Crystal structures of mixed-valency and mixed-metal salts A2MIII0.5SbV0.5X6 (A=Rb, Cs; M=Sb, Bi, In, Tl, Fe, Rh; X=Cl, Br). A powder neutron diffraction study
Crystal structures of mixed-valency and mixed-metal salts A2MIII0.5SbV0.5X6 (A=Rb, Cs; M=Sb, Bi, In, Tl, Fe, Rh; X=Cl, Br). A powder neutron diffraction study
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DOI：
10.1021/ic00198a023
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发表时间：
1985-02
影响因子：
4.6
通讯作者：
K. Prassides;P. Day;A. Cheetham
中科院分区：
文献类型：
--
作者：
K. Prassides;P. Day;A. Cheetham
测定了11种混合价态和混合金属盐的晶体结构。用粉末中子衍射法测定了4.7K及298和423K下的5Sbvo，5X6（A = Rb，Cs; M = Sb，Bi，In，Ti，Fe，Rh; X = Cl，Br）。通过Rietveld方法对结构进行精制。在五种情况下（A = Cs; M = Sb、Bi、Ti; X = Cl和A = Rb，Cs; M = Sb; X = Br），发现SbX_（63）~+和MX_（63）~+是超晶格有序的（空间群IAJamd），其余的是无序的（空间群Fm_（3m））。有序或无序的存在与平均1·-键长相关。单位：Rb2Sbm0。5Sbvo。SbBr 6-基团也在4.7K下从4重轴倾斜（空间群/4，/a）。Cs2Sbm0，5Sbv0，5Cl6在423 K时仍保持可区分的SbCl 63-和SbCl 66-。其他物理性质（振动光谱）进行了讨论，在光的结构结果。
The crystal structures of 11 mixed-valency and mixed-metal saltsA2Mmo. 5Sbvo, 5X6 (A= Rb, Cs; M= Sb, Bi, In, TI, Fe, Rh; X= Cl, Br) have been determined by powder neutrondiffraction at 4.7 K and in several cases also at 298 and 423 K. Structures were refined by the Rietveld method. In five cases (A= Cs; M= Sb, Bi, Ti; X= Cl and A= Rb, Cs; M= Sb; X= Br), superlattice ordering of SbX6" and MX63~ was found (space group IAJamd) while the remainder were disordered (space group Fm3m). The presence of order or disorder correlates with the average 1·-bond length. In Rb2Sbm0. 5Sbvo. 5Br6, the SbBr6”~ groups are also tilted from the 4-fold axis at 4.7 K (space group/4,/a). Cs2Sbm0, 5Sbv0, 5CI6 retains distinguishable SbCl6" and SbCl63" up to 423 K. Other physical properties (vibrational spectra) are discussed in the light of the structural results.