Li2VF4 crystallizes in the monoclinic P2/c space group. Li(1) is bonded to two equivalent F(1) and two equivalent F(2) atoms to form LiF4 tetrahedra that share corners with six equivalent V(1)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-72°. V(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form VF6 octahedra that share corners with twelve equivalent Li(1)F4 tetrahedra and edges with two equivalent V(1)F6 octahedra. There are two inequivalent F sites. In the first F site, F(2) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom. In the second F site, F(1) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing FLi2V2 tetrahedra.
Li2VF4 crystallizes in the monoclinic P2/c space group. Li(1) is bonded to two equivalent F(1) and two equivalent F(2) atoms to form LiF4 tetrahedra that share corners with six equivalent V(1)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-72°. There is one shorter (1.99 Å) and one longer (2.02 Å) Li(1)-F(1) bond length. There is one shorter (1.86 Å) and one longer (1.87 Å) Li(1)-F(2) bond length. V(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form VF6 octahedra that share corners with twelve equivalent Li(1)F4 tetrahedra and edges with two equivalent V(1)F6 octahedra. Both V(1)-F(2) bond lengths are 2.09 Å. There are two shorter (2.15 Å) and two longer (2.18 Å) V(1)-F(1) bond lengths. There are two inequivalent F sites. In the first F site, F(2) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom. In the second F site, F(1) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing FLi2V2 tetrahedra.