Li5VO3F2 crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a square co-planar geometry to one O(2), one O(3), one F(1), and one F(2) atom. In the second Li site, Li(2) is bonded to one O(1), one O(3), two equivalent O(2), and one F(2) atom to form LiO4F trigonal bipyramids that share  a cornercorner with one Li(4)O2F3 trigonal bipyramid,  a cornercorner with one Li(5)O2F3 trigonal bipyramid,  a cornercorner with one Li(3)O4F trigonal bipyramid, corners with two equivalent Li(2)O4F trigonal bipyramids, edges with three equivalent V(1)O4F2 octahedra,  an edgeedge with one Li(4)O2F3 trigonal bipyramid, edges with two equivalent Li(5)O2F3 trigonal bipyramids, and edges with two equivalent Li(3)O4F trigonal bipyramids. In the third Li site, Li(3) is bonded to one O(1), one O(2), two equivalent O(3), and one F(1) atom to form distorted LiO4F trigonal bipyramids that share  a cornercorner with one Li(4)O2F3 trigonal bipyramid,  a cornercorner with one Li(5)O2F3 trigonal bipyramid,  a cornercorner with one Li(2)O4F trigonal bipyramid, corners with two equivalent Li(3)O4F trigonal bipyramids, edges with three equivalent V(1)O4F2 octahedra,  an edgeedge with one Li(5)O2F3 trigonal bipyramid, edges with two equivalent Li(4)O2F3 trigonal bipyramids, and edges with two equivalent Li(2)O4F trigonal bipyramids. In the fourth Li site, Li(4) is bonded to one O(1), one O(3), one F(2), and two equivalent F(1) atoms to form distorted LiO2F3 trigonal bipyramids that share corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(5)O2F3 trigonal bipyramid,  a cornercorner with one Li(2)O4F trigonal bipyramid,  a cornercorner with one Li(3)O4F trigonal bipyramid, corners with two equivalent Li(4)O2F3 trigonal bipyramids, edges with two equivalent V(1)O4F2 octahedra,  an edgeedge with one Li(2)O4F trigonal bipyramid, edges with two equivalent Li(5)O2F3 trigonal bipyramids, and edges with two equivalent Li(3)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 8-15°. In the fifth Li site, Li(5) is bonded to one O(1), one O(2), one F(1), and two equivalent F(2) atoms to form distorted LiO2F3 trigonal bipyramids that share corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(4)O2F3 trigonal bipyramid,  a cornercorner with one Li(2)O4F trigonal bipyramid,  a cornercorner with one Li(3)O4F trigonal bipyramid, corners with two equivalent Li(5)O2F3 trigonal bipyramids, edges with two equivalent V(1)O4F2 octahedra,  an edgeedge with one Li(3)O4F trigonal bipyramid, edges with two equivalent Li(4)O2F3 trigonal bipyramids, and edges with two equivalent Li(2)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 8-14°. V(1) is bonded to one O(2), one O(3), two equivalent O(1), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent Li(4)O2F3 trigonal bipyramids, corners with two equivalent Li(5)O2F3 trigonal bipyramids, edges with two equivalent Li(4)O2F3 trigonal bipyramids, edges with two equivalent Li(5)O2F3 trigonal bipyramids, edges with three equivalent Li(2)O4F trigonal bipyramids, and edges with three equivalent Li(3)O4F trigonal bipyramids. The corner-sharing octahedra are not tilted. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), and two equivalent V(1) atoms to form OLi4V2 octahedra that share corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li5V octahedra, corners with two equivalent F(2)Li5V octahedra, edges with two equivalent F(1)Li5V octahedra, edges with two equivalent F(2)Li5V octahedra, edges with three equivalent O(2)Li5V octahedra, and edges with three equivalent O(3)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-26°. