Li5VF8 crystallizes in the orthorhombic Immm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with six equivalent Li(1)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent V(1)F6 octahedra, and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. In the second Li site, Li(2) is bonded to two equivalent F(3) and four equivalent F(2) atoms to form LiF6 octahedra that share edges with two equivalent V(1)F6 octahedra and edges with eight equivalent Li(1)F6 octahedra. V(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form VF6 octahedra that share edges with two equivalent Li(2)F6 octahedra and edges with eight equivalent Li(1)F6 octahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Li(1) and one V(1) atom to form FLi4V square pyramids that share corners with five equivalent F(1)Li4V square pyramids and edges with four equivalent F(3)Li5 square pyramids. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one V(1) atom. In the third F site, F(3) is bonded to one Li(2) and four equivalent Li(1) atoms to form FLi5 square pyramids that share corners with five equivalent F(3)Li5 square pyramids and edges with four equivalent F(1)Li4V square pyramids.
Li5VF8 crystallizes in the orthorhombic Immm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with six equivalent Li(1)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent V(1)F6 octahedra, and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. Both Li(1)-F(1) bond lengths are 2.08 Å. Both Li(1)-F(2) bond lengths are 2.17 Å. Both Li(1)-F(3) bond lengths are 2.08 Å. In the second Li site, Li(2) is bonded to two equivalent F(3) and four equivalent F(2) atoms to form LiF6 octahedra that share edges with two equivalent V(1)F6 octahedra and edges with eight equivalent Li(1)F6 octahedra. Both Li(2)-F(3) bond lengths are 1.98 Å. All Li(2)-F(2) bond lengths are 2.04 Å. V(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form VF6 octahedra that share edges with two equivalent Li(2)F6 octahedra and edges with eight equivalent Li(1)F6 octahedra. Both V(1)-F(1) bond lengths are 2.02 Å. All V(1)-F(2) bond lengths are 1.94 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Li(1) and one V(1) atom to form FLi4V square pyramids that share corners with five equivalent F(1)Li4V square pyramids and edges with four equivalent F(3)Li5 square pyramids. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one V(1) atom. In the third F site, F(3) is bonded to one Li(2) and four equivalent Li(1) atoms to form FLi5 square pyramids that share corners with five equivalent F(3)Li5 square pyramids and edges with four equivalent F(1)Li4V square pyramids.