Li6V2O5F2 crystallizes in the triclinic P-1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), two equivalent O(5), and one F(2) atom to form distorted LiO4F square pyramids that share corners with three equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(4)O3F2 square pyramid,  a cornercorner with one Li(5)O4F square pyramid, corners with two equivalent Li(2)O4F square pyramids,  a cornercorner with one Li(6)O4F trigonal bipyramid,  an edgeedge with one V(2)O4F2 octahedra, edges with two equivalent V(1)O4F2 octahedra,  an edgeedge with one Li(1)O4F square pyramid, edges with two equivalent Li(4)O3F2 square pyramids, and edges with two equivalent Li(5)O4F square pyramids. The corner-sharing octahedral tilt angles range from 5-16°. In the second Li site, Li(2) is bonded to one O(3), one O(4), two equivalent O(2), and one F(2) atom to form LiO4F square pyramids that share  a cornercorner with one Li(4)O3F2 square pyramid,  a cornercorner with one Li(5)O4F square pyramid, corners with two equivalent Li(1)O4F square pyramids, corners with four equivalent Li(6)O4F trigonal bipyramids,  an edgeedge with one V(1)O4F2 octahedra, edges with three equivalent V(2)O4F2 octahedra,  an edgeedge with one Li(2)O4F square pyramid, and  an edgeedge with one Li(6)O4F trigonal bipyramid. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(3), one F(1), and one F(2) atom. In the fourth Li site, Li(4) is bonded to one O(5), two equivalent O(1), one F(1), and one F(2) atom to form distorted LiO3F2 square pyramids that share  a cornercorner with one Li(1)O4F square pyramid,  a cornercorner with one Li(2)O4F square pyramid, corners with four equivalent Li(5)O4F square pyramids,  a cornercorner with one Li(6)O4F trigonal bipyramid,  an edgeedge with one V(2)O4F2 octahedra, edges with three equivalent V(1)O4F2 octahedra,  an edgeedge with one Li(4)O3F2 square pyramid,  an edgeedge with one Li(5)O4F square pyramid, and edges with two equivalent Li(1)O4F square pyramids. In the fifth Li site, Li(5) is bonded to one O(4), one O(5), two equivalent O(1), and one F(1) atom to form LiO4F square pyramids that share  a cornercorner with one Li(1)O4F square pyramid,  a cornercorner with one Li(2)O4F square pyramid, corners with four equivalent Li(4)O3F2 square pyramids, corners with two equivalent Li(6)O4F trigonal bipyramids,  an edgeedge with one V(2)O4F2 octahedra, edges with three equivalent V(1)O4F2 octahedra,  an edgeedge with one Li(4)O3F2 square pyramid,  an edgeedge with one Li(5)O4F square pyramid, and edges with two equivalent Li(1)O4F square pyramids. In the sixth Li site, Li(6) is bonded to one O(3), one O(4), two equivalent O(2), and one F(1) atom to form LiO4F trigonal bipyramids that share  a cornercorner with one Li(4)O3F2 square pyramid,  a cornercorner with one Li(1)O4F square pyramid, corners with two equivalent Li(5)O4F square pyramids, corners with four equivalent Li(2)O4F square pyramids,  an edgeedge with one V(1)O4F2 octahedra, edges with three equivalent V(2)O4F2 octahedra,  an edgeedge with one Li(2)O4F square pyramid, and  an edgeedge with one Li(6)O4F trigonal bipyramid. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(4), two equivalent O(5), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with three equivalent V(2)O4F2 octahedra, corners with three equivalent Li(1)O4F square pyramids,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Li(2)O4F square pyramid, edges with two equivalent Li(1)O4F square pyramids, edges with three equivalent Li(4)O3F2 square pyramids, edges with three equivalent Li(5)O4F square pyramids, and  an edgeedge with one Li(6)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 4-11°. In the second V site, V(2) is bonded to one O(2), one O(4), two equivalent O(3), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with three equivalent V(1)O4F2 octahedra,  an edgeedge with one V(2)O4F2 octahedra,  an edgeedge with one Li(4)O3F2 square pyramid,  an edgeedge with one Li(1)O4F square pyramid,  an edgeedge with one Li(5)O4F square pyramid, edges with three equivalent Li(2)O4F square pyramids, and edges with three equivalent Li(6)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 4-11°. