Preparation of salts of the 5,5′-(1,4-phenylene)bis(1,3,2,4-dithiadiazolylium) dication and of its 1,2- and 1,3-phenylene analogues. Preparation and crystal structure of the stacked, neutral 5,5′-(1,4-phenylene)bis(1,3,2,4-dithiadiazole)

Abstract
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([graphic omitted])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-([graphic omitted])2]Cl2 with SbPh3 gave the bis(dithiadiazole), p-C6H4([graphic omitted])2, which crystallises in the triclinic space group P, with a= 5.772(1), b= 6.382(1)c= 7.491(1)Å, α= 79.21(1), β= 82.86(1), γ= 70.25(1)°, 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 Å) and S N (3.346 Å) intermolecular interactions.

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