Li7V(O2F)2 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(4), and one F(1) atom to form LiO3F tetrahedra that share corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(4)O4F square pyramid, corners with three equivalent Li(5)O3F tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Li(4)O4F square pyramid,  an edgeedge with one Li(2)O2F2 tetrahedra,  an edgeedge with one Li(3)O3F tetrahedra, and  an edgeedge with one Li(7)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 12-58°. In the second Li site, Li(2) is bonded to one O(1), one O(3), one F(1), and one F(2) atom to form LiO2F2 tetrahedra that share corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(4)O4F square pyramid, corners with three equivalent Li(3)O3F tetrahedra, corners with three equivalent Li(7)O3F tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Li(4)O4F square pyramid,  an edgeedge with one Li(1)O3F tetrahedra, and  an edgeedge with one Li(5)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 16-57°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), and one F(2) atom to form distorted LiO3F tetrahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent Li(4)O4F square pyramids, corners with three equivalent Li(2)O2F2 tetrahedra, corners with three equivalent Li(7)O3F tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Li(4)O4F square pyramid,  an edgeedge with one Li(1)O3F tetrahedra, and  an edgeedge with one Li(5)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 17-60°. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), and one F(2) atom to form distorted LiO4F square pyramids that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one Li(2)O2F2 tetrahedra,  a cornercorner with one Li(1)O3F tetrahedra, corners with two equivalent Li(3)O3F tetrahedra, corners with two equivalent Li(7)O3F tetrahedra, corners with three equivalent Li(5)O3F tetrahedra, edges with two equivalent V(1)O4F2 octahedra,  an edgeedge with one Li(2)O2F2 tetrahedra,  an edgeedge with one Li(1)O3F tetrahedra,  an edgeedge with one Li(3)O3F tetrahedra, and  an edgeedge with one Li(7)O3F tetrahedra. The corner-sharing octahedral tilt angles are 77°. In the fifth Li site, Li(5) is bonded to one O(2), one O(3), one O(4), and one F(1) atom to form LiO3F tetrahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with three equivalent Li(4)O4F square pyramids, corners with three equivalent Li(1)O3F tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Li(2)O2F2 tetrahedra,  an edgeedge with one Li(3)O3F tetrahedra, and  an edgeedge with one Li(7)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 26-50°. In the sixth Li site, Li(6) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(4), and one F(1) atom. In the seventh Li site, Li(7) is bonded to one O(1), one O(3), one O(4), and one F(2) atom to form LiO3F tetrahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent Li(4)O4F square pyramids, corners with three equivalent Li(2)O2F2 tetrahedra, corners with three equivalent Li(3)O3F tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Li(4)O4F square pyramid,  an edgeedge with one Li(1)O3F tetrahedra, and  an edgeedge with one Li(5)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 24-51°. 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  a cornercorner with one Li(4)O4F square pyramid, corners with two equivalent Li(2)O2F2 tetrahedra, corners with two equivalent Li(1)O3F tetrahedra, corners with two equivalent Li(3)O3F tetrahedra, corners with two equivalent Li(5)O3F tetrahedra, corners with two equivalent Li(7)O3F tetrahedra, edges with two equivalent Li(4)O4F square pyramids,  an edgeedge with one Li(2)O2F2 tetrahedra,  an edgeedge with one Li(1)O3F tetrahedra,  an edgeedge with one Li(3)O3F tetrahedra,  an edgeedge with one Li(5)O3F tetrahedra, and  an edgeedge with one Li(7)O3F tetrahedra. There are four 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(6), one Li(7), and one V(1) atom to form distorted OLi6V pentagonal bipyramids that share  a cornercorner with one O(2)Li5V octahedra,  a cornercorner with one O(3)Li5V pentagonal pyramid,  a cornercorner with one O(4)Li5V pentagonal pyramid,  a cornercorner with one F(2)Li4V trigonal bipyramid, edges with two equivalent O(2)Li5V octahedra, edges with two equivalent O(3)Li5V pentagonal pyramids, edges with two equivalent O(4)Li5V pentagonal pyramids, and edges with two equivalent F(2)Li4V trigonal bipyramids. The corner-sharing octahedral tilt angles are 23°. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), one Li(6), and one V(1) atom to form distorted OLi5V octahedra that share  a cornercorner with one O(1)Li6V pentagonal bipyramid,  a cornercorner with one O(4)Li5V pentagonal pyramid, corners with two equivalent O(3)Li5V pentagonal pyramids,  a cornercorner with one F(2)Li4V trigonal bipyramid, edges with two equivalent O(1)Li6V pentagonal bipyramids,  an edgeedge with one O(3)Li5V pentagonal pyramid, edges with two equivalent O(4)Li5V pentagonal pyramids, and  an edgeedge with one F(2)Li4V trigonal bipyramid. