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A total of 88 crystal lattice structures of indium(III) anionic fluoride and mixed-ligand fluoride complexes have been discussed and systematized. Most of these structures have been established by single-crystal X-ray diffraction techniques, but some were characterized by powder X-ray diffraction methods. The presented crystallography data were compared with known isotypical compounds. This paper offers a discussion of the geometry of indium and outer sphere cation coordination polyhedra; the association of indium atoms in dimer, oligomer, and polymer formations (chains, layers, frameworks); types of cation-anion interactions; and their contributions in actual three-dimensional crystal structures including types of the crystal lattices formed. We also used structural examples of potassium fluoroindates(III) to describe the basics of the structural depolymerization model for fluoride compounds, which is used to depict the formation and transformation of complex metal fluorides and predict structural types of novel or uncharacterized fluorides in the corresponding compound series. For the readers’ convenience, we have compiled structural information in a single table containing phase compositions and corresponding standard crystallographic data (such as crystal system, space group, unit cell parameters, number of formula units per cell [ Z ], reliability factors [ R ], and In-F and In-O bond lengths).

Structural chemistry of anionic fluoride and mixed-ligand fluoride complexes of indium(III)