The crystal structure of 1,4-benzenedithiol by rietveld analysis and studies on the mechanism of solid-state addition polymerization of 1,4-benzenedithiol to 1,4-diethynylbenzene

Abstract

The crystal structure of 1,4‐benzenedithiol (BDT) was determined by the Rietveld method based on the calculation of the atomic coordinates of the BDT molecule using the Molecular Mechanics Program (MMP2). The refined crystal structure of BDT was monoclinic P21/c with dimensions, a = 7.795, b = 7.290, c = 5.955 Å, β = 92.16°, z = 2. The R factor of the refined structure was 0.038. Using above results, the mechanism of solid‐state addition polymerization of BDT to 1,4‐diethynylbenzene (DEB) was studied. Sublimed BDT piles up onto glass plate substrate and forms the layer structure along with the a axis. An inclination angle of the piled BDT column was 60° toward the substrate surface. DEB crystal structure was also monoclinic P21/c with a = 4.007, b = 6.018; c = 15.340 Å, β = 91.42°, z = 2. Sublimation of equimolar mixture of BDT and DEB gave a crystal having 1 : 1 composition, in which DEB column is situated between the columns of BDT. Relative arrangement of both monomers was suitable for the addition of SH and CCH groups, since the distance between the two groups is 3.3 Å by CERIUS II calculation. Therefore, the addition polymerization of BDT to DEB easily proceeded by UV irradiation and the resulting polymer had a highly layer structure along with the a axis of BDT crystal. Tentatively estimated crystal structure of polymer obtained is monoclinic with a = 7.73, b = 7.30, c = 5.95 Å, β = 92.16°. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1621–1625, 1997

Self-Assembled Oligomeric Structures from 1,4-Benzenedithiol on Au(111) and the Formation of Conductive Linkers between Gold Nanoparticles

“…Figure b shows a high-resolution image of one of the chains, with clearly evident alternating “hobnail” features along the chains. The distance between bright spots in the image (measured across the chain axis) is ∼0.57 nm, in good accord with the calculated gas-phase distance of 0.62 nm . The model proposed in Figure places the gold adatoms at 3-fold hollow sites on the underlying lattice.…”

A η4‐Dithio‐para‐benzoquinone Metal Complex

“…The average CS bond lengths for the three independent molecules are 1.719, 1.705, and 1.710 Å, which gives an overall average of 1.711 Å and characteristic of a partial double bond character (see below). This bond length is shorter than simple CS bond of 1.796 Å reported for 1,4‐benzenedithiol11 and of 1.766 Å for 4,4′‐biphenyldithiol12 but comparable to CS bonds of 1.674–1.702 Å reported for thiourea compounds 13. To our knowledge this is the first X‐ray structure of the parent thioquinone complex.…”

Metal-Stabilized o-Quinone Methides, Thioquinones, and Selenoquinones: Trapping Important Reactive Intermediates and Beyond

“…3b The C-S bond distances for the three independent molecules I, II, and III are 1.719, 1.705, and 1.710 Å, respectively, which on average is 1.711 Å and characteristic of a partial double bond character. This bond distance is shorter than the simple C-S bond distances of 1.796 Å reported for benzene-1,4-dithiol 34 and 1.766 Å reported for biphenyl-4,4¢-dithiol, 35 but comparable to the C=S bond distances of 1.674-1.702 Å reported for several thiourea compounds and aromatic polysulfides. 36 To the best of our knowledge, this is the first X-ray structure of this parent thioquinone complex reported in the literature.…”