Li3VF6 crystallizes in the trigonal P-31m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent F(1) atoms to form LiF6 octahedra that share corners with six equivalent V(1)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and edges with three equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles are 45°. In the second Li site, Li(2) is bonded to six equivalent F(1) atoms to form LiF6 octahedra that share edges with six equivalent Li(1)F6 octahedra and faces with two equivalent V(1)F6 octahedra. V(1) is bonded to six equivalent F(1) atoms to form VF6 octahedra that share corners with twelve equivalent Li(1)F6 octahedra and faces with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles are 45°. F(1) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one V(1) atom.
Li3VF6 crystallizes in the trigonal P-31m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent F(1) atoms to form LiF6 octahedra that share corners with six equivalent V(1)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and edges with three equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles are 45°. All Li(1)-F(1) bond lengths are 2.09 Å. In the second Li site, Li(2) is bonded to six equivalent F(1) atoms to form LiF6 octahedra that share edges with six equivalent Li(1)F6 octahedra and faces with two equivalent V(1)F6 octahedra. All Li(2)-F(1) bond lengths are 1.94 Å. V(1) is bonded to six equivalent F(1) atoms to form VF6 octahedra that share corners with twelve equivalent Li(1)F6 octahedra and faces with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles are 45°. All V(1)-F(1) bond lengths are 2.01 Å. F(1) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one V(1) atom.