Li3V3O5F3 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), and two equivalent F(2) atoms to form LiOF3 tetrahedra that share corners with three equivalent Li(3)O3F3 octahedra, corners with three equivalent Li(2)O4F2 octahedra, and corners with six equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 55-62°. In the second Li site, Li(2) is bonded to one O(1), one O(2), two equivalent O(4), and two equivalent F(2) atoms to form LiO4F2 octahedra that share corners with three equivalent Li(1)OF3 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, edges with two equivalent Li(3)O3F3 octahedra, and edges with four equivalent V(1)O4F2 octahedra. In the third Li site, Li(3) is bonded to one O(3), two equivalent O(4), one F(1), and two equivalent F(2) atoms to form LiO3F3 octahedra that share corners with three equivalent Li(1)OF3 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, edges with two equivalent Li(2)O4F2 octahedra, and edges with four equivalent V(1)O4F2 octahedra. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with three equivalent Li(1)OF3 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(2)O4F2 octahedra, and edges with two equivalent V(1)O4F2 octahedra. In the second V site, V(2) is bonded to one O(2), one O(3), and two equivalent O(4) atoms to form VO4 tetrahedra that share corners with three equivalent Li(3)O3F3 octahedra, corners with three equivalent Li(2)O4F2 octahedra, and corners with six equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 51-58°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(2), and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(3), one V(2), and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one V(1), and one V(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom.
Li3V3O5F3 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), and two equivalent F(2) atoms to form LiOF3 tetrahedra that share corners with three equivalent Li(3)O3F3 octahedra, corners with three equivalent Li(2)O4F2 octahedra, and corners with six equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 55-62°. The Li(1)-O(1) bond length is 1.94 Å. The Li(1)-F(1) bond length is 1.97 Å. Both Li(1)-F(2) bond lengths are 1.96 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), two equivalent O(4), and two equivalent F(2) atoms to form LiO4F2 octahedra that share corners with three equivalent Li(1)OF3 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, edges with two equivalent Li(3)O3F3 octahedra, and edges with four equivalent V(1)O4F2 octahedra. The Li(2)-O(1) bond length is 2.01 Å. The Li(2)-O(2) bond length is 2.20 Å. Both Li(2)-O(4) bond lengths are 2.15 Å. Both Li(2)-F(2) bond lengths are 2.10 Å. In the third Li site, Li(3) is bonded to one O(3), two equivalent O(4), one F(1), and two equivalent F(2) atoms to form LiO3F3 octahedra that share corners with three equivalent Li(1)OF3 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, edges with two equivalent Li(2)O4F2 octahedra, and edges with four equivalent V(1)O4F2 octahedra. The Li(3)-O(3) bond length is 2.12 Å. Both Li(3)-O(4) bond lengths are 2.16 Å. The Li(3)-F(1) bond length is 2.08 Å. Both Li(3)-F(2) bond lengths are 2.04 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with three equivalent Li(1)OF3 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(2)O4F2 octahedra, and edges with two equivalent V(1)O4F2 octahedra. The V(1)-O(1) bond length is 1.93 Å. The V(1)-O(2) bond length is 2.10 Å. The V(1)-O(3) bond length is 2.07 Å. The V(1)-O(4) bond length is 1.97 Å. The V(1)-F(1) bond length is 2.11 Å. The V(1)-F(2) bond length is 2.04 Å. In the second V site, V(2) is bonded to one O(2), one O(3), and two equivalent O(4) atoms to form VO4 tetrahedra that share corners with three equivalent Li(3)O3F3 octahedra, corners with three equivalent Li(2)O4F2 octahedra, and corners with six equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 51-58°. The V(2)-O(2) bond length is 1.87 Å. The V(2)-O(3) bond length is 1.87 Å. Both V(2)-O(4) bond lengths are 1.83 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(2), and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(3), one V(2), and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one V(1), and one V(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom.