The synthetically useful SNSSbF6 is prepared, in good yield, from the reactions of S3N2Cl2 or S3N2Cl3 with stoichiometric amounts of AgSbF6 and S-8 in liquid SO2. SNSSbF6 crystallizes monoclinic in space group C2/m (a = 9.740(2) angstrom, b = 6,644(2) angstrom, c = 5.334(1) angstrom, beta = 90.58(2)degrees Z = 2). The crystal structure was determined by standard methods and refined to R-1 = 0.019 and wR(2) = 0.048. The structure consists of discrete linear centrosymmetric SNS+ cations [S-N = 1.4871(10) angstrom] and almost octahedral SbF6- anions, with weak cation-anion interactions. The lattice energy of SNSSbF6 was determined from the volume-based method as 525 +/- 32 KJ mol(-1) and the heat of formation of SNSSbF6(s) has been estimated as -1566 +/- 24 KJ mol(-1). The FT-IR, Raman, and N-14 NMR spectra are reported, as well as an in situ study of the reaction of S3N2Cl2 with AsF5 in SO2 solution.