Magnesium Hexafluoridozirconates MgZrF6·5H2O, MgZrF6·2H2O, and MgZrF6: Structures, Phase Transitions, and Internal Mobility of Water Molecules

Abstract

The MgZrF6·nH2O (n = 5, 2 and 0) compounds were studied by the methods of X‐ray diffraction and 19F, MAS 19F, and 1H NMR spectroscopy. At room temperature, the compound MgZrF6·5H2O has a monoclinic C‐centered unit cell and is composed of isolated chains of edge‐sharing ZrF8 dodecahedra reinforced with MgF2(H2O)4 octahedra and uncoordinated H2O molecules and characterized by a disordered system of hydrogen bonds. In the temperature range 259 to 255 K, a reversible monoclinic ↔ two‐domain triclinic phase transition is observed. The phase transition is accompanied with ordering of hydrogen atoms positions and the system of hydrogen bonds. The structure of MgZrF6·2H2O comprises a three‐dimensional framework consisting of chains of edge‐sharing ZrF8 dodecahedra linked to each other through MgF4(H2O)2 octahedra. The compound MgZrF6 belongs to the NaSbF6 type and is built from regular ZrF6 and MgF6 octahedra linked into a three‐dimensional framework through linear Zr–F–Mg bridges. The peaks in 19F MAS spectra were attributed to the fluorine structural positions. The motions of structural water molecules were studied by variable‐temperature 1H NMR spectroscopy.