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(4), two equivalent Li(5), and one V(1) atom to form OLi5V octahedra that share corners with three equivalent F(1)Li4V2 octahedra,  an edgeedge with one F(1)Li4V2 octahedra, edges with two equivalent O(4)Li4V2 octahedra, edges with two equivalent O(1)Li5V octahedra, edges with two equivalent F(2)Li4V2 octahedra, and edges with four equivalent O(5)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 6-19°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(2), two equivalent Li(6), and one V(2) atom to form OLi5V octahedra that share corners with three equivalent O(4)Li4V2 octahedra,  an edgeedge with one O(4)Li4V2 octahedra, edges with two equivalent O(2)Li5V octahedra, edges with two equivalent F(1)Li4V2 octahedra, edges with two equivalent F(2)Li4V2 octahedra, and edges with four equivalent O(3)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 10-23°. In the third O site, O(3) is bonded to one Li(2), one Li(6), two equivalent Li(3), and two equivalent V(2) atoms to form OLi4V2 octahedra that share corners with three equivalent F(1)Li4V2 octahedra, corners with three equivalent F(2)Li4V2 octahedra,  an edgeedge with one F(1)Li4V2 octahedra,  an edgeedge with one F(2)Li4V2 octahedra, edges with two equivalent O(3)Li4V2 octahedra, edges with two equivalent O(4)Li4V2 octahedra, and edges with four equivalent O(2)Li5V octahedra. The corner-sharing octahedral tilt angles range from 2-27°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(5), one Li(6), one V(1), and one V(2) atom to form OLi4V2 octahedra that share corners with three equivalent O(5)Li4V2 octahedra, corners with three equivalent O(2)Li5V octahedra,  an edgeedge with one O(5)Li4V2 octahedra,  an edgeedge with one O(2)Li5V octahedra, edges with two equivalent O(3)Li4V2 octahedra, edges with two equivalent O(1)Li5V octahedra, edges with two equivalent F(1)Li4V2 octahedra, and edges with two equivalent F(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 9-24°. In the fifth O site, O(5) is bonded to one Li(4), one Li(5), two equivalent Li(1), and two equivalent V(1) atoms to form OLi4V2 octahedra that share corners with three equivalent O(4)Li4V2 octahedra, corners with three equivalent F(2)Li4V2 octahedra,  an edgeedge with one O(4)Li4V2 octahedra,  an edgeedge with one F(2)Li4V2 octahedra, edges with two equivalent O(5)Li4V2 octahedra, edges with two equivalent F(1)Li4V2 octahedra, and edges with four equivalent O(1)Li5V octahedra. The corner-sharing octahedral tilt angles range from 9-24°. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(3), one Li(4), one Li(5), one Li(6), one V(1), and one V(2) atom to form distorted FLi4V2 octahedra that share corners with three equivalent O(3)Li4V2 octahedra, corners with three equivalent O(1)Li5V octahedra,  an edgeedge with one O(3)Li4V2 octahedra,  an edgeedge with one O(1)Li5V octahedra, edges with two equivalent O(4)Li4V2 octahedra, edges with two equivalent O(5)Li4V2 octahedra, edges with two equivalent O(2)Li5V octahedra, and edges with two equivalent F(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 2-23°. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(1), and one V(2) atom to form distorted FLi4V2 octahedra that share corners with three equivalent O(3)Li4V2 octahedra, corners with three equivalent O(5)Li4V2 octahedra,  an edgeedge with one O(3)Li4V2 octahedra,  an edgeedge with one O(5)Li4V2 octahedra, edges with two equivalent O(4)Li4V2 octahedra, edges with two equivalent O(1)Li5V octahedra, edges with two equivalent O(2)Li5V octahedra, and edges with two equivalent F(1)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 3-27°.
Li6V2O5F2 crystallizes in the triclinic P-1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), two equivalent O(5), and one F(2) atom to form distorted LiO4F square pyramids that share corners with three equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(4)O3F2 square pyramid,  a cornercorner with one Li(5)O4F square pyramid, corners with two equivalent Li(2)O4F square pyramids,  a cornercorner with one Li(6)O4F trigonal bipyramid,  an edgeedge with one V(2)O4F2 octahedra, edges with two equivalent V(1)O4F2 octahedra,  an edgeedge with one Li(1)O4F square pyramid, edges with two equivalent Li(4)O3F2 square pyramids, and edges with two equivalent Li(5)O4F square pyramids. The corner-sharing octahedral tilt angles range from 5-16°. The Li(1)-O(1) bond length is 