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The crystral structure of CCl2= NH–CCl3+SbCl6-is reported. The compound crystallizes in the monoclinic space group P21/n with a = 11.086(11), b = 9.973(12), c = 14.478(17)Å, β = 106.69(9)°, Ζ = 4. The framework of the cation is planar, with C–N bond lengths of 1.488(7) and 1.280(5)Å. The cation and the anion have one short H ••• Cl contact of 2.313(2)Å.

The crystal structure of (C6H5)3CSI is reported. It is the first structure determination of an iodine sulfane. (C6H5)3CSI crystallizes in the monoclinic space group P21/c with a - 1226.4(7) pm, b = 1398.8(18) pm, c = 941.6(8) pm, β = 96.38(8)° and Z = 4. The sulfur-iodine bond length is 240.6(4) pm corresponding to the sum of the covalent radii with 237 pm. The molecules are linked via short I···S contacts of 321.0(4) pm such that a zig-zag chain is formed.

The synthesis of CF3SCl2+AsF6-is reported. The sulfonium salt is characterised by IR, Raman, 19F and 13C NMR spectroscopy. The vibrational assignment is based on a Csmodel for the cation and assisted by a normal coordinate analysis. The crystal structure has been determined from three-dimensional diffractometer data at -133 K. The structural data for the cation are: C-F = 128.8(5) pm, C-S = 197,8(3) pm, S-Cl = 195,9(1) pm and F-C-F = 111,8(3)°, Cl-S-Cl = 104,22(5)°, C-S-Cl = 99,8(1)°.

The crystal structure of CH3C6H4S(O)2NCl2is reported. Crystals are monoclinic, space group P21/c, with a = 710.0(7), b = 1615.3(13), c = 867.2(7) pm, V = 988(2) pm3and Z = 4. The reaction with HF/SbF5yields CH3C6H4S(O)2NCl2H+SbF-6the first protonated dichloroamine salt, its vibrational -and NMR spectra are discussed

CH3S(0)C1 reacts in HF as solvent with MF5(M = As, Sb) to give products CH3S(Cl)OMF5(M = As, Sb). The new compounds are stable below 253 K and were charac­ terized by Raman and NMR spectroscopy.

Chlorosulfonium hexachloroantimonate crystallizes in the monoclinic space group C 2/m with a = 1405.5(3) pm, b = 1055.1(2) pm , c = 882.2(2) pm, β = 110.05(3)° at 169 K with 4 formula units per unit cell. A distorted octahedral coordination around sulphur is formed by three S - C l bonds and three interionic sulphur chlorine contacts. The interionic interactions in SCl3+salts of known crystal structures are discussed.