Li7VO5F crystallizes in the triclinic P1 space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form LiO4 tetrahedra that share corners with two equivalent V(1)O5F octahedra, corners with three equivalent Li(6)O4 tetrahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one Li(2)O3F tetrahedra, and  an edgeedge with one Li(7)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 23-46°. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), and one F(1) atom to form distorted LiO3F tetrahedra that share corners with two equivalent V(1)O5F octahedra, corners with three equivalent Li(7)O3F tetrahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-49°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(1) atom. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(1) atom. In the fifth Li site, Li(5) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), one O(5), and one F(1) atom. In the sixth Li site, Li(6) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form LiO4 tetrahedra that share corners with two equivalent V(1)O5F octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one Li(2)O3F tetrahedra, and  an edgeedge with one Li(7)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 12-50°. In the seventh Li site, Li(7) is bonded to one O(1), one O(4), one O(5), and one F(1) atom to form LiO3F tetrahedra that share corners with two equivalent V(1)O5F octahedra, corners with three equivalent Li(2)O3F tetrahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 17-57°. V(1) 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 distorted VO5F octahedra that share corners with two equivalent Li(2)O3F tetrahedra, corners with two equivalent Li(7)O3F tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra,  an edgeedge with one Li(2)O3F tetrahedra,  an edgeedge with one Li(7)O3F tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(6)O4 tetrahedra. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(7), and one V(1) atom to form a mixture of distorted corner and edge-sharing OLi5V pentagonal pyramids. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(3), one Li(4), one Li(5), one Li(6), and one V(1) atom. In the third O site, O(3) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one V(1) atom. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(6), one Li(7), and one V(1) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), one Li(6), one Li(7), and one V(1) atom to form a mixture of distorted corner and edge-sharing OLi6V pentagonal bipyramids. F(1) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(5), one Li(7), and one V(1) atom.
Li7VO5F crystallizes in the triclinic P1 space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form LiO4 tetrahedra that share corners with two equivalent V(1)O5F octahedra, corners with three equivalent Li(6)O4 tetrahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one Li(2)O3F tetrahedra, and  an edgeedge with one Li(7)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 23-46°. The Li(1)-O(1) bond length is 2.02 Å. The Li(1)-O(2) bond length is 1.91 Å. The Li(1)-O(3) bond length is 1.98 Å. The Li(1)-O(5) bond length is 1.99 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), and one F(1) atom to form distorted LiO3F tetrahedra that share corners with two equivalent V(1)O5F octahedra, corners with three equivalent Li(7)O3F tetrahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-49°. The Li(2)-O(1) bond length is 1.93 Å. The Li(2)-O(3) bond length is 2.06 Å. The Li(2)-O(4) bond length is 1.96 Å. The Li(2)-F(1) bond length is 1.90 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(1) atom. The Li(3)-O(1) bond length is 2.00 Å. The Li(3)-O(2) bond length is 2.23 Å. The Li(3)-O(3) bond length is 2.56 Å. The Li(3)-O(4) bond length is 2.34 Å. The Li(3)-O(5) bond length is 2.17 Å. The Li(3)-F(1) bond length is 2.08 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(1) atom. The Li(4)-O(1) bond length is 2.02 Å. The Li(4)-O(2) bond length is 2.41 Å. The Li(4)-O(3) bond length is 2.39 Å. The Li(4)-O(4) bond length is 2.13 Å. The Li(4)-O(5) bond length is 1.97 Å. The Li(4)-F(1) bond length is 2.52 Å. In the fifth Li site, Li(5) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), one O(5), and one F(1) atom. The Li(5)-O(2) bond length is 1.91 Å. The Li(5)-O(3) bond length is 1.99 Å. The Li(5)-O(5) bond length is 2.03 Å. The Li(5)-F(1) bond length is 1.96 Å. In the sixth Li site, Li(6) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form LiO4 tetrahedra that share corners with two equivalent V(1)O5F octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one Li(2)O3F tetrahedra, and  an edgeedge with one Li(7)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 12-50°. The Li(6)-O(2) bond length is 1.93 Å. The Li(6)-O(3) bond length is 1.99 Å. The Li(6)-O(4) bond length is 1.99 Å. The Li(6)-O(5) bond length is 2.03 Å. In the seventh Li site, Li(7) is bonded to one O(1), one O(4), one O(5), and one F(1) atom to form LiO3F tetrahedra that share corners with two equivalent V(1)O5F octahedra, corners with three equivalent Li(2)O3F tetrahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 17-57°. The Li(7)-O(1) bond length is 1.84 Å. The Li(7)-O(4) bond length is 1.94 Å. The Li(7)-O(5) bond length is 1.94 Å. The Li(7)-F(1) bond length is 1.85 Å. V(1) 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 distorted VO5F octahedra that share corners with two equivalent Li(2)O3F tetrahedra, corners with two equivalent Li(7)O3F tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra,  an edgeedge with one Li(2)O3F tetrahedra,  an edgeedge with one Li(7)O3F tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(6)O4 tetrahedra. The V(1)-O(1) bond length is 2.02 Å. The V(1)-O(2) bond length is 1.89 Å. The V(1)-O(3) bond length is 1.92 Å. The V(1)-O(4) bond length is 1.90 Å. The V(1)-O(5) bond length is 2.06 Å. The V(1)-F(1) bond length is 2.41 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(7), and one V(1) atom to form a mixture of distorted corner and edge-sharing OLi5V pentagonal pyramids. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(3), one Li(4), one Li(5), one Li(6), and one V(1) atom. In the third O site, O(3) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one V(1) atom. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(6), one Li(7), and one V(1) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), one Li(6), one Li(7), and one V(1) atom to form a mixture of distorted corner and edge-sharing OLi6V pentagonal bipyramids. F(1) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(5), one Li(7), and one V(1) atom.