1.98 Å. The Li(1)-O(4) bond length is 2.20 Å. There is one shorter (2.03 Å) and one longer (2.07 Å) Li(1)-O(5) bond length. The Li(1)-F(2) bond length is 2.25 Å. In the second Li site, Li(2) is bonded to one O(3), one O(4), two equivalent O(2), and one F(2) atom to form LiO4F square pyramids that share  a cornercorner with one Li(4)O3F2 square pyramid,  a cornercorner with one Li(5)O4F square pyramid, corners with two equivalent Li(1)O4F square pyramids, corners with four equivalent Li(6)O4F trigonal bipyramids,  an edgeedge with one V(1)O4F2 octahedra, edges with three equivalent V(2)O4F2 octahedra,  an edgeedge with one Li(2)O4F square pyramid, and  an edgeedge with one Li(6)O4F trigonal bipyramid. The Li(2)-O(3) bond length is 2.03 Å. The Li(2)-O(4) bond length is 2.23 Å. Both Li(2)-O(2) bond lengths are 1.99 Å. The Li(2)-F(2) bond length is 2.18 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(3), one F(1), and one F(2) atom. The Li(3)-O(2) bond length is 1.92 Å. There is one shorter (2.00 Å) and one longer (2.01 Å) Li(3)-O(3) bond length. The Li(3)-F(1) bond length is 2.44 Å. The Li(3)-F(2) bond length is 2.24 Å. In the fourth Li site, Li(4) is bonded to one O(5), two equivalent O(1), one F(1), and one F(2) atom to form distorted LiO3F2 square pyramids that share  a cornercorner with one Li(1)O4F square pyramid,  a cornercorner with one Li(2)O4F square pyramid, corners with four equivalent Li(5)O4F square pyramids,  a cornercorner with one Li(6)O4F trigonal bipyramid,  an edgeedge with one V(2)O4F2 octahedra, edges with three equivalent V(1)O4F2 octahedra,  an edgeedge with one Li(4)O3F2 square pyramid,  an edgeedge with one Li(5)O4F square pyramid, and edges with two equivalent Li(1)O4F square pyramids. The Li(4)-O(5) bond length is 2.01 Å. There is one shorter (1.93 Å) and one longer (1.95 Å) Li(4)-O(1) bond length. The Li(4)-F(1) bond length is 2.20 Å. The Li(4)-F(2) bond length is 2.49 Å. In the fifth Li site, Li(5) is bonded to one O(4), one O(5), two equivalent O(1), and one F(1) atom to form LiO4F square pyramids that share  a cornercorner with one Li(1)O4F square pyramid,  a cornercorner with one Li(2)O4F square pyramid, corners with four equivalent Li(4)O3F2 square pyramids, corners with two equivalent Li(6)O4F trigonal bipyramids,  an edgeedge with one V(2)O4F2 octahedra, edges with three equivalent V(1)O4F2 octahedra,  an edgeedge with one Li(4)O3F2 square pyramid,  an edgeedge with one Li(5)O4F square pyramid, and edges with two equivalent Li(1)O4F square pyramids. The Li(5)-O(4) bond length is 2.28 Å. The Li(5)-O(5) bond length is 2.09 Å. There is one shorter (1.95 Å) and one longer (2.01 Å) Li(5)-O(1) bond length. The Li(5)-F(1) bond length is 2.06 Å. In the sixth Li site, Li(6) is bonded to one O(3), one O(4), two equivalent O(2), and one F(1) atom to form LiO4F trigonal bipyramids that share  a cornercorner with one Li(4)O3F2 square pyramid,  a cornercorner with one Li(1)O4F square pyramid, corners with two equivalent Li(5)O4F square pyramids, corners with four equivalent Li(2)O4F square pyramids,  an edgeedge with one V(1)O4F2 octahedra, edges with three equivalent V(2)O4F2 octahedra,  an edgeedge with one Li(2)O4F square pyramid, and  an edgeedge with one Li(6)O4F trigonal bipyramid. The Li(6)-O(3) bond length is 2.05 Å. The Li(6)-O(4) bond length is 2.11 Å. There is one shorter (1.99 Å) and one longer (2.02 Å) Li(6)-O(2) bond length. The Li(6)-F(1) bond length is 2.22 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(4), two equivalent O(5), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with three equivalent V(2)O4F2 octahedra, corners with three equivalent Li(1)O4F square pyramids,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Li(2)O4F square pyramid, edges with two equivalent Li(1)O4F square pyramids, edges with three equivalent Li(4)O3F2 square pyramids, edges with three equivalent Li(5)O4F square pyramids, and  an edgeedge with one Li(6)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 4-11°. The V(1)-O(1) bond length is 1.92 Å. The V(1)-O(4) bond length is 2.00 Å. There is one shorter (2.02 Å) and one longer (2.07 Å) V(1)-O(5) bond length. The V(1)-F(1) bond length is 2.22 Å. The V(1)-F(2) bond length is 2.18 Å. In the second V site, V(2) is bonded to one O(2), one O(4), two equivalent