10, x =2, 3). Crystals of (14) are triclinic with a = 1133.6(5), b = 1332.6(5), c = 1715.1(8) pm, α = 109.31(3), β = 105.30(3), γ = 97.84(3)° at 170 K, Z = 8, space group P1̄. The structure was refined to R = 0.028 for 8290 diffractometer data with F &gt; 4σ (F). The four crystallographically independent molecules adopt similar unsymmetrical conformations.

Reactions of Fluorinated Nitriles with Sulphur(II) Chlorides; Crystal Structure of 2,4,6-Tris(difluorosulphoximido)-1,3,5-triazene at 170 K