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首页> 外文期刊>Acta Crystallographica, Section B. Structural Science >Three new polymorphic forms of molybdenum pentachloride
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Three new polymorphic forms of molybdenum pentachloride

机译：五氯化钼的三种新的多晶型形式

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摘要

Three new polymorphic modifications of molybdenum pentachloride could be obtained by solvothermal syntheses in CCl4 and SbCl5 as solvents. The structures have been solved by single-crystal X-ray diffraction. The already known structure of monoclinic alpha-MoCl5 (C2/m) is not isomorphous with alpha-NbCl5 and is better derived from the closest packing of Cl atoms of the Sm type with molybdenum occupying 1/5 of the octahedral holes. The triclinic structure of beta-MoCl5 (P (1) over bar) can be derived from hexagonal closest packing. The orthorhombic structure of gamma-MoCl5 (Pnma) and the monoclinic structure of delta-MoCl5 (P2(1)/c) can both be derived from double-hexagonal closest packing. All four forms of MoCl5 have in common the discrete Mo2Cl10 moieties built from edge-sharing double octahedra with the metal atoms displaced from the octahedron centres away from each other. The differences between the modifications lie in the different stacking sequences of the close-packed Cl-atom layers and the different occupation of the octahedral interstices. This is reflected in the group-subgroup relationships of the space groups of the closest packings and the molybdenum pentachlorides. X-ray powder diffraction shows that sublimed MoCl5 is a mixture of all four modifications in variable amounts and probably a further unknown form.
机译：溶剂热合成在CCl4和SbCl5中可以得到五种新的五氯化钼多晶型物。该结构已经通过单晶X射线衍射解决。单斜晶α-MoCl5（C2 / m）的已知结构与α-NbCl5不是同晶的，最好从Sm型Cl原子最紧密堆积的钼衍生而来，钼占八面体孔的1/5。 β-MoCl5的三斜结构（P（1）在条上）可以源自六角形最紧密堆积。 γ-MoCl5（Pnma）的正交结构和δ-MoCl5的单斜结构（P2（1）/ c）都可以从双六边形最紧密堆积得到。 MoCl5的所有四种形式共有一个离散的Mo2Cl10部分，这些部分由边共享双八面体构建而成，金属原子从八面体中心移开。修饰之间的差异在于密排的Cl原子层的不同堆积顺序和八面体间隙的不同占据。这反映在最接近的填料和五氯化钼的空间群的族-亚群关系中。 X射线粉末衍射表明，升华的MoCl5是所有四种变体的混合物，并以可变的量存在，并且可能是其他未知形式。

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