O(3), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with three equivalent V(1)O4F2 octahedra,  an edgeedge with one V(2)O4F2 octahedra,  an edgeedge with one Li(4)O3F2 square pyramid,  an edgeedge with one Li(1)O4F square pyramid,  an edgeedge with one Li(5)O4F square pyramid, edges with three equivalent Li(2)O4F square pyramids, and edges with three equivalent Li(6)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 4-11°. The V(2)-O(2) bond length is 1.95 Å. The V(2)-O(4) bond length is 2.03 Å. There is one shorter (1.97 Å) and one longer (2.09 Å) V(2)-O(3) bond length. The V(2)-F(1) bond length is 2.18 Å. The V(2)-F(2) bond length is 2.15 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(4), two equivalent Li(5), and one V(1) atom to form OLi5V octahedra that share corners with three equivalent F(1)Li4V2 octahedra,  an edgeedge with one F(1)Li4V2 octahedra, edges with two equivalent O(4)Li4V2 octahedra, edges with two equivalent O(1)Li5V octahedra, edges with two equivalent F(2)Li4V2 octahedra, and edges with four equivalent O(5)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 6-19°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(2), two equivalent Li(6), and one V(2) atom to form OLi5V octahedra that share corners with three equivalent O(4)Li4V2 octahedra,  an edgeedge with one O(4)Li4V2 octahedra, edges with two equivalent O(2)Li5V octahedra, edges with two equivalent F(1)Li4V2 octahedra, edges with two equivalent F(2)Li4V2 octahedra, and edges with four equivalent O(3)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 10-23°. In the third O site, O(3) is bonded to one Li(2), one Li(6), two equivalent Li(3), and two equivalent V(2) atoms to form OLi4V2 octahedra that share corners with three equivalent F(1)Li4V2 octahedra, corners with three equivalent F(2)Li4V2 octahedra,  an edgeedge with one F(1)Li4V2 octahedra,  an edgeedge with one F(2)Li4V2 octahedra, edges with two equivalent O(3)Li4V2 octahedra, edges with two equivalent O(4)Li4V2 octahedra, and edges with four equivalent O(2)Li5V octahedra. The corner-sharing octahedral tilt angles range from 2-27°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(5), one Li(6), one V(1), and one V(2) atom to form OLi4V2 octahedra that share corners with three equivalent O(5)Li4V2 octahedra, corners with three equivalent O(2)Li5V octahedra,  an edgeedge with one O(5)Li4V2 octahedra,  an edgeedge with one O(2)Li5V octahedra, edges with two equivalent O(3)Li4V2 octahedra, edges with two equivalent O(1)Li5V octahedra, edges with two equivalent F(1)Li4V2 octahedra, and edges with two equivalent F(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 9-24°. In the fifth O site, O(5) is bonded to one Li(4), one Li(5), two equivalent Li(1), and two equivalent V(1) atoms to form OLi4V2 octahedra that share corners with three equivalent O(4)Li4V2 octahedra, corners with three equivalent F(2)Li4V2 octahedra,  an edgeedge with one O(4)Li4V2 octahedra,  an edgeedge with one F(2)Li4V2 octahedra, edges with two equivalent O(5)Li4V2 octahedra, edges with two equivalent F(1)Li4V2 octahedra, and edges with four equivalent O(1)Li5V octahedra. The corner-sharing octahedral tilt angles range from 9-24°. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(3), one Li(4), one Li(5), one Li(6), one V(1), and one V(2) atom to form distorted FLi4V2 octahedra that share corners with three equivalent O(3)Li4V2 octahedra, corners with three equivalent O(1)Li5V octahedra,  an edgeedge with one O(3)Li4V2 octahedra,  an edgeedge with one O(1)Li5V octahedra, edges with two equivalent O(4)Li4V2 octahedra, edges with two equivalent O(5)Li4V2 octahedra, edges with two equivalent O(2)Li5V octahedra, and edges with two equivalent F(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 2-23°. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(1), and one V(2) atom to form distorted FLi4V2 octahedra that share corners with three equivalent O(3)Li4V2 octahedra, corners with three equivalent O(5)Li4V2 octahedra,  an edgeedge with one O(3)Li4V2 octahedra,  an edgeedge with one O(5)Li4V2 octahedra, edges with two equivalent O(4)Li4V2 octahedra, edges with two equivalent O(1)Li5V octahedra, edges with two equivalent O(2)Li5V octahedra, and edges with two equivalent F(1)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 3-27°.