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

The addition of CF SCl (2) to the fluorinated nitriles R CN[R = CF (3), NSF (4), NSOF (5)] leads to N-perfluoromethanesulphenyl-formylimidoylchlorides CF S-N = C(Cl)R (6, 11, 12). From the reactions of SCl (1) with (3) and (5), which yielded the N-sulphenyl-chlorides ClS-N = C(Cl)-R (7, 13), it proved possible also to isolate the oxidation product [CF CCl NSCl (8)] and an oligomer of the nitrile [(NCNSOF (14)]. Dechlorination of 7 with Hg gives the corresponding di-and tri-sulphides (CF C(Cl) = N-) ; (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 > 4σ (F). The four crystallographically independent molecules adopt similar unsymmetrical conformations.