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Enhancement of the Dimensionality of Molecular π Conductors by the Selone Substitution of M(dmit)2 (M = Ni, Pd) Systems:  Newly Synthesized dmise Compounds [MexH4-xN][Ni(dmise)2]2 (x = 1−3) and Cs[Pd(dmise)2]2 (dmise = 4,5-Dimercapto-1,3-dithiole-2-selone)

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posted on 05.11.1997, 00:00 by Akane Sato, Hayao Kobayashi, Toshio Naito, Fumiko Sakai, Akiko Kobayashi
Single crystals of [Me3HN][Ni(dmise)2]2, [Me2H2N][Ni(dmise)2]2, [MeH3N][Ni(dmise)2]2, and Cs[Pd(dmise)2]2 were grown electrochemically. The crystal structures of [Me3HN][Ni(dmise)2]2, [Me2H2N][Ni(dmise)2]2, and [MeH3N][Ni(dmise)2]2 were determined. Crystal data are as follows:  [Me3HN][Ni(dmise)2]2 (C15H10NNi2S16Se4), triclinic, P1̄, a = 7.606(3) Å, b = 17.761(3) Å, c = 6.660(2) Å, α = 100.27(2)°, β = 114.93(2)°, γ = 81.84(2)°, Z = 1; [Me2H2N][Ni(dmise)2]2 (C14H8NNi2S16Se4), triclinic, P1̄, a = 7.625(3) Å, b = 17.583(5) Å, c = 6.526(2) Å, α = 100.01(2)°, β = 114.81(5)°, γ = 80.82(5)°, Z = 1; [MeH3N][Ni(dmise)2]2 (C13H6NNi2S16Se4), monoclinic, P21/c, a = 7.636(2) Å, b = 9.545(3) Å, c = 22.555(6) Å, β = 92.95(2)°, Z = 2. Short contacts between Se atoms across the cation sheet were found in [Me3HN][Ni(dmise)2]2 and [Me2H2N][Ni(dmise)2]2. A tight-binding band structure calculation by extended Hückel methods indicated that [Me3HN][Ni(dmise)2]2 has even stronger intermolecular interactions along the long molecular axis than along the transverse direction owing to a close selenium−selenium contact. Cs[Pd(dmise)2]2 kept metallic behavior down to 4 K at ambient pressure.

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