Li5V4O12F crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(5), one O(6), and one F(1) atom. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form distorted corner-sharing LiO4F2 octahedra. The corner-sharing octahedra are not tilted. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(6), and one F(1) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(5), one O(6), and two equivalent O(4) atoms. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one V(2) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(3), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent V(1) and two equivalent V(2) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one V(1), and one V(2) atom to form OLi2V2 tetrahedra that share corners with two equivalent F(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 42-58°. F(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Li(3) atoms to form FLi6 octahedra that share corners with two equivalent F(1)Li6 octahedra and corners with four equivalent O(6)Li2V2 tetrahedra. The corner-sharing octahedra are not tilted.
Li5V4O12F crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(5), one O(6), and one F(1) atom. The Li(1)-O(1) bond length is 2.45 Å. The Li(1)-O(2) bond length is 2.05 Å. The Li(1)-O(5) bond length is 1.96 Å. The Li(1)-O(6) bond length is 2.45 Å. The Li(1)-F(1) bond length is 2.12 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form distorted corner-sharing LiO4F2 octahedra. The corner-sharing octahedra are not tilted. Both Li(2)-O(1) bond lengths are 2.00 Å. Both Li(2)-O(2) bond lengths are 2.07 Å. Both Li(2)-F(1) bond lengths are 2.35 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(6), and one F(1) atom. The Li(3)-O(1) bond length is 2.38 Å. The Li(3)-O(2) bond length is 2.39 Å. The Li(3)-O(3) bond length is 1.97 Å. The Li(3)-O(6) bond length is 2.24 Å. The Li(3)-F(1) bond length is 2.13 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms. The V(1)-O(2) bond length is 1.69 Å. The V(1)-O(3) bond length is 1.79 Å. The V(1)-O(5) bond length is 2.08 Å. The V(1)-O(6) bond length is 1.87 Å. There is one shorter (1.95 Å) and one longer (2.21 Å) V(1)-O(4) bond length. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(5), one O(6), and two equivalent O(4) atoms. The V(2)-O(1) bond length is 1.67 Å. The V(2)-O(3) bond length is 2.03 Å. The V(2)-O(5) bond length is 1.77 Å. The V(2)-O(6) bond length is 1.92 Å. There is one shorter (1.94 Å) and one longer (2.24 Å) V(2)-O(4) bond length. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one V(2) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(3), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent V(1) and two equivalent V(2) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one V(1), and one V(2) atom to form OLi2V2 tetrahedra that share corners with two equivalent F(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 42-58°. F(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Li(3) atoms to form FLi6 octahedra that share corners with two equivalent F(1)Li6 octahedra and corners with four equivalent O(6)Li2V2 tetrahedra. The corner-sharing octahedra are not tilted.