All of the Group 5 anions [MOF5](2-) (M = V, Nb, Ta) show the metal distorted from the center of the octahedron to the corner defined by the oxide ion. While [NbOF5](2-) and [TaOF5](2-) direct coordination through the oxide and trans fluoride ligands, the increase in vanadium oxide bond valence results in coordination through cis fluoride ligands in [VOF5](2-). The structure-directing properties of [VOF5](2-) more closely resemble those of the Group 6 anion [MoO2F4](2-).