Li3V2(O2F)2 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one F(1), one F(2), and one F(3) atom to form LiOF3 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent Li(2)OF3 tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra, corners with two equivalent Li(5)OF3 tetrahedra,  an edgeedge with one Li(4)OF3 tetrahedra, and  an edgeedge with one Li(6)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 45-67°. In the second Li site, Li(2) is bonded to one O(4), one F(1), one F(2), and one F(4) atom to form LiOF3 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent Li(1)OF3 tetrahedra, corners with two equivalent Li(4)OF3 tetrahedra, corners with two equivalent Li(6)OF3 tetrahedra,  an edgeedge with one Li(3)OF3 tetrahedra, and  an edgeedge with one Li(5)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 44-67°. In the third Li site, Li(3) is bonded to one O(6), one F(1), one F(3), and one F(4) atom to form LiOF3 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one Li(4)OF3 tetrahedra, corners with two equivalent Li(1)OF3 tetrahedra, corners with two equivalent Li(5)OF3 tetrahedra, corners with two equivalent Li(6)OF3 tetrahedra,  an edgeedge with one Li(2)OF3 tetrahedra, and  an edgeedge with one Li(4)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 46-67°. In the fourth Li site, Li(4) is bonded to one O(5), one F(1), one F(3), and one F(4) atom to form LiOF3 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one Li(3)OF3 tetrahedra, corners with two equivalent Li(2)OF3 tetrahedra, corners with two equivalent Li(5)OF3 tetrahedra, corners with two equivalent Li(6)OF3 tetrahedra,  an edgeedge with one Li(1)OF3 tetrahedra, and  an edgeedge with one Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 45-67°. In the fifth Li site, Li(5) is bonded to one O(8), one F(2), one F(3), and one F(4) atom to form LiOF3 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Li(6)OF3 tetrahedra, corners with two equivalent Li(1)OF3 tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra, corners with two equivalent Li(4)OF3 tetrahedra,  an edgeedge with one Li(2)OF3 tetrahedra, and  an edgeedge with one Li(6)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 46-66°. In the sixth Li site, Li(6) is bonded to one O(7), one F(2), one F(3), and one F(4) atom to form LiOF3 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Li(5)OF3 tetrahedra, corners with two equivalent Li(2)OF3 tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra, corners with two equivalent Li(4)OF3 tetrahedra,  an edgeedge with one Li(1)OF3 tetrahedra, and  an edgeedge with one Li(5)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 45-67°. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Li(1)OF3 tetrahedra,  a cornercorner with one Li(3)OF3 tetrahedra,  a cornercorner with one Li(4)OF3 tetrahedra,  a cornercorner with one Li(5)OF3 tetrahedra,  a cornercorner with one Li(6)OF3 tetrahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. In the second V site, V(2) is bonded to one O(2), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Li(2)OF3 tetrahedra,  a cornercorner with one Li(3)OF3 tetrahedra,  a cornercorner with one Li(4)OF3 tetrahedra,  a cornercorner with one Li(5)OF3 tetrahedra,  a cornercorner with one Li(6)OF3 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Li(1)OF3 tetrahedra,  a cornercorner with one Li(2)OF3 tetrahedra,  a cornercorner with one Li(5)OF3 tetrahedra,  a cornercorner with one Li(6)OF3 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. In the fourth V site, V(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one Li(1)OF3 tetrahedra,  a cornercorner with one Li(2)OF3 tetrahedra,  a cornercorner with one Li(3)OF3 tetrahedra,  a cornercorner with one Li(4)OF3 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(3), and one V(4) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one V(2), one V(3), and one V(4) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one V(3), and one V(4) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), one V(3), and one V(4) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one V(1), one V(2), and one V(4) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one V(1), one V(2), and one V(4) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(6), one V(1), one V(2), and one V(3) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(5), one V(1), one V(2), and one V(3) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a square co-planar geometry to one Li(1), one Li(2), one Li(3), and one Li(4) atom. In the second F site, F(2) is bonded in a square co-planar geometry to one Li(1), one Li(2), one Li(5), and one Li(6) atom. In the third F site, F(3) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), and one Li(6) atom to form distorted edge-sharing FLi5 trigonal bipyramids. In the fourth F site, F(4) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), and one Li(6) atom to form distorted edge-sharing FLi5 trigonal bipyramids.
