Structure Investigations on 4‐Halo‐1,2,3,5‐dithiadiazolyl Radicals XCNSSN• (X = F,Cl, Br): The Shortest Intradimer S···S Distance in Dithiadiazolyl Dimers

Crystals of the 4‐halo‐1,2,3,5‐dithiadiazolyl radicals (X = F, Cl, Br) were obtained by sublimation at 80 °C and 10^?2 Torr, and the structures were determined by X‐ray diffraction. The fluoro derivative crystallizes as a cisoid dimer in the space group P2₁/n, whereas the chloro and bromo derivatives crystallize isomorphous as twisted dimers in the space group C2/c. The chloro and bromo derivatives show the shortest intradimer S···S contacts of all known 1,2,3,5‐dithiadiazolyl dimers. In addition the obtained structure of ClCN₂S₂^? represents the fifth polymorph of ClCN₂S₂^? characterized by X‐ray crystallography. The structures and the packing including secondary interactions are discussed.