Li7VO5F crystallizes in the triclinic P-1 space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), two equivalent O(1), and one F(1) atom to form distorted LiO3F tetrahedra that share  a cornercorner with one Li(5)O3F tetrahedra,  a cornercorner with one Li(7)O4 tetrahedra,  a cornercorner with one V(1)O5 trigonal bipyramid,  an edgeedge with one Li(1)O3F tetrahedra, and  an edgeedge with one V(1)O5 trigonal bipyramid. In the second Li site, Li(2) is bonded to one O(4), one O(5), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(5)O3F tetrahedra, corners with two equivalent Li(7)O4 tetrahedra, corners with two equivalent V(1)O5 trigonal bipyramids,  an edgeedge with one Li(5)O3F tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(7)O4 tetrahedra, and  an edgeedge with one V(1)O5 trigonal bipyramid. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(4), two equivalent O(1), and one F(1) atom. In the fourth Li site, Li(4) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(3), one O(5), and one F(1) atom. In the fifth Li site, Li(5) is bonded to one O(2), one O(4), one O(5), and one F(1) atom to form distorted LiO3F tetrahedra that share  a cornercorner with one Li(1)O3F tetrahedra,  a cornercorner with one Li(7)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent V(1)O5 trigonal bipyramids,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(7)O4 tetrahedra. In the sixth Li site, Li(6) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(4), and two equivalent O(5) atoms. In the seventh Li site, Li(7) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(1)O3F tetrahedra,  a cornercorner with one Li(5)O3F tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent V(1)O5 trigonal bipyramids,  an edgeedge with one Li(5)O3F tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one V(1)O5 trigonal bipyramid. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form VO5 trigonal bipyramids that share  a cornercorner with one Li(1)O3F tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(7)O4 tetrahedra, corners with three equivalent Li(5)O3F tetrahedra,  an edgeedge with one Li(1)O3F tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(7)O4 tetrahedra. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(4), two equivalent Li(1), two equivalent Li(3), and one V(1) atom. In the second O site, O(2) is bonded to one Li(5), one Li(6), one Li(7), two equivalent Li(2), and one V(1) atom to form distorted OLi5V pentagonal pyramids that share  a cornercorner with one O(3)Li4V trigonal bipyramid,  a cornercorner with one F(1)Li4 trigonal pyramid,  an edgeedge with one O(2)Li5V pentagonal pyramid, and  an edgeedge with one O(3)Li4V trigonal bipyramid. In the third O site, O(3) is bonded to one Li(1), one Li(4), one Li(6), one Li(7), and one V(1) atom to form distorted OLi4V trigonal bipyramids that share  a cornercorner with one O(2)Li5V pentagonal pyramid, corners with two equivalent F(1)Li4 trigonal pyramids, and  an edgeedge with one O(2)Li5V pentagonal pyramid. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), one Li(5), one Li(6), one Li(7), and one V(1) atom. In the fifth O site, O(5) is bonded in a 7-coordinate geometry to one Li(2), one Li(4), one Li(5), one Li(7), two equivalent Li(6), and one V(1) atom. F(1) is bonded to one Li(1), one Li(3), one Li(4), and one Li(5) atom to form FLi4 trigonal pyramids that share  a cornercorner with one O(2)Li5V pentagonal pyramid and corners with two equivalent O(3)Li4V trigonal bipyramids.
