Dinuclear oxofluorometallates as a new structural type of d(0) transition metal oxofluoride compound.

IF 1.9 3区化学

Acta Crystallographica Section B-structural Science Pub Date : 2012-12-01 Epub Date: 2012-11-16 DOI:10.1107/S0108768112042577

Anatoly A Udovenko, Natalia M Laptash

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引用次数: 6

Abstract

Five isomorphous d(0) transition metal oxofluoride compounds A(3)[M(2)O(x)F(11-x)]·(AF)(0.333) (A = K, Rb, NH(4); M = Nb, Mo, W; x = 2, 4) have been synthesized from acid fluoride solutions, and their crystal structures have been determined by single-crystal X-ray diffraction. The basic structural building units are dinuclear M(2)X(11) (dimers) formed from NbOF(5) or Mo(W)O(2)F(4) octahedra connected by the fluorine bridging atom. In the Nb(2)O(2)F(9) dimer, the O atoms occupy apical corners. In the M(2)O(4)F(7) (M = Mo, W) dimers two O atoms are also apically placed, whereas the other two O atoms are statistically disordered in equatorial planes. The arrangement of dimers is so that the hexagonal tunnels containing `free' fluoride ions are formed. During the irradiation process the orthorhombic structure of K(3)Nb(2)O(2)F(9)·(KF)(0.333) transforms into a pseudo-trigonal one with a = 23.15 Å, which is the [101] diagonal of the orthorhombic unit cell. The other four trigonal crystals are merohedral twins.

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双核氟金属氧化物是一种新型结构的d(0)过渡金属氟化氧化合物。

五种同形d(0)过渡金属氟化氧化合物A(3)[M(2)O(x)F(11-x)]·(AF)(0.333) (A = K, Rb, NH(4);M = Nb, Mo, W;x = 2,4)，并通过单晶x射线衍射测定了它们的晶体结构。基本结构单元是由NbOF(5)或Mo(W)O(2)F(4)八面体形成的双核M(2)X(11)(二聚体)，由氟桥接原子连接。在Nb(2)O(2)F(9)二聚体中，O原子占据顶端角。在M(2)O(4)F(7) (M = Mo, W)二聚体中，两个O原子也位于顶端，而其他两个O原子在赤道平面上统计上是无序的。二聚体的排列使得含有“游离”氟离子的六角形通道形成。在辐照过程中，K(3)Nb(2)O(2)F(9)·(KF)(0.333)的正交结构转变为伪三角结构，a = 23.15 Å，为正交单元胞的[101]对角线。另外四个三角晶体是双面体孪晶。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Acta Crystallographica Section B-structural Science 化学-晶体学

自引率

5.30%

发文量

审稿时长

6-12 weeks

期刊介绍： Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials publishes scientific articles related to the structural science of compounds and materials in the widest sense. Knowledge of the arrangements of atoms, including their temporal variations and dependencies on temperature and pressure, is often the key to understanding physical and chemical phenomena and is crucial for the design of new materials and supramolecular devices. Acta Crystallographica B is the forum for the publication of such contributions. Scientific developments based on experimental studies as well as those based on theoretical approaches, including crystal-structure prediction, structure-property relations and the use of databases of crystal structures, are published.