Department of Applied Chemistry, Faculty of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, Japan.
Inorg Chem. 2013 Jul 15;52(14):7918-22. doi: 10.1021/ic400423n. Epub 2013 Jun 28.
A new polymorph of Mo3S4 was synthesized at 13 GPa and 1450 °C from a stoichiometric mixture of elements. It crystallizes in a triclinic unit cell (space group P1 (No. 2)) with cell constants of a = 6.364(2) Ǻ, b = 6.608(2) Ǻ, c = 6.809(2) Ǻ, α = 103.899(3) °, β = 117.753(3) °, γ = 103.958(3) °, and V = 224.25(13) Ǻ(3). The structure of Mo3S4 is composed of edge- and face-sharing MoS6 octahedra. It was closely related to the structure of MMo2S4 type compounds (M = V, Cr, Fe, and Co). Mo3S4 can be regarded as a derivative with M = Mo. The calculated density of 6.160 g/cm(3) was much larger than 5.191 g/cm(3) of famous polymorphic Mo6S8 (Chevrel phase). Mo3S4 was metallic and did not show any superconducting transition down to 2 K. The bond-valence sums suggested that Mo3S4 can be classified in the class III-B of mixed-valence compounds; all Mo ions have a similar nonintegral valence. Electronic structure calculations revealed that the conduction band of Mo3S4 contains much contribution of the relatively narrow Mo 4d bands as well as the bands composed of hybridized Mo4d-S3d orbitals.
一种新的 Mo3S4 多形体在 13 GPa 和 1450°C 由等摩尔的元素混合物合成。它在一个三斜晶系单位晶胞（空间群 P1（No.2））中结晶，晶胞常数为 a = 6.364(2) Ǻ, b = 6.608(2) Ǻ, c = 6.809(2) Ǻ, α = 103.899(3) °, β = 117.753(3) °, γ = 103.958(3) °, 以及 V = 224.25(13) Ǻ(3)。Mo3S4 的结构由边共享和面共享的 MoS6 八面体组成。它与 MMo2S4 型化合物（M = V、Cr、Fe 和 Co）的结构密切相关。Mo3S4 可以被看作是 M = Mo 的衍生物。计算出的密度为 6.160 g/cm(3)，远大于著名的多形体 Mo6S8（Chevrel 相）的 5.191 g/cm(3)。Mo3S4 是金属的，在 2 K 以下没有显示任何超导转变。键价和表明 Mo3S4 可以归类为混合价化合物的 III-B 类；所有的 Mo 离子都具有相似的非整数价。电子结构计算表明，Mo3S4 的导带包含了 Mo 4d 带的窄带以及由杂化 Mo4d-S3d 轨道组成的带的很大贡献。
