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 distorted LiO4 trigonal pyramids that share corners with two equivalent V(1)O5F octahedra, corners with three equivalent Li(6)O3F tetrahedra, corners with three equivalent Li(5)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 2-60°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(4), and one F(1) atom to form 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(6)O3F tetrahedra,  an edgeedge with one Li(5)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 16-53°. 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 5-coordinate geometry to one O(1), one O(2), one O(4), one O(5), and one F(1) atom. In the fifth Li site, Li(5) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form distorted LiO4 tetrahedra that share corners with two equivalent V(1)O5F octahedra, corners with three equivalent Li(6)O3F tetrahedra, corners with three equivalent Li(1)O4 trigonal pyramids,  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 18-47°. In the sixth Li site, Li(6) is bonded to one O(2), one O(3), 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(5)O4 tetrahedra, corners with three equivalent Li(1)O4 trigonal pyramids,  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 17-51°. 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 distorted 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(6)O3F tetrahedra,  an edgeedge with one Li(5)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 34-57°. 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(6)O3F tetrahedra, corners with two equivalent Li(7)O3F tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Li(2)O3F tetrahedra,  an edgeedge with one Li(6)O3F tetrahedra,  an edgeedge with one Li(7)O3F tetrahedra,  an edgeedge with one Li(5)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. 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 octahedra. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one V(1) atom to form distorted OLi6V pentagonal bipyramids that share  a cornercorner with one O(1)Li5V octahedra, edges with two equivalent O(1)Li5V octahedra, and edges with three equivalent O(5)Li6V pentagonal bipyramids. The corner-sharing octahedral tilt angles are 9°. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Li(1), one Li(3), one Li(5), one Li(6), and one V(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(5), 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 distorted OLi6V pentagonal bipyramids that share  a cornercorner with one O(1)Li5V octahedra, edges with two equivalent O(1)Li5V octahedra, and edges with three equivalent O(2)Li6V pentagonal bipyramids. The corner-sharing octahedral tilt angles are 11°. F(1) 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.
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 distorted LiO4 trigonal pyramids that share corners with two equivalent V(1)O5F octahedra, corners with three equivalent Li(6)O3F tetrahedra, corners with three equivalent Li(5)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 2-60°. The Li(1)-O(1) bond length is 1.97 Å. The Li(1)-O(2) bond length is 2.09 Å. The Li(1)-O(3) bond length is 1.90 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(2), one O(4), and one F(1) atom to form 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(6)O3F tetrahedra,  an edgeedge with one Li(5)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 16-53°. The Li(2)-O(1) bond length is 1.84 Å. The Li(2)-O(2) bond length is 2.00 Å. The Li(2)-O(4) bond length is 1.90 Å. The Li(2)-F(1) bond length is 1.88 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 2.12 Å. The Li(3)-O(2) bond length is 2.09 Å. The Li(3)-O(3) bond length is 2.08 Å. The Li(3)-O(4) bond length is 2.57 Å. The Li(3)-O(5) bond length is 2.31 Å. The Li(3)-F(1) bond length is 2.23 Å. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), one O(5), and one F(1) atom. The Li(4)-O(1) bond length is 2.04 Å. The Li(4)-O(2) bond length is 2.18 Å. The Li(4)-O(4) bond length is 2.13 Å. The Li(4)-O(5) bond length is 2.14 Å. The Li(4)-F(1) bond length is 2.20 Å. In the fifth Li site, Li(5) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form distorted LiO4 tetrahedra that share corners with two equivalent V(1)O5F octahedra, corners with three equivalent Li(6)O3F tetrahedra, corners with three equivalent Li(1)O4 trigonal pyramids,  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 18-47°. The Li(5)-O(2) bond length is 2.06 Å. The Li(5)-O(3) bond length is 1.87 Å. The Li(5)-O(4) bond length is 2.03 Å. The Li(5)-O(5) bond length is 1.92 Å. In the sixth Li site, Li(6) is bonded to one O(2), one O(3), 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(5)O4 tetrahedra, corners with three equivalent Li(1)O4 trigonal pyramids,  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 17-51°. The Li(6)-O(2) bond length is 2.02 Å. The Li(6)-O(3) bond length is 1.95 Å. The Li(6)-O(5) bond length is 1.93 Å. The Li(6)-F(1) bond length is 1.91 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 distorted 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(6)O3F tetrahedra,  an edgeedge with one Li(5)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 34-57°. The Li(7)-O(1) bond length is 1.91 Å. The Li(7)-O(4) bond length is 1.92 Å. The Li(7)-O(5) bond length is 2.05 Å. The Li(7)-F(1) bond length is 1.95 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(6)O3F tetrahedra, corners with two equivalent Li(7)O3F tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Li(2)O3F tetrahedra,  an edgeedge with one Li(6)O3F tetrahedra,  an edgeedge with one Li(7)O3F tetrahedra,  an edgeedge with one Li(5)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The V(1)-O(1) bond length is 2.00 Å. The V(1)-O(2) bond length is 1.93 Å. The V(1)-O(3) bond length is 1.89 Å. The V(1)-O(4) bond length is 1.86 Å. The V(1)-O(5) bond length is 2.10 Å. The V(1)-F(1) bond length is 2.47 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 octahedra. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one V(1) atom to form distorted OLi6V pentagonal bipyramids that share  a cornercorner with one O(1)Li5V octahedra, edges with two equivalent O(1)Li5V octahedra, and edges with three equivalent O(5)Li6V pentagonal bipyramids. The corner-sharing octahedral tilt angles are 9°. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Li(1), one Li(3), one Li(5), one Li(6), and one V(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(5), 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 distorted OLi6V pentagonal bipyramids that share  a cornercorner with one O(1)Li5V octahedra, edges with two equivalent O(1)Li5V octahedra, and edges with three equivalent O(2)Li6V pentagonal bipyramids. The corner-sharing octahedral tilt angles are 11°. F(1) 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.