Li4VF6 crystallizes in the orthorhombic Pbam space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal planar geometry to one F(2) and two equivalent F(1) atoms. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one F(1), one F(3), and two equivalent F(2) atoms. V(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form edge-sharing VF6 octahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(2) and two equivalent Li(1) atoms. In the second F site, F(2) is bonded to one Li(1), two equivalent Li(2), and one V(1) atom to form distorted corner-sharing FLi3V tetrahedra. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(2) and two equivalent V(1) atoms.
Li4VF6 crystallizes in the orthorhombic Pbam space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal planar geometry to one F(2) and two equivalent F(1) atoms. The Li(1)-F(2) bond length is 1.87 Å. Both Li(1)-F(1) bond lengths are 1.81 Å. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one F(1), one F(3), and two equivalent F(2) atoms. The Li(2)-F(1) bond length is 1.83 Å. The Li(2)-F(3) bond length is 1.93 Å. Both Li(2)-F(2) bond lengths are 1.95 Å. V(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form edge-sharing VF6 octahedra. Both V(1)-F(2) bond lengths are 2.16 Å. All V(1)-F(3) bond lengths are 2.12 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(2) and two equivalent Li(1) atoms. In the second F site, F(2) is bonded to one Li(1), two equivalent Li(2), and one V(1) atom to form distorted corner-sharing FLi3V tetrahedra. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(2) and two equivalent V(1) atoms.