Polyanion Condensation in Inorganic and Hybrid Fluoridometallates (IV) of Octahedrally Coordinated Ti, Zr, Hf, V, Cr, W, Mn, Ge, Sn, and Pb.

In fluorides, the M 4+ cations of M = Ti, V, Cr, Mn, Ge, Sn, and Pb favour the octahedral coordination of six F ligands. Some examples of M 4+ with larger cations (M = Zr, Hf, W) in octahedral coordination are also known. If not enough F ligands are available to have isolated M IV F 6 octahedra, they must share their F ligands. The crystal structures of such fluoride metalates (IV) show the variety of possible structural motifs of the zero-dimensional oligomeric anions [M 2 F 11 ] 3- (M = Ti, Cr), [M 3 F 15 ] 3- (M = Zr, Hf), [M 3 F 16 ] 4- (M = Ge), [M 4 F 18 ] 2- (M = Ti, W), [M 4 F 19 ] 3- (M = Ti), [M 4 F 20 ] 4- (M = Ti), [M 5 F 23 ] 3- (M = Ti), [M 6 F 27 ] 3- (M = Ti), [M 6 F 28 ] 4- (M = Ti), [M 8 F 36 ] 4- (M = Ti, Mn), [M 10 F 45 ] 5- (M = Ti) to one-dimensional chains ([MF 5 ] - ) ∞ (M = V, Ti, Cr, Ge, Sn, Pb), double chains ([M 2 F 9 ] - ) ∞ (M = Ti, Mn), columns ([M 3 F 13 ] - ) ∞ (M = Ti), ([M 4 F 19 ] 3- ) ∞ (M = Ti), ([M 7 F 30 ] 2- ) ∞ (M = Ti), ([M 9 F 38 ] 2- ) ∞ ) (M = Ti), two-dimensional layers ([M 2 F 9 ] - ) ∞ (M = Cr), ([M 8 F 33 ] - ) ∞ (M = Ti), and three-dimensional ([M 6 F 27 ] 3- ) ∞ (M = Ti) architectures. A discrete monomeric [M 2 F 9 ] - anion with two M IV F 6 octahedra sharing a common face has not yet been experimentally demonstrated, while two examples containing discrete dimeric [M 2 F 10 ] 2- anions (M = Ti) with two M IV F 6 octahedra sharing an edge are still in question.