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Li(5), two equivalent Li(2), and one V(1) atom to form OLi5V octahedra that share corners with two equivalent O(2)Li5V octahedra, corners with two equivalent O(3)Li5V octahedra, edges with two equivalent O(3)Li5V octahedra, edges with two equivalent F(1)Li5V octahedra, edges with three equivalent O(1)Li4V2 octahedra, and edges with three equivalent F(2)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-21°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(4), two equivalent Li(3), and one V(1) atom to form OLi5V octahedra that share corners with two equivalent O(2)Li5V octahedra, corners with two equivalent O(3)Li5V octahedra, edges with two equivalent O(2)Li5V octahedra, edges with two equivalent F(2)Li5V octahedra, edges with three equivalent O(1)Li4V2 octahedra, and edges with three equivalent F(1)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-21°. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(3), one Li(5), two equivalent Li(4), and one V(1) atom to form FLi5V octahedra that share corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li5V octahedra, corners with two equivalent F(2)Li5V octahedra, edges with two equivalent O(1)Li4V2 octahedra, edges with two equivalent O(2)Li5V octahedra, edges with two equivalent F(2)Li5V octahedra, and edges with three equivalent O(3)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-25°. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(4), two equivalent Li(5), and one V(1) atom to form FLi5V octahedra that share corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li5V octahedra, corners with two equivalent F(2)Li5V octahedra, edges with two equivalent O(1)Li4V2 octahedra, edges with two equivalent O(3)Li5V octahedra, edges with two equivalent F(1)Li5V octahedra, and edges with three equivalent O(2)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-26°.
Li5VO3F2 crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a square co-planar geometry to one O(2), one O(3), one F(1), and one F(2) atom. The Li(1)-O(2) bond length is 1.90 Å. The Li(1)-O(3) bond length is 1.90 Å. The Li(1)-F(1) bond length is 2.19 Å. The Li(1)-F(2) bond length is 2.25 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), two equivalent O(2), and one F(2) atom to form LiO4F trigonal bipyramids that share  a cornercorner with one Li(4)O2F3 trigonal bipyramid,  a cornercorner with one Li(5)O2F3 trigonal bipyramid,  a cornercorner with one Li(3)O4F trigonal bipyramid, corners with two equivalent Li(2)O4F trigonal bipyramids, edges with three equivalent V(1)O4F2 octahedra,  an edgeedge with one Li(4)O2F3 trigonal bipyramid, edges with two equivalent Li(5)O2F3 trigonal bipyramids, and edges with two equivalent Li(3)O4F trigonal bipyramids. The Li(2)-O(1) bond length is 2.04 Å. The Li(2)-O(3) bond length is 2.03 Å. Both Li(2)-O(2) bond lengths are 2.04 Å. The Li(2)-F(2) bond length is 2.31 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), two equivalent O(3), and one F(1) atom to form distorted LiO4F trigonal bipyramids that share  a cornercorner with one Li(4)O2F3 trigonal bipyramid,  a cornercorner with one Li(5)O2F3 trigonal bipyramid,  a cornercorner with one Li(2)O4F trigonal bipyramid, corners with two equivalent Li(3)O4F trigonal bipyramids, edges with three equivalent V(1)O4F2 octahedra,  an edgeedge with one Li(5)O2F3 trigonal bipyramid, edges with two equivalent Li(4)O2F3 trigonal bipyramids, and edges with two equivalent Li(2)O4F trigonal bipyramids. The Li(3)-O(1) bond length is 2.03 Å. The Li(3)-O(2) bond length is 2.03 Å. Both Li(3)-O(3) bond lengths are 2.04 Å. The Li(3)-F(1) bond length is 2.32 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(3), one F(2), and two equivalent F(1) atoms to form distorted LiO2F3 trigonal bipyramids that share corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(5)O2F3 trigonal bipyramid,  a cornercorner with one Li(2)O4F trigonal bipyramid,  a cornercorner with one Li(3)O4F trigonal bipyramid, corners with two equivalent Li(4)O2F3 trigonal bipyramids, edges with two equivalent V(1)O4F2 octahedra,  an edgeedge with one Li(2)O4F trigonal bipyramid, edges with two equivalent Li(5)O2F3 trigonal bipyramids, and edges with two equivalent Li(3)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 8-15°. The Li(4)-O(1) bond length is 2.16 Å. The Li(4)-O(3) bond length is 1.92 Å. The