High Z’ structures of 1,2,3,5-dithiadiazolyls and of 1,2,3,5-diselenadiazolyls containing the first structurally characterized monomeric diselenadiazolyls

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Boeré, René T.
Hill, Nathan D. D.
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Royal Society of Chemistry
Crystals of 4-[3-(trifluoromethyl)phenyl]-3H-1,2,3,5-dithiadiazol-3-yl grown by slow sublimation in a three-zone furnace form in P1 ̅ with Z = 12. The six independent molecules combine into two cis-oid and one twisted dimer, which arrange in a layer structure as two elegant clusters, with non-crystallographic four-fold and two-fold symmetry, respectively. Crystals of 4-(3-cyano-5-tertbutyl-phenyl)-3H-1,2,3,5-diselenadiazol-3-yl, formed from decomposition of a bis-diselenadiazolyl, grow in two forms under different sublimation conditions using the same furnace. The α form crystallizes in P1 ̅ with Z = 6 and the β in P21/c with Z = 20. The α polymorph consists of a distorted cis-oid dimer linked electrostatically to a monomer in the asymmetric unit. These cluster with a second unit to a centrosymmetric aggregate of six heterocycles. The β polymorph consists of clusters of four cis-oid dimers that link into chains along the b axis, whereas the fifth molecule links via -C≡N∙∙∙Se supramolecular synthons into an infinite chain of monomers also along the b axis but out-of-register with the dimer chain. A carefully curated compilation of all 83 distinct 1,2,3,5-dithiadiazolyl and of all 24 distinct 1,2,3,5diselenadiazolyl crystal structures reveals an extraordinarily large number of structures with Z' > 1 (72%) and also those with Z' ≥ 3 (24%), compared to the average for organic molecules over the whole collection in the Cambridge Structure Database. This high incidence is analyzed and attributed to competing intermolecular synthons.
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Dithiadiazolyl , Diselenadiazolyl , Radical dimer , High Z' , Monomeric free radicals , Sublimation , Crystallography
Boeré, R. T., & Hill, N. D. D. (2017). High Z’ structures of 1,2,3,5-dithiadiazolyls and of 1,2,3,5-diselenadiazolyls. CrystEngComm, 19, 3698-3707. https://doi.org/10.1039/C7CE00863E