Die kristallinen Hydrate von Tetramethylammoniumfluorid. Bildung, Struktur, Wasserstoffbrückenbindung [1] / The Crystalline Hydrates of Tetramethylammonium Fluoride. Formation, Structure, Hydrogen Bonding
The melting diagram of the system Me4NF-H2O in the region 50-100 mol% H2O has been investigated for the first time, using DTA, DSC and temperature-dependent X-ray powder diffraction. Four crystalline hydrates Me4NF·xH2O were found, with x = 1,2.33,4 and 5, which decompose irreversibly above ca. 160°C and melt incongruently at 36°C, congruently at 46°C and again incongruently at 10°C, respectively. The crystal structure of each hydrate, except the already known one of the tetrahydrate, has been determined with MoKa diffractometer data. The monohydrate is rhombohedral with space group R3̄̄m and Z = 6 formula units per unit cell (hexagonal axes), the 2.33-hydrate monoclinic with P21/n and Z = 12, and the pentahydrate tetragonal with I4̄2 m and Z = 2. The hydrogen-bonded H2O/F- structure is an isolated centrosymmetric [F2(H2O)2]2- four-membered ring in the monohydrate, a rather open three-dimensional network in the 2.33-hydrate and a corrugated dense layer of fused fivemembered rings in the pentahydrate.