Li3V2(O2F)2 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one F(1), one F(2), and one F(3) atom to form LiOF3 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent Li(2)OF3 tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra, corners with two equivalent Li(5)OF3 tetrahedra,  an edgeedge with one Li(4)OF3 tetrahedra, and  an edgeedge with one Li(6)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 45-67°. The Li(1)-O(3) bond length is 1.93 Å. The Li(1)-F(1) bond length is 1.90 Å. The Li(1)-F(2) bond length is 1.90 Å. The Li(1)-F(3) bond length is 1.91 Å. In the second Li site, Li(2) is bonded to one O(4), one F(1), one F(2), and one F(4) atom to form LiOF3 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent Li(1)OF3 tetrahedra, corners with two equivalent Li(4)OF3 tetrahedra, corners with two equivalent Li(6)OF3 tetrahedra,  an edgeedge with one Li(3)OF3 tetrahedra, and  an edgeedge with one Li(5)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 44-67°. The Li(2)-O(4) bond length is 1.93 Å. The Li(2)-F(1) bond length is 1.89 Å. The Li(2)-F(2) bond length is 1.90 Å. The Li(2)-F(4) bond length is 1.92 Å. In the third Li site, Li(3) is bonded to one O(6), one F(1), one F(3), and one F(4) atom to form LiOF3 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one Li(4)OF3 tetrahedra, corners with two equivalent Li(1)OF3 tetrahedra, corners with two equivalent Li(5)OF3 tetrahedra, corners with two equivalent Li(6)OF3 tetrahedra,  an edgeedge with one Li(2)OF3 tetrahedra, and  an edgeedge with one Li(4)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 46-67°. The Li(3)-O(6) bond length is 1.93 Å. The Li(3)-F(1) bond length is 1.92 Å. The Li(3)-F(3) bond length is 2.01 Å. The Li(3)-F(4) bond length is 2.00 Å. In the fourth Li site, Li(4) is bonded to one O(5), one F(1), one F(3), and one F(4) atom to form LiOF3 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one Li(3)OF3 tetrahedra, corners with two equivalent Li(2)OF3 tetrahedra, corners with two equivalent Li(5)OF3 tetrahedra, corners with two equivalent Li(6)OF3 tetrahedra,  an edgeedge with one Li(1)OF3 tetrahedra, and  an edgeedge with one Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 45-67°. The Li(4)-O(5) bond length is 1.93 Å. The Li(4)-F(1) bond length is 1.92 Å. The Li(4)-F(3) bond length is 2.00 Å. The Li(4)-F(4) bond length is 2.01 Å. In the fifth Li site, Li(5) is bonded to one O(8), one F(2), one F(3), and one F(4) atom to form LiOF3 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Li(6)OF3 tetrahedra, corners with two equivalent Li(1)OF3 tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra, corners with two equivalent Li(4)OF3 tetrahedra,  an edgeedge with one Li(2)OF3 tetrahedra, and  an edgeedge with one Li(6)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 46-66°. The Li(5)-O(8) bond length is 1.93 Å. The Li(5)-F(2) bond length is 1.92 Å. The Li(5)-F(3) bond length is 2.01 Å. The Li(5)-F(4) bond length is 2.00 Å. In the sixth Li site, Li(6) is bonded to one O(7), one F(2), one F(3), and one F(4) atom to form LiOF3 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Li(5)OF3 tetrahedra, corners with two equivalent Li(2)OF3 tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra, corners with two equivalent Li(4)OF3 tetrahedra,  an edgeedge with one Li(1)OF3 tetrahedra, and  an edgeedge with one Li(5)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 45-67°. The Li(6)-O(7) bond length is 1.93 Å. The Li(6)-F(2) bond length is 1.92 Å. The Li(6)-F(3) bond length is 2.00 Å. The Li(6)-F(4) bond length is 2.01 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Li(1)OF3 tetrahedra,  a cornercorner with one Li(3)OF3 tetrahedra,  a cornercorner with one Li(4)OF3 tetrahedra,  a cornercorner with one Li(5)OF3 tetrahedra,  a cornercorner with one Li(6)OF3 tetrahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The V(1)-O(1) bond length is 1.87 Å. The V(1)-O(3) bond length is 1.92 Å. The V(1)-O(5) bond length is 2.00 Å. The V(1)-O(6) bond length is 2.04 Å. The V(1)-O(7) bond length is 2.00 Å. The V(1)-O(8) bond length is 2.04 Å. In the second V site, V(2) is bonded to one O(2), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Li(2)OF3 tetrahedra,  a cornercorner with one Li(3)OF3 tetrahedra,  a cornercorner with one Li(4)OF3 tetrahedra,  a cornercorner with one Li(5)OF3 tetrahedra,  a cornercorner with one Li(6)OF3 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The V(2)-O(2) bond length is 1.87 Å. The V(2)-O(4) bond length is 1.92 Å. The V(2)-O(5) bond length is 2.04 Å. The V(2)-O(6) bond length is 2.00 Å. The V(2)-O(7) bond length is 2.04 Å. The V(2)-O(8) bond length is 2.00 Å. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Li(1)OF3 tetrahedra,  a cornercorner with one Li(2)OF3 tetrahedra,  a cornercorner with one Li(5)OF3 tetrahedra,  a cornercorner with one Li(6)OF3 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The V(3)-O(1) bond length is 2.03 Å. The V(3)-O(2) bond length is 2.03 Å. The V(3)-O(3) bond length is 2.10 Å. The V(3)-O(4) bond length is 2.09 Å. The V(3)-O(7) bond length is 2.04 Å. The V(3)-O(8) bond length is 2.04 Å. In the fourth V site, V(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one Li(1)OF3 tetrahedra,  a cornercorner with one Li(2)OF3 tetrahedra,  a cornercorner with one Li(3)OF3 tetrahedra,  a cornercorner with one Li(4)OF3 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The V(4)-O(1) bond length is 2.03 Å. The V(4)-O(2) bond length is 2.03 Å. The V(4)-O(3) bond length is 2.09 Å. The V(4)-O(4) bond length is 2.09 Å. The V(4)-O(5) bond length is 2.04 Å. The V(4)-O(6) bond length is 2.04 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(3), and one V(4) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one V(2), one V(3), and one V(4) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one V(3), and one V(4) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), one V(3), and one V(4) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one V(1), one V(2), and one V(4) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one V(1), one V(2), and one V(4) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(6), one V(1), one V(2), and one V(3) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(5), one V(1), one V(2), and one V(3) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a square co-planar geometry to one Li(1), one Li(2), one Li(3), and one Li(4) atom. In the second F site, F(2) is bonded in a square co-planar geometry to one Li(1), one Li(2), one Li(5), and one Li(6) atom. In the third F site, F(3) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), and one Li(6) atom to form distorted edge-sharing FLi5 trigonal bipyramids. In the fourth F site, F(4) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), and one Li(6) atom to form distorted edge-sharing FLi5 trigonal bipyramids.