Li(4)-F(2) bond length is 1.99 Å. Both Li(4)-F(1) bond lengths are 2.05 Å. In the fifth Li site, Li(5) is bonded to one O(1), one O(2), one F(1), and two equivalent F(2) atoms to form distorted LiO2F3 trigonal bipyramids that share corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(4)O2F3 trigonal bipyramid,  a cornercorner with one Li(2)O4F trigonal bipyramid,  a cornercorner with one Li(3)O4F trigonal bipyramid, corners with two equivalent Li(5)O2F3 trigonal bipyramids, edges with two equivalent V(1)O4F2 octahedra,  an edgeedge with one Li(3)O4F trigonal bipyramid, edges with two equivalent Li(4)O2F3 trigonal bipyramids, and edges with two equivalent Li(2)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 8-14°. The Li(5)-O(1) bond length is 2.15 Å. The Li(5)-O(2) bond length is 1.92 Å. The Li(5)-F(1) bond length is 1.99 Å. There is one shorter (2.04 Å) and one longer (2.05 Å) Li(5)-F(2) bond length. V(1) is bonded to one O(2), one O(3), two equivalent O(1), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent Li(4)O2F3 trigonal bipyramids, corners with two equivalent Li(5)O2F3 trigonal bipyramids, edges with two equivalent Li(4)O2F3 trigonal bipyramids, edges with two equivalent Li(5)O2F3 trigonal bipyramids, edges with three equivalent Li(2)O4F trigonal bipyramids, and edges with three equivalent Li(3)O4F trigonal bipyramids. The corner-sharing octahedra are not tilted. The V(1)-O(2) bond length is 2.01 Å. The V(1)-O(3) bond length is 2.01 Å. Both V(1)-O(1) bond lengths are 2.01 Å. The V(1)-F(1) bond length is 2.13 Å. The V(1)-F(2) bond length is 2.13 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), and two equivalent V(1) atoms to form OLi4V2 octahedra that share corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li5V octahedra, corners with two equivalent F(2)Li5V octahedra, edges with two equivalent F(1)Li5V octahedra, edges with two equivalent F(2)Li5V octahedra, edges with three equivalent O(2)Li5V octahedra, and edges with three equivalent O(3)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-26°. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Li(5), two equivalent Li(2), and one V(1) atom to form OLi5V octahedra that share corners with two equivalent O(2)Li5V octahedra, corners with two equivalent O(3)Li5V octahedra, edges with two equivalent O(3)Li5V octahedra, edges with two equivalent F(1)Li5V octahedra, edges with three equivalent O(1)Li4V2 octahedra, and edges with three equivalent F(2)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-21°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(4), two equivalent Li(3), and one V(1) atom to form OLi5V octahedra that share corners with two equivalent O(2)Li5V octahedra, corners with two equivalent O(3)Li5V octahedra, edges with two equivalent O(2)Li5V octahedra, edges with two equivalent F(2)Li5V octahedra, edges with three equivalent O(1)Li4V2 octahedra, and edges with three equivalent F(1)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-21°. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(3), one Li(5), two equivalent Li(4), and one V(1) atom to form FLi5V octahedra that share corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li5V octahedra, corners with two equivalent F(2)Li5V octahedra, edges with two equivalent O(1)Li4V2 octahedra, edges with two equivalent O(2)Li5V octahedra, edges with two equivalent F(2)Li5V octahedra, and edges with three equivalent O(3)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-25°. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(4), two equivalent Li(5), and one V(1) atom to form FLi5V octahedra that share corners with two equivalent O(1)Li4V2 octahedra, corners with two equivalent F(1)Li5V octahedra, corners with two equivalent F(2)Li5V octahedra, edges with two equivalent O(1)Li4V2 octahedra, edges with two equivalent O(3)Li5V octahedra, edges with two equivalent F(1)Li5V octahedra, and edges with three equivalent O(2)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-26°.