Li3VF6 is Ilmenite-like structured and crystallizes in the trigonal P-31c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to six equivalent F(1) atoms. In the second Li site, Li(2) is bonded to six equivalent F(1) atoms to form LiF6 octahedra that share edges with three equivalent V(1)F6 octahedra. V(1) is bonded to six equivalent F(1) atoms to form VF6 octahedra that share edges with three equivalent Li(2)F6 octahedra. F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one V(1) atom.
Li3VF6 is Ilmenite-like structured and crystallizes in the trigonal P-31c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to six equivalent F(1) atoms. There are three shorter (1.96 Å) and three longer (2.39 Å) Li(1)-F(1) bond lengths. In the second Li site, Li(2) is bonded to six equivalent F(1) atoms to form LiF6 octahedra that share edges with three equivalent V(1)F6 octahedra. All Li(2)-F(1) bond lengths are 2.11 Å. V(1) is bonded to six equivalent F(1) atoms to form VF6 octahedra that share edges with three equivalent Li(2)F6 octahedra. All V(1)-F(1) bond lengths are 1.97 Å. F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one V(1) atom.