Beschreibung:
<jats:title>Abstract</jats:title><jats:p>The synthesis and study of structure and properties of a crystal hydrate of the composition Zn<jats:sub>2</jats:sub>ZrF<jats:sub>8</jats:sub><jats:bold>·</jats:bold>12H<jats:sub>2</jats:sub>O were performed by XRD, DTA analysis as well as IR, Raman, and <jats:sup>1</jats:sup>H, and <jats:sup>19</jats:sup>F NMR, including <jats:sup>19</jats:sup>F MAS NMR spectroscopy. The compound crystallizes in the monoclinic syngony with the following unit cell parameters: <jats:italic>a</jats:italic> = 20.9649 (12), <jats:italic>b</jats:italic> = 9.6851 (6), <jats:italic>c</jats:italic> = 24.0209 (14) Å, <jats:italic>β</jats:italic> = 103.742 (2)°, space group <jats:italic>C</jats:italic>2/<jats:italic>c</jats:italic>, <jats:italic>Z</jats:italic> = 12. The structure is built from monomeric complex [ZrF<jats:sub>8</jats:sub>]<jats:sup>4–</jats:sup> and [Zn(H<jats:sub>2</jats:sub>O)<jats:sub>6</jats:sub>]<jats:sup>2+</jats:sup> linked through hydrogen bonds of different lengths (O–H<jats:bold>···</jats:bold>F and O–H<jats:bold>···</jats:bold>O). The peculiarity of the structure consists in the presence of short hydrogen bonds (interatomic O<jats:bold>···</jats:bold>F distances 2.5–2.6 Å). Analysis of the IR and Raman spectra allowed interpretation of bands corresponding to vibrations of the [ZrF<jats:sub>8</jats:sub>]<jats:sup>4–</jats:sup> anion and to describe hydrogen bonds in the structure of Zn<jats:sub>2</jats:sub>ZrF<jats:sub>8</jats:sub><jats:bold>·</jats:bold>12H<jats:sub>2</jats:sub>O. Phase transformations in the process of thermal dehydration were studied on the basis of changes in vibrational and NMR spectra. It has been established that the interligand exchange in the complex anion takes place as early as at –103 °C, whereas no reorientation of hexaaquacations was observed up to 47 °C. At 58 °C, the compound undergoes an incongruent melting accompanied with formation of much more stable ZnZrF<jats:sub>6</jats:sub><jats:bold>·</jats:bold>6H<jats:sub>2</jats:sub>O and an aqueous salty liquid phase characterized with high mobility of fluorine atoms and protons, in accordance with the NMR spectroscopic data.</jats:p>