PREPARATION OF SALTS OF THE 5,5'-(1,4-PHENYLENE)BIS(1,3,2,4-DITHIADIAZOLYLIUM) DICATION AND OF ITS 1,2-PHENYLENE AND 1,3-PHENYLENE ANALOGS - PREPARATION AND CRYSTAL-STRUCTURE OF THE STACKED, NEUTRAL 5,5'-(1,4-PHENYLENE)BIS(1,3,2,4-DITHIADIAZOLE)

Reactions of o-, m- and p-C6H4(CN)2 with [SNS][AsF6] in liquid SO2 produced the AsF6- salts of o-, m- and p-[C6H4(activated CNSNS)2]2+ in high yield. The para-phenylene AsF6- salt was readily converted (> 75%) into other salts (Cl-, Br-, SbCl6- or S3N3-) by anion metathesis. Reduction of [p-C6H4(activated CNSNS)2]Cl2 with SbPh3 gave the bis(dithiadiazole), p-C6H4(activated CNSNS)2, which crystallizes in the triclinic space group P1BAR, with a = 5.772(1), b = 6.382(1), c = 7.491(1) angstrom, alpha = 79.21(1), beta = 82.86(1), gamma = 70.25(1)-degrees, Z = 1; R = 0.077 for 678 observed reflections. The structure shows equidistant molecular stacking of the trans isomer with weak S...S (3.214 angstrom) and S...N (3.346 angstrom) intermolecular interactions.