Seven-coordinated (NH)TaF, RbTaF and RbTaOF were synthesized in single-crystal form and their structures were determined. A monocapped trigonal prism (CTP) or a pentagonal bipyramid (PB) of the TaF anion are stereochemically nonrigid and coexist in the first two compounds as a result of strong intraspheric dynamics. Upon cooling, tetragonal RbTaF undergoes a first-order phase transition at 145 K and the seven-coordinated polyhedron transforms into a regular CTP. The seven-coordinated polyhedron in (NH)TaF approaches the PB configuration as the temperature decreases. Cubic elpasolite-like RbTaOF is characterized by the simultaneous two-state coexistence of TaOF of the PB shape as rigidly reoriented and as fluxional. In the former case, the central atom is disordered over the octahedron in the unit cell, allowing the determination of the short Ta-O distance, whereas in the latter case, tantalum remains in the polyhedron center, resulting in synchronous Ta-O and Ta-F stretching vibrations appearing as the infrared band at 723 cm.
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Ammonium tantalum oxide fluorides: new features of dynamic disorder.
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