Preparation and solid-state structures of (cyanophenyl)dithia- and (cyanophenyl)diselenadiazolyl radicals

A. W. Cordes, R. C. Haddon, R. G. Hicks, R. T. Oakley*, T. T.M. Palstra

*Corresponding author for this work

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Abstract

The preparation and solid-state characterization of the dimers of the cyanophenyl-substituted 1,2,3,5-dithia- and 1,2,3,5-diselenadiazolyl radicals [NCC6H4CN2E2] (E = S, Se) are described. Crystals of the 4-cyanophenyl derivatives 4 are triclinic, space group P1. The radicals dimerize in a cofacial fashion, with mean intradimer E- - -E spacings of 3.104/3.233 Å (E = S/Se). The dimer units form ribbonlike arrays connected by head-to-tail CN- - -E contacts. The ribbons are packed in an antiparallel fashion with no close interdimer E- - -E contacts. The 3-cyanophenyl sulfur derivative 5 crystallizes in two phases. The α-phase, along with the isomorphous selenium compound, belongs to the monoclinic space group P21/n. As in the 4-cyano derivatives, the radicals dimerize cofacially, generating ribbons connected by head-to-tail CN- - -E contacts. The ribbons, however, are layered with CN2E2 rings oriented into stacks parallel to the a axis. In addition to short intradimer E- - -E contacts (mean values = 3.13 (2)/3.27 (4) Å for E = S/Se), there are relatively short interdimer E- - -E contacts (mean values = 4.26 (5)/4.15 (5) Å (E = S/Se) along the stacking axis. The β-phase of the 3-cyanophenyl sulfur compound 5, monoclinic space group P21/n, forms discrete dimers associated in a trans antarafacial fashion, with intradimer S- - -S contacts of 3.121 (1) Å; there are no close interdimer S- - -S contacts. The 2-cyanophenyl selenium derivative 6 crystallizes in the polar space group P21. In this structure also the dimer units are laced together by short CN- - -Se contacts. The dimers form stacks parallel to the b axis, with mean intradimer and interdimer Se- - -Se contacts of 3.312/4.083 Å, respectively. Lattice constants for the six structures are: 4 (E = S), C8H4N3S2, a = 10.466 (3) Å, b = 10.342 (2) Å, c = 9.169 (2) Å, α = 104.97 (2)°, β = 112.97 (2)°, γ = 69.84 (2)°, V = 849.0 (3) Å3, Z = 4; 4 (E = Se), C8H4N3Se2, a = 10.478 (4) Å, b = 10.780 (4) Å, c = 9.432 (4) Å, α = 107.16 (3)°, β = 115.23 (2)°, γ = 68.39 (3)°, V = 883.8 (6) Å3, Z = 4; 5 (E = S, α-phase), C8H4N3S2, a = 7.295 (3) Å, b = 20.488 (2) Å, c = 11.276 (2) Å, β = 95.54 (2)°, V = 1676.0 (7) Å3, Z = 8; 5 (E = Se), C8H4N3Se2, a = 7.364 (8) Å, b = 21.085 (2) Å, c = 11.119 (4) Å, β = 94.91 (5)°, V = 1720 (7) Å3, Z = 8; 5 (E = S, β-phase), C8H4N3S2, a = 8.782 (1) Å, b = 5.638 (1) Å, c = 17.128 (4) Å, β = 102.94 (2)°, V = 826.5 (6) Å3, Z = 4; 6 (E = Se), C8H4N3Se2, a = 7.301 (1) Å, b = 11.883 (2) Å, c = 10.186 (1) Å, β = 101.50 (1)°, V = 866.1 (5) Å3, Z = 4.

Original languageEnglish
Pages (from-to)1802-1808
Number of pages7
JournalInorganic chemistry
Volume31
Issue number10
DOIs
Publication statusPublished - 1 Dec 1992
Externally publishedYes

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