Ni₃Cl_2.1(OH)_3.9·4H₂O, the Ni Analogue to Mg₃Cl₂(OH)₄·4H₂O

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.