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Sublimation of 1,2,3,5-dithiadiazolyl in vacuo affords a triclinic phase of the dimer [HCN[sub 2]S[sub 2]][sub 2]. The crystals belong to the space group P[bar 1], a = 6.816(3), b = 13.940(2), c = 14,403(3) [angstrom], [alpha] = 116,830(14), [beta] = 98,64(3), [gamma] = 99,18(3)[degrees], FW = 212.4 (for [HCN[sub 2]S[sub 2]][sub 2][center dot][N[sub 2]][sub 0.08]), Z = 6. The crystal structure consists of stacked dimers, with three dimers per aymmetric unit. Pairs of asymmetric units, related by an inversion center, generate a pinwheel motif consisting of six dimers. The columnar structure associated with these pinwheels forms close-packed sets of [open quotes]molecular tubes[close quotes]. Cosublimation of the radical in the presence of iodine in the mole ratio (HCN[sub 2]S[sub 2]:I = 5:1) yields an iodine-doped hexagonal phase of composition [HCN[sub 2]S[sub 2]][sub 6][I][sub 1.1]. Crystals of this material belong to the space group P6[sub 1], a = b = 14.132(16), c = 3.352(5) [angstrom]. FW = 128.20, Z = 6. The crystal structure consists of sixfold pinwheels in which the now evenly spaced HCN[sub 2]S[sub 2] rings form a spiral about the 6[sub 1] axis. The iodine atoms lie within the columnar cavity of the pinwheels in a disordered array wrappedmore » tightly about the sixfold screw axis. The single-crystal conductivity of the doped material is 15 S cm[sup [minus]1] at room temperature. Raman spectroscopic and magnetic susceptibility measurements on the doped material are reported. 22 refs., 6 figs., 4 tabs.« less

journal of the american chemical society

Molecular conductors from neutral-radical charge-transfer salts: preparation and characterization of an I doped hexagonal phase of 1,2,3,5-dithiadiazolyl ([HCN2S2].bul.)