Li7VO5F crystallizes in the triclinic P-1 space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), two equivalent O(1), and one F(1) atom to form distorted LiO3F tetrahedra that share  a cornercorner with one Li(5)O3F tetrahedra,  a cornercorner with one Li(7)O4 tetrahedra,  a cornercorner with one V(1)O5 trigonal bipyramid,  an edgeedge with one Li(1)O3F tetrahedra, and  an edgeedge with one V(1)O5 trigonal bipyramid. The Li(1)-O(3) bond length is 1.92 Å. There is one shorter (1.93 Å) and one longer (2.20 Å) Li(1)-O(1) bond length. The Li(1)-F(1) bond length is 1.88 Å. In the second Li site, Li(2) is bonded to one O(4), one O(5), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(5)O3F tetrahedra, corners with two equivalent Li(7)O4 tetrahedra, corners with two equivalent V(1)O5 trigonal bipyramids,  an edgeedge with one Li(5)O3F tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(7)O4 tetrahedra, and  an edgeedge with one V(1)O5 trigonal bipyramid. The Li(2)-O(4) bond length is 1.94 Å. The Li(2)-O(5) bond length is 1.92 Å. There is one shorter (1.97 Å) and one longer (2.03 Å) Li(2)-O(2) bond length. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(4), two equivalent O(1), and one F(1) atom. The Li(3)-O(4) bond length is 2.03 Å. There is one shorter (1.96 Å) and one longer (2.23 Å) Li(3)-O(1) bond length. The Li(3)-F(1) bond length is 1.97 Å. In the fourth Li site, Li(4) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(3), one O(5), and one F(1) atom. The Li(4)-O(1) bond length is 2.07 Å. The Li(4)-O(3) bond length is 1.86 Å. The Li(4)-O(5) bond length is 2.10 Å. The Li(4)-F(1) bond length is 1.90 Å. In the fifth Li site, Li(5) is bonded to one O(2), one O(4), one O(5), and one F(1) atom to form distorted LiO3F tetrahedra that share  a cornercorner with one Li(1)O3F tetrahedra,  a cornercorner with one Li(7)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent V(1)O5 trigonal bipyramids,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(7)O4 tetrahedra. The Li(5)-O(2) bond length is 2.07 Å. The Li(5)-O(4) bond length is 1.96 Å. The Li(5)-O(5) bond length is 2.14 Å. The Li(5)-F(1) bond length is 1.88 Å. In the sixth Li site, Li(6) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(4), and two equivalent O(5) atoms. The Li(6)-O(2) bond length is 2.08 Å. The Li(6)-O(3) bond length is 2.02 Å. The Li(6)-O(4) bond length is 2.00 Å. There is one shorter (2.24 Å) and one longer (2.53 Å) Li(6)-O(5) bond length. In the seventh Li site, Li(7) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(1)O3F tetrahedra,  a cornercorner with one Li(5)O3F tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent V(1)O5 trigonal bipyramids,  an edgeedge with one Li(5)O3F tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one V(1)O5 trigonal bipyramid. The Li(7)-O(2) bond length is 2.00 Å. The Li(7)-O(3) bond length is 1.89 Å. The Li(7)-O(4) bond length is 1.94 Å. The Li(7)-O(5) bond length is 2.05 Å. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form VO5 trigonal bipyramids that share  a cornercorner with one Li(1)O3F tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(7)O4 tetrahedra, corners with three equivalent Li(5)O3F tetrahedra,  an edgeedge with one Li(1)O3F tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(7)O4 tetrahedra. The V(1)-O(1) bond length is 1.87 Å. The V(1)-O(2) bond length is 1.89 Å. The V(1)-O(3) bond length is 1.96 Å. The V(1)-O(4) bond length is 2.08 Å. The V(1)-O(5) bond length is 1.87 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(4), two equivalent Li(1), two equivalent Li(3), and one V(1) atom. In the second O site, O(2) is bonded to one Li(5), one Li(6), one Li(7), two equivalent Li(2), and one V(1) atom to form distorted OLi5V pentagonal pyramids that share  a cornercorner with one O(3)Li4V trigonal bipyramid,  a cornercorner with one F(1)Li4 trigonal pyramid,  an edgeedge with one O(2)Li5V pentagonal pyramid, and  an edgeedge with one O(3)Li4V trigonal bipyramid. In the third O site, O(3) is bonded to one Li(1), one Li(4), one Li(6), one Li(7), and one V(1) atom to form distorted OLi4V trigonal bipyramids that share  a cornercorner with one O(2)Li5V pentagonal pyramid, corners with two equivalent F(1)Li4 trigonal pyramids, and  an edgeedge with one O(2)Li5V pentagonal pyramid. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), one Li(5), one Li(6), one Li(7), and one V(1) atom. In the fifth O site, O(5) is bonded in a 7-coordinate geometry to one Li(2), one Li(4), one Li(5), one Li(7), two equivalent Li(6), and one V(1) atom. F(1) is bonded to one Li(1), one Li(3), one Li(4), and one Li(5) atom to form FLi4 trigonal pyramids that share  a cornercorner with one O(2)Li5V pentagonal pyramid and corners with two equivalent O(3)Li4V trigonal bipyramids.