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首页> 外文期刊>Acta Crystallographica, Section B. Structural Science >Phase transitions and structures at 10, 92 and 293 K in eight trigonal double salts M-I[M-III(NH3)(6)](ClO4)(2)X-2
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Phase transitions and structures at 10, 92 and 293 K in eight trigonal double salts M-I[M-III(NH3)(6)](ClO4)(2)X-2

机译：八种三角复盐M-1 [M-III（NH3）（6）]（ClO4）（2）X-2中在10、92和293 K处的相变和结构

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摘要

The crystal structures of eight hexaammine-M-III double salts have been determined by X-ray diffraction at 293 K, where M-I, M-III and X are NH4, Co, Cl (I), ammonium hexaamminecobalt(III) diperchlorate dichloride; Cs, Co, Cl (II), caesium hexaamminecobalt (III) diperchlorate dichloride; NH4, Ru, Cl (III), ammonium hexaammineruthenium(III) diperchlorate dichloride; K, Ru, Cl (TV), potassium hexaammineruthenium(III) diperchlorate dichloride; Rb, Ru, Cl (V), rubidium hexaammineruthenium(III) diperchlorate dichloride; Cs, Ru, Cl (VI), caesium hexaammineruthenium(III) diperchlorate dichloride; Cs, Cr, Cl (VII) caesium hexaamminechromium(III) diperchlorate dichloride; Cs, Cr, Br (III), caesium hexaamminechromium(LII) diperchlorate dibromide. The structures of (I), (IV), (V) and (VI) have also been determined at 92 K and those of (V), (VII) and (WI) at 10 K. At room temperature all are isomorphous, trigonal R (3) over bar m, Z = 3, with only seven positional parameters for the seven unique non-II atoms. The ammine K atoms are disordered only in the Cs+ and NH4+ salts, and the NH4+ H atoms in the ammonium salts. At lower temperatures a reversible phase change is observed in all except the K+ member, by the lowering of symmetry to a twinned, but atomically ordered, R (3) over bar phase. In this R (3) over bar phase the hexaammine-M-III and perchlorate ions have rotated about the threefold arris removing the former mirror plane in the crystal. Displacement parameters, unit cells and observed structures all change smoothly with changes in M-I ionic radii and M-III-N distances. [References: 21]
机译：已经通过在293K下的X射线衍射测定了八种六胺-M-III复盐的晶体结构，其中M-1，M-III和X是NH 4，Co，Cl（I），六氯化二铵六氨合钴（III）铵; Cs，Co，Cl（II），六氯化铯二氨基铯（III）; NH4，Ru，Cl（III），六氯化铵二氯化六氨合钌（III）铵; K，Ru，Cl（TV），二氯化二氯六氨合钌（III）; Rb，Ru，Cl（V），六氯化dip六氯化钌钌（III）; Cs，Ru，Cl（VI），二氯化二氯六氨合铯钌（III）; Cs，Cr，Cl（VII）六氨合铯二氯化铬二氯化铬; Cs，Cr，Br（III），六溴化铯二溴化铯铯（LII） （I），（IV），（V）和（VI）的结构也已在92 K下确定，（V），（VII）和（WI）的结构在10 K下已确定。在室温下，它们都是同构的，条m上的三角形R（3），Z = 3，对于七个唯一的非II原子只有七个位置参数。氨基K原子仅在Cs +和NH4 +盐中无序，而铵盐中的NH4 + H原子无序。在较低的温度下，通过将对称性降低为双相但原子有序排列的R（3）跨棒相，可观察到除K +成员以外的所有可逆相变。在棒相的R（3）中，六胺M-III和高氯酸根离子围绕三重Ar旋转，从而除去了晶体中的前一镜面。位移参数，晶胞和观察到的结构都随M-I离子半径和M-III-N距离的变化而平稳变化。 [参考：21]

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