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), one Li(7), and one V(1) atom to form distorted OLi5V pentagonal pyramids that share corners with two equivalent O(2)Li5V octahedra,  a cornercorner with one O(1)Li6V pentagonal bipyramid,  a cornercorner with one F(2)Li4V trigonal bipyramid,  an edgeedge with one O(2)Li5V octahedra, edges with two equivalent O(1)Li6V pentagonal bipyramids, edges with two equivalent O(4)Li5V pentagonal pyramids, and edges with two equivalent F(2)Li4V trigonal bipyramids. The corner-sharing octahedral tilt angles range from 8-79°. In the fourth O site, O(4) is bonded to one Li(1), one Li(4), one Li(5), one Li(6), one Li(7), and one V(1) atom to form distorted OLi5V pentagonal pyramids that share  a cornercorner with one O(2)Li5V octahedra,  a cornercorner with one O(1)Li6V pentagonal bipyramid, corners with three equivalent F(2)Li4V trigonal bipyramids, edges with two equivalent O(2)Li5V octahedra, edges with two equivalent O(1)Li6V pentagonal bipyramids, and edges with two equivalent O(3)Li5V pentagonal pyramids. The corner-sharing octahedral tilt angles are 48°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(5), one Li(6), and one V(1) atom. In the second F site, F(2) is bonded to one Li(2), one Li(3), one Li(4), one Li(7), and one V(1) atom to form distorted FLi4V trigonal bipyramids that share  a cornercorner with one O(2)Li5V octahedra,  a cornercorner with one O(1)Li6V pentagonal bipyramid,  a cornercorner with one O(3)Li5V pentagonal pyramid, corners with three equivalent O(4)Li5V pentagonal pyramids,  an edgeedge with one O(2)Li5V octahedra, edges with two equivalent O(1)Li6V pentagonal bipyramids, and edges with two equivalent O(3)Li5V pentagonal pyramids. The corner-sharing octahedral tilt angles are 64°.
Li7V(O2F)2 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(4), and one F(1) atom to form LiO3F tetrahedra that share corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(4)O4F square pyramid, corners with three equivalent Li(5)O3F tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Li(4)O4F square pyramid,  an edgeedge with one Li(2)O2F2 tetrahedra,  an edgeedge with one Li(3)O3F tetrahedra, and  an edgeedge with one Li(7)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 12-58°. The Li(1)-O(1) bond length is 2.02 Å. The Li(1)-O(2) bond length is 1.86 Å. The Li(1)-O(4) bond length is 1.91 Å. The Li(1)-F(1) bond length is 1.94 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one F(1), and one F(2) atom to form LiO2F2 tetrahedra that share corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(4)O4F square pyramid, corners with three equivalent Li(3)O3F tetrahedra, corners with three equivalent Li(7)O3F tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Li(4)O4F square pyramid,  an edgeedge with one Li(1)O3F tetrahedra, and  an edgeedge with one Li(5)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 16-57°. The Li(2)-O(1) bond length is 1.97 Å. The Li(2)-O(3) bond length is 1.95 Å. The Li(2)-F(1) bond length is 1.96 Å. The Li(2)-F(2) bond length is 1.92 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), and one F(2) atom to form distorted LiO3F tetrahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent Li(4)O4F square pyramids, corners with three equivalent Li(2)O2F2 tetrahedra, corners with three equivalent Li(7)O3F tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Li(4)O4F square pyramid,  an edgeedge with one Li(1)O3F tetrahedra, and  an edgeedge with one Li(5)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 17-60°. The Li(3)-O(1) bond length is 2.00 Å. The Li(3)-O(2) bond length is 2.02 Å. The Li(3)-O(3) bond length is 1.98 Å. The Li(3)-F(2) bond length is 1.91 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), and one F(2) atom to form distorted LiO4F square pyramids that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one Li(2)O2F2 tetrahedra,  a cornercorner with one Li(1)O3F tetrahedra, corners with two equivalent Li(3)O3F tetrahedra, corners with two equivalent Li(7)O3F tetrahedra, corners with three equivalent Li(5)O3F tetrahedra, edges with two equivalent V(1)O4F2 octahedra,  an edgeedge with one Li(2)O2F2 tetrahedra,  an edgeedge with one Li(1)O3F tetrahedra,  an edgeedge with one Li(3)O3F tetrahedra, and  an edgeedge with one Li(7)O3F tetrahedra. The corner-sharing octahedral tilt angles are 77°. The Li(4)-O(1) bond length is 2.26 Å. The Li(4)-O(2) bond length is 2.24 Å. The Li(4)-O(3) bond length is 2.04 Å. The Li(4)-O(4) bond length is 2.04 Å. The Li(4)-F(2) bond length is 2.26 Å. In the fifth Li site, Li(5) is bonded to one O(2), one O(3), one O(4), and one F(1) atom to form LiO3F tetrahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with three equivalent Li(4)O4F square pyramids, corners with three equivalent Li(1)O3F tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Li(2)O2F2 tetrahedra,  an edgeedge with one Li(3)O3F