Iron(III) Fluoride - Structure

Structure

The anhydrous form is adopts a simple structure with octahedral Fe(III)F6 centres interconnected by linear Fe-F-Fe linkages. In the language of crystallography, the crystals are classified as rhombohedral with an R-3c space group. The structural motif is similar to that seen in ReO3. Although the solid is nonvolatile, it evaporates at high temperatures, the gas at 987 °C consists of FeF3, a planar molecule of D3h symmetry with three equal Fe-F bonds, each of length 176.3 pm. At very high temperatures, it decomposes to give FeF2 and F2.

Two crystalline forms - or more technically, polymorphs - of FeF3·3H2O are known, the α and β forms. These are prepared by evaporation of an HF solution containing Fe3+ at room temperature (α form) and above 50°C (β form). The space group of the β form is P4/m, and the α form maintains a P4/m space group with a J6 substructure. The solid α form is unstable and converts to the β form within days. The two forms are distinguished by their difference in quadrupole splitting from their Mössbauer spectra.

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