Niobium fluoride structure

Tantalum and niobium fluoride compounds that crystallize in coordination-type structures also seem to be perspective candidates for the investigation of ferroelectric properties. Ravez and Mogus-Milancovic [404] showed that some fluoride and oxyfluoride compounds with crystal structures similar to the Re03 type exhibit ferroelastic properties. For instance, ferroelastic properties were found in some solid solutions based on Nb02F and Ta02F [405,406]. 

Niobium, tris(oxaIato)oxy-slereochemistry, 82 Niobium, tris(phenylenedithio)-structure, 63 Niobium(IV) complexes magnetic behavior, 271 Niobium fluoride Nb4F20... 

One of the most important parameters that defines the structure and stability of inorganic crystals is their stoichiometry - the quantitative relationship between the anions and the cations [134]. Oxygen and fluorine ions, O2 and F, have very similar ionic radii of 1.36 and 1.33 A, respectively. The steric similarity enables isomorphic substitution of oxygen and fluorine ions in the anionic sub-lattice as well as the combination of complex fluoride, oxyfluoride and some oxide compounds in the same system. On the other hand, tantalum or niobium, which are the central atoms in the fluoride and oxyfluoride complexes, have identical ionic radii equal to 0.66 A. Several other cations of transition metals are also sterically similar or even identical to tantalum and niobium, which allows for certain isomorphic substitutions in the cation sublattice. 

Among the different families of tantalum and niobium complex fluorides and oxyfluorides, the family of compounds with an X Me ratio equal to 6 is the largest. Table 22 presents the main structural characteristics of hexafluoroniobates and hexafluorotantalates. All known cases of niobium- and tantalum-containing formulary analogs have the same crystal structure type, at least at ambient temperature. 

Since the coordination number of tantalum or niobium in fluoride and oxyfluoride compounds cannot be lower than 6 due to steric limitations, further decrease of the X Me ratio (lower than 6) leads to linkage between complex ions in order to achieve coordination saturation by sharing of ligands between different central atoms of the complexes. The resulting compounds have X Me ratios between 6 and 4, and form crystals with a chain-type structure. 

Compounds of the same stoichiometry type usually have the same type crystal structure within the row of alkali metals K - Rb - Cs rarely the same type structure with sodium-containing analogues and never ciystallize similarly with lithium-containing compounds. The crystal structure analysis of different fluoride and oxyfluoride compounds clearly indicates that the steric similarity between all cations and tantalum or niobium must be taken into account when calculating the X Me ratio. 

NMR, Raman and IR spectroscopy are most frequently used to investigate the complex structures of fluoride solutions containing tantalum and niobium. Most investigations of such solutions were performed on the liquid-liquid extraction of tantalum and niobium, with the objective of describing the mechanism of the process. These publications will be discussed separately. 

For a long period of time, molten salts containing niobium and tantalum were widely used for the production by electrolysis of metals and alloys. This situation initiated intensive investigations into the electrochemical processes that take place in molten fluorides containing dissolved tantalum and niobium in the form of complex fluoride compounds. Well-developed sodium reduction processes currently used are also based on molten salt media. In addition, molten salts are a suitable reagent media for the synthesis of various compounds, in the form of both single crystals and powdered material. The mechanisms of the chemical interactions and the compositions of the compounds depend on the structure of the melt. 

Three conceptual steps can be discerned in the definition of the ionic structure of fluoride melts containing tantalum or niobium. Based on the very first thermodynamic calculations and melting diagram analysis, it was initially believed that the coordination numbers of tantalum and niobium, in a molten system containing alkali metal fluorides, increase up to 8. 

An irreversible extinction of the SHG signal at 150-200°C is observed for a number of other fluoride and oxyfluoride compounds of tantalum and niobium that crystallize in centrosymmetric space groups. This phenomenon is especially typical for the compounds prepared by precipitation from solutions [206]. The appearance of the weak SHG signal for such compounds is related to imperfections in their crystal structure and the creation of dipoles. Nevertheless, appropriate thermal treatment improves the structure and leads to the disappearance of dipoles and to the irreversible disappearance of the corresponding SHG signal. 

This monograph compiles the latest research on the chemistry of complex fluorides and oxyfluorides of tantalum and niobium, and covers synthesis and fluorination processes, crystal structure peculiarities and crystal chemical classification, as well as the behavior of complex ions in fluorine solutions and melts. 

Simple Binary and Related Compounds.—Reviews have been published which describe crystal structures of, and chemical bonding in, the Ta-O system. Structural aspects of niobium and tantalum oxides and oxide fluorides have... 

Fig. 5. Idealized, close-packed structures for (a) niobium and (b) rhodium penta-fluorides. Atoms in the first, second, third, and fourth layers are shown as single, double, crossed, and hatched circles, respectively. The symbols for overlapped atoms are shown dashed. The bridge bonds are shaded.

The pentafluorides are made by direct fluorination of the metals or the pentachlor-ides. Both are volatile white solids (Nb mp 80°C, bp 235°C Ta mp 95°C, bp 229°C), giving colorless liquids and vapors. They have the tetranuclear structures shown in Fig. 18-B-3. Niobium(IV) fluoride is a black, nonvolatile, paramagnetic solid TaF4 is unknown. 

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