Li4VF7 crystallizes in the cubic F-43m space group. Li(1) is bonded to one F(2) and three equivalent F(1) atoms to form LiF4 tetrahedra that share corners with three equivalent V(1)F6 octahedra and corners with six equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. V(1) is bonded to six equivalent F(1) atoms to form VF6 octahedra that share corners with twelve equivalent Li(1)F4 tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a tetrahedral geometry to four equivalent Li(1) atoms.
Li4VF7 crystallizes in the cubic F-43m space group. Li(1) is bonded to one F(2) and three equivalent F(1) atoms to form LiF4 tetrahedra that share corners with three equivalent V(1)F6 octahedra and corners with six equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. The Li(1)-F(2) bond length is 1.78 Å. All Li(1)-F(1) bond lengths are 1.85 Å. V(1) is bonded to six equivalent F(1) atoms to form VF6 octahedra that share corners with twelve equivalent Li(1)F4 tetrahedra. All V(1)-F(1) bond lengths are 1.96 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a tetrahedral geometry to four equivalent Li(1) atoms.