Ni3Cl2.1(OH)3.9·4H2O，即Mg3Cl2(OH)4·4H2O的镍类似物。

Ni3Cl2.1(OH)3.9·4H2O, the Ni analogue to Mg3Cl2(OH)4·4H2O.

作者信息

Bette Sebastian, Dinnebier Robert E, Freyer Daniela

机构信息

TU Bergakademie Freiberg , Institute of Inorganic Chemistry, Leipziger Strasse 29, 09596 Freiberg, Germany.

出版信息

Inorg Chem. 2014 May 5;53(9):4316-24. doi: 10.1021/ic500251x. Epub 2014 Apr 22.

DOI:10.1021/ic500251x

PMID:24754378

Abstract

For the first time a basic transition-metal hydrate, Ni3Cl2.1(OH)3.9·4H2O, is found to be isostructural to a main-group metal phase, Mg3Cl2.0(OH)4.0·4H2O. The Ni phase was found as crystalline solid in the course of investigations into the formation of basic nickel(II) chloride phases at 25 and 40 °C in alkaline, concentrated nickel(II) chloride solutions. Ni3Cl2.1(OH)3.9·4H2O was characterized by thermal analysis, IR spectroscopy, scanning electron microscopy, and X-ray powder diffraction. The crystal structure was determined from high-resolution laboratory X-ray powder diffraction data. Ni3Cl2.1(OH)3.9·4H2O crystallizes in space group C2/m (12) with Z = 2, a = 14.9575(4) Å, b = 3.1413(1) Å, c = 10.4818(5) Å, β = 101.482(1)°, and V = 482.50(3) Å(3). The main building unit of the structure is an infinite triple chain of edge-linked distorted NiO6 octahedra. These chains are separated by interstitial one-dimensional zigzag chains of disordered Cl(-) ions and H2O molecules. The crystal structures of Ni3Cl2.1(OH)3.9·4H2O and the isostructural magnesium salt hydrate Mg3Cl2(OH)4·4H2O (2-1-4 phase) are compared in detail.

摘要

首次发现一种基本的过渡金属水合物Ni3Cl2.1(OH)3.9·4H2O与一种主族金属相Mg3Cl2.0(OH)4.0·4H2O具有相同的晶体结构。在对碱性浓氯化镍溶液中25和40℃下碱性氯化镍(II)相的形成进行研究过程中，发现镍相为结晶固体。通过热分析、红外光谱、扫描电子显微镜和X射线粉末衍射对Ni3Cl2.1(OH)3.9·4H2O进行了表征。晶体结构由高分辨率实验室X射线粉末衍射数据确定。Ni3Cl2.1(OH)3.9·4H2O结晶于空间群C2/m(12)，Z = 2，a = 14.9575(4) Å，b = 3.1413(1) Å，c = 10.4818(5) Å，β = 101.482(1)°，V = 482.50(3) Å(3)。该结构的主要构建单元是由边缘相连的扭曲NiO6八面体组成的无限三链。这些链被无序的Cl(-)离子和H2O分子的间隙一维锯齿链隔开。详细比较了Ni3Cl2.1(OH)3.9·4H2O和同结构的镁盐水合物Mg3Cl2(OH)4·4H2O(2-1-4相)的晶体结构。