LiV2O3F is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent F(1) atoms to form LiO4F2 octahedra that share corners with three equivalent Li(2)O2F2 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, edges with two equivalent V(3)O4F2 octahedra, and edges with four equivalent V(2)O5F octahedra. In the second Li site, Li(2) is bonded to one O(2), one O(3), and two equivalent F(1) atoms to form LiO2F2 tetrahedra that share corners with three equivalent Li(1)O4F2 octahedra, corners with three equivalent V(3)O4F2 octahedra, and corners with six equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 52-65°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(4), one O(5), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with three equivalent Li(1)O4F2 octahedra, corners with three equivalent V(3)O4F2 octahedra, and corners with six equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 54-61°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(1) atom to form VO5F octahedra that share corners with three equivalent Li(2)O2F2 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent V(3)O4F2 octahedra, and edges with two equivalent V(2)O5F octahedra. In the third V site, V(3) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent F(1) atoms to form VO4F2 octahedra that share corners with three equivalent Li(2)O2F2 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, edges with two equivalent Li(1)O4F2 octahedra, and edges with four equivalent V(2)O5F octahedra. There are five inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), and two equivalent V(2) atoms to form a mixture of distorted edge and corner-sharing OLi2V2 tetrahedra. In the third O site, O(3) is bonded to one Li(2), one V(3), and two equivalent V(2) atoms to form a mixture of distorted edge and corner-sharing OLiV3 tetrahedra. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one V(1), one V(3), and two equivalent V(2) atoms. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), and two equivalent V(2) atoms. F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(2), and one V(3) atom.
LiV2O3F is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent F(1) atoms to form LiO4F2 octahedra that share corners with three equivalent Li(2)O2F2 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, edges with two equivalent V(3)O4F2 octahedra, and edges with four equivalent V(2)O5F octahedra. The Li(1)-O(2) bond length is 2.04 Å. The Li(1)-O(5) bond length is 2.21 Å. Both Li(1)-O(1) bond lengths are 2.07 Å. Both Li(1)-F(1) bond lengths are 2.14 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), and two equivalent F(1) atoms to form LiO2F2 tetrahedra that share corners with three equivalent Li(1)O4F2 octahedra, corners with three equivalent V(3)O4F2 octahedra, and corners with six equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 52-65°. The Li(2)-O(2) bond length is 1.96 Å. The Li(2)-O(3) bond length is 1.97 Å. Both Li(2)-F(1) bond lengths are 2.01 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(4), one O(5), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with three equivalent Li(1)O4F2 octahedra, corners with three equivalent V(3)O4F2 octahedra, and corners with six equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 54-61°. The V(1)-O(4) bond length is 1.98 Å. The V(1)-O(5) bond length is 1.94 Å. Both V(1)-O(1) bond lengths are 1.95 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(1) atom to form VO5F octahedra that share corners with three equivalent Li(2)O2F2 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent V(3)O4F2 octahedra, and edges with two equivalent V(2)O5F octahedra. The V(2)-O(1) bond length is 2.02 Å. The V(2)-O(2) bond length is 1.94 Å. The V(2)-O(3) bond length is 2.03 Å. The V(2)-O(4) bond length is 2.14 Å. The V(2)-O(5) bond length is 2.06 Å. The V(2)-F(1) bond length is 2.15 Å. In the third V site, V(3) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent F(1) atoms to form VO4F2 octahedra that share corners with three equivalent Li(2)O2F2 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, edges with two equivalent Li(1)O4F2 octahedra, and edges with four equivalent V(2)O5F octahedra. The V(3)-O(3) bond length is 1.97 Å. The V(3)-O(4) bond length is 2.06 Å. Both V(3)-O(1) bond lengths are 2.00 Å. Both V(3)-F(1) bond lengths are 2.12 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), and two equivalent V(2) atoms to form a mixture of distorted edge and corner-sharing OLi2V2 tetrahedra. In the third O site, O(3) is bonded to one Li(2), one V(3), and two equivalent V(2) atoms to form a mixture of distorted edge and corner-sharing OLiV3 tetrahedra. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one V(1), one V(3), and two equivalent V(2) atoms. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), and two equivalent V(2) atoms. F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(2), and one V(3) atom.