LiVF4 crystallizes in the orthorhombic Imma space group. Li(1) is bonded to two equivalent F(3) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with six equivalent Li(1)F6 octahedra and edges with four equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 4-18°. V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share edges with two equivalent V(1)F6 octahedra and edges with four equivalent Li(1)F6 octahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to two equivalent Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a water-like geometry to two equivalent V(1) atoms. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent V(1) atoms.
LiVF4 crystallizes in the orthorhombic Imma space group. Li(1) is bonded to two equivalent F(3) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with six equivalent Li(1)F6 octahedra and edges with four equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 4-18°. Both Li(1)-F(3) bond lengths are 2.24 Å. All Li(1)-F(1) bond lengths are 2.12 Å. V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share edges with two equivalent V(1)F6 octahedra and edges with four equivalent Li(1)F6 octahedra. Both V(1)-F(1) bond lengths are 1.91 Å. Both V(1)-F(2) bond lengths are 1.97 Å. Both V(1)-F(3) bond lengths are 2.05 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to two equivalent Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a water-like geometry to two equivalent V(1) atoms. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent V(1) atoms.