A three‐dimensional bromo‐bridged mixed‐valence gold(I,III) compound, Cs2AuIAuIIIBr6
A three‐dimensional bromo‐bridged mixed‐valence gold(I,III) compound, Cs2AuIAuIIIBr6
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三维溴桥混合价金(I,III)化合物Cs2AuIAuIIIBr6
DOI：
10.1107/s1600536805016594
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发表时间：
2005
影响因子：
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通讯作者：
N. Kojima
中科院分区：
文献类型：
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作者：
N. Matsushita;A. Tanaka;N. Kojima
标题化合物Cs2[AuIBr 2][AuIIIBr 4]为六溴化二铯金（I）金（III）或四溴化二溴金（III）二铯金（I），具有畸变钙钛矿型结构，与其氯化物和碘化物类似物Cs2 AuIAuIIIX 6（X为Cl或I）是同型的。该结构包含压缩和拉长的[AuBr 6]八面体，通过共享所有的角Br−离子，沿着[001]和[110]方向交替沿着堆叠。该化合物的特征还在于金络合离子[AuIBr 2]−和[AuIIIBr 4]−的组装。表示由于两个晶体学独立的卤素（X）离子从两个相邻Au离子之间的中点位移而导致的Au I和Au III的混合价畸变的结构参数（用（Au-X）/（Au X）表示）沿c轴沿着为0.738（2），在ab平面为0.799（1）。 这些值表明，标题溴化物的混合价态畸变介于氯化物和碘化物之间。标题溴化物从立方晶系到四立方晶系的畸变（21/2a/c = 0.9704（1））也介于氯化物和碘化物的畸变之间。
The title compound, dicaesium gold(I) gold(III) hexabromide or dicaesium dibromoaurate(I) tetrabromoaurate(III), Cs2[AuIBr2][AuIIIBr4], has a distorted perovskite-type structure which is isotypic with its chloride and iodide analogues, Cs2AuIAuIIIX6 (X is Cl or I). The structure contains compressed and elongated [AuBr6] octahedra stacked alternately along the [001] and [110] directions by sharing all the corner Br− ions. The compound is also characterized by the assembly of the gold complex ions [AuIBr2]− and [AuIIIBr4]−. Structural parameters indicating the mixed-valence distortion of AuI and AuIII due to displacement of two crystallographically independent halide (X) ions from the mid-point between the two adjacent Au ions, expressed by (Au—X)/(Au⋯X), are 0.738 (2) along the c axis and 0.799 (1) in the ab plane. These values show that the mixed-valence distortion of the title bromide is intermediate between those of the chloride and the iodide. The distortion of the title bromide from the cubic system to the tetragonal system, expressed by 21/2a/c = 0.9704 (1), is also intermediate between those of the chloride and the iodide.