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首页> 外文期刊>Zeitschrift fur Kristallographie: International Journal for Structural, Physical, and Chemical Aspects of Crystalline Materials >Lone electron pair stereoactivity, cation arrangements and distortion of heteropolyhedral sheets in the structures of Tl-2[(UO2)(AO(4))(2)] (A = Cr, MO)
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Lone electron pair stereoactivity, cation arrangements and distortion of heteropolyhedral sheets in the structures of Tl-2[(UO2)(AO(4))(2)] (A = Cr, MO)

机译：Tl-2 [（UO2）（AO（4））（2）]（A = Cr，MO）结构中的孤对电子立体活性，阳离子排列和杂多面体片的变形

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摘要

Two new Tl uranyl compounds, Tl-2(UO2)(MoO4)(2) and Tl-2(UO2)(CrO4)(2), have been prepared by high-temperature solid-state reaction and hydrothermal synthesis, respectively. The structure of Tl-2(UO2)(MoO4)(2) (orthorhombic, Pca2(1), a = 10.977(3), b = 14.004(3), c = 14.041(3) angstrom, V = 2158.5(8) angstrom(3), Z = 8) has been solved by direct methods and refined to R-1 = 0.051 on the basis of 5229 unique observed reflections (vertical bar F(O)vertical bar >= 4 sigma(F)). The structure of Tl-2(UO2)(CrO4)(2) (orthorhombic, Pca2(1), a = 10.7034(5), b = 13.4252(6), c = 13.9364(6) angstrom, V = 2002.6(2) angstrom(3), Z = 8) has been solved by direct methods and refined to R-1 = 0.035 on the basis of 6330 unique observed reflections (vertical bar F(O)vertical bar >= 4 sigma(F)). The compounds are isostructural and are based upon [(UO2)(AO(4))(2)] sheets (A = Cr, Mo) of UrO(5) pentagonal bipyramids (Ur = U-2(2+), uranyl ion) that share equatorial corners with AO(4) tetrahedra. The sheets are parallel to (001) and are linked by TV cations located in the interlayer. Stereoactive lone electron pairs on the Tl+ cations form lone pair-containing cavities that form channels parallel to the a axis and are located at the level of y similar to 0.5. The repulsion of the Tl+ cations across the cavities leads to the distortion of the cation arrangements and, as a consequence, distortion of the flexible [(UO2)(AO(4))(2)] uranyl molybdate/chromate sheets.
机译：通过高温固相反应和水热合成分别制备了两种新的T1铀酰化合物T1-2（UO2）（MoO4）（2）和T1-2（UO2）（CrO4）（2）。 Tl-2（UO2）（MoO4）（2）的结构（斜方晶，Pca2（1），a = 10.977（3），b = 14.004（3），c = 14.041（3）埃，V = 2158.5（8 ）埃（3），Z = 8）已通过直接方法求解，并基于5229次唯一观察到的反射（垂直条F（O）垂直条> = 4 sigma（F））细化为R-1 = 0.051。 Tl-2（UO2）（CrO4）（2）的结构（斜方晶，Pca2（1），a = 10.7034（5），b = 13.4252（6），c = 13.9364（6）埃，V = 2002.6（2 ）埃（3），Z = 8）已通过直接方法求解，并根据6330个观察到的独特反射（竖线F（O）竖线> = 4σ（F））细化为R-1 = 0.035。这些化合物是同构的，基于UrO（5）五角双锥体（Ur = U-2（2+），铀酰离子）的[（UO2）（AO（4））（2）]片材（A = Cr，Mo） ）与AO（4）四面体共享赤道角。这些薄片与（001）平行，并通过位于夹层中的TV阳离子链接。 Tl +阳离子上的立体孤电子对形成含孤对的空腔，这些空腔形成平行于a轴的通道，并位于y的水平，类似于0.5。 Tl +阳离子在腔中的排斥导致阳离子排列的变形，结果导致柔性[（UO2）（AO（4））（2）]钼酸钼/铬酸铀酯片的变形。

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