tetrahedra, and  an edgeedge with one Li(7)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 26-50°. The Li(5)-O(2) bond length is 1.88 Å. The Li(5)-O(3) bond length is 1.97 Å. The Li(5)-O(4) bond length is 1.93 Å. The Li(5)-F(1) bond length is 1.90 Å. In the sixth Li site, Li(6) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(4), and one F(1) atom. The Li(6)-O(1) bond length is 2.00 Å. The Li(6)-O(2) bond length is 1.91 Å. The Li(6)-O(4) bond length is 1.94 Å. The Li(6)-F(1) bond length is 2.43 Å. In the seventh Li site, Li(7) is bonded to one O(1), one O(3), one O(4), and one F(2) atom to form LiO3F tetrahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent Li(4)O4F square pyramids, corners with three equivalent Li(2)O2F2 tetrahedra, corners with three equivalent Li(3)O3F tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Li(4)O4F square pyramid,  an edgeedge with one Li(1)O3F tetrahedra, and  an edgeedge with one Li(5)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 24-51°. The Li(7)-O(1) bond length is 2.02 Å. The Li(7)-O(3) bond length is 1.95 Å. The Li(7)-O(4) bond length is 2.01 Å. The Li(7)-F(2) bond length is 1.97 Å. 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  a cornercorner with one Li(4)O4F square pyramid, corners with two equivalent Li(2)O2F2 tetrahedra, corners with two equivalent Li(1)O3F tetrahedra, corners with two equivalent Li(3)O3F tetrahedra, corners with two equivalent Li(5)O3F tetrahedra, corners with two equivalent Li(7)O3F tetrahedra, edges with two equivalent Li(4)O4F square pyramids,  an edgeedge with one Li(2)O2F2 tetrahedra,  an edgeedge with one Li(1)O3F tetrahedra,  an edgeedge with one Li(3)O3F tetrahedra,  an edgeedge with one Li(5)O3F tetrahedra, and  an edgeedge with one Li(7)O3F tetrahedra. The V(1)-O(1) bond length is 2.11 Å. The V(1)-O(2) bond length is 2.01 Å. The V(1)-O(3) bond length is 2.04 Å. The V(1)-O(4) bond length is 2.01 Å. The V(1)-F(1) bond length is 2.17 Å. The V(1)-F(2) bond length is 2.18 Å. There are four 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(6), one Li(7), and one V(1) atom to form distorted OLi6V pentagonal bipyramids that share  a cornercorner with one O(2)Li5V octahedra,  a cornercorner with one O(3)Li5V pentagonal pyramid,  a cornercorner with one O(4)Li5V pentagonal pyramid,  a cornercorner with one F(2)Li4V trigonal bipyramid, edges with two equivalent O(2)Li5V octahedra, edges with two equivalent O(3)Li5V pentagonal pyramids, edges with two equivalent O(4)Li5V pentagonal pyramids, and edges with two equivalent F(2)Li4V trigonal bipyramids. The corner-sharing octahedral tilt angles are 23°. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), one Li(6), and one V(1) atom to form distorted OLi5V octahedra that share  a cornercorner with one O(1)Li6V pentagonal bipyramid,  a cornercorner with one O(4)Li5V pentagonal pyramid, corners with two equivalent O(3)Li5V pentagonal pyramids,  a cornercorner with one F(2)Li4V trigonal bipyramid, edges with two equivalent O(1)Li6V pentagonal bipyramids,  an edgeedge with one O(3)Li5V pentagonal pyramid, edges with two equivalent O(4)Li5V pentagonal pyramids, and  an edgeedge with one F(2)Li4V trigonal bipyramid. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), one Li(7), and one V(1) atom to form distorted OLi5V pentagonal pyramids that share corners with two equivalent O(2)Li5V octahedra,  a cornercorner with one O(1)Li6V pentagonal bipyramid,  a cornercorner with one F(2)Li4V trigonal bipyramid,  an edgeedge with one O(2)Li5V octahedra, edges with two equivalent O(1)Li6V pentagonal bipyramids, edges with two equivalent O(4)Li5V pentagonal pyramids, and edges with two equivalent F(2)Li4V trigonal bipyramids. The corner-sharing octahedral tilt angles range from 8-79°. In the fourth O site, O(4) is bonded to one Li(1), one Li(4), one Li(5), one Li(6), one Li(7), and one V(1) atom to form distorted OLi5V pentagonal pyramids that share  a cornercorner with one O(2)Li5V octahedra,  a cornercorner with one O(1)Li6V pentagonal bipyramid, corners with three equivalent F(2)Li4V trigonal bipyramids, edges with two equivalent O(2)Li5V octahedra, edges with two equivalent O(1)Li6V pentagonal bipyramids, and edges with two equivalent O(3)Li5V pentagonal pyramids. The corner-sharing octahedral tilt angles are 48°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(5), one Li(6), and one V(1) atom. In the second F site, F(2) is bonded to one Li(2), one Li(3), one Li(4), one Li(7), and one V(1) atom to form distorted FLi4V trigonal bipyramids that share  a cornercorner with one O(2)Li5V octahedra,  a cornercorner with one O(1)Li6V pentagonal bipyramid,  a cornercorner with one O(3)Li5V pentagonal pyramid, corners with three equivalent O(4)Li5V pentagonal pyramids,  an edgeedge with one O(2)Li5V octahedra, edges with two equivalent O(1)Li6V pentagonal bipyramids, and edges with two equivalent O(3)Li5V pentagonal pyramids. The corner-sharing octahedral tilt angles are 64°.