Li2VO3F crystallizes in the monoclinic Cc space group. There are four inequivalent Li sites. In the first Li site, Li(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 LiO4F2 octahedra that share  a cornercorner with one Li(3)O4F2 octahedra,  a cornercorner with one Li(2)O5F octahedra, corners with four equivalent V(2)O5F octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent Li(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 5-17°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(1) atom to form distorted LiO5F octahedra that share  a cornercorner with one Li(1)O4F2 octahedra,  a cornercorner with one V(2)O5F octahedra, corners with four equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 4-20°. In the third Li site, Li(3) is bonded to one O(1), one O(3), one O(4), one O(6), one F(1), and one F(2) atom to form LiO4F2 octahedra that share  a cornercorner with one Li(1)O4F2 octahedra,  a cornercorner with one V(2)O5F octahedra, corners with four equivalent Li(2)O5F octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 7-20°. In the fourth Li site, Li(4) is bonded to one O(2), one O(4), one O(5), one O(6), one F(1), and one F(2) atom to form LiO4F2 octahedra that share edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(2)O5F octahedra, and edges with two equivalent V(2)O5F octahedra. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), and one F(2) atom. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one F(1) atom to form distorted VO5F octahedra that share  a cornercorner with one Li(3)O4F2 octahedra,  a cornercorner with one Li(2)O5F octahedra, corners with four equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent Li(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 4-17°. There are six inequivalent O sites. In the first O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(4), one V(1), and one V(2) atom. In the second O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one V(1), and one V(2) atom to form OLi3V2 trigonal bipyramids that share  a cornercorner with one O(3)Li3V2 square pyramid, corners with four equivalent O(4)Li4V square pyramids, edges with two equivalent O(3)Li3V2 square pyramids, and edges with two equivalent F(1)Li4V square pyramids. In the third O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one V(1) atom. In the fourth O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(1), and one V(2) atom to form OLi3V2 square pyramids that share corners with four equivalent F(1)Li4V square pyramids,  a cornercorner with one O(1)Li3V2 trigonal bipyramid, edges with two equivalent O(4)Li4V square pyramids, and edges with two equivalent O(1)Li3V2 trigonal bipyramids. In the fifth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one V(2) atom to form OLi4V square pyramids that share  a cornercorner with one F(1)Li4V square pyramid, corners with four equivalent O(1)Li3V2 trigonal bipyramids, edges with two equivalent O(3)Li3V2 square pyramids, and edges with two equivalent F(1)Li4V square pyramids. In the sixth O site, O(5) is bonded in a distorted square co-planar geometry to one Li(2), one Li(4), one V(1), and one V(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one V(2) atom to form FLi4V square pyramids that share  a cornercorner with one O(4)Li4V square pyramid, corners with four equivalent O(3)Li3V2 square pyramids, edges with two equivalent O(4)Li4V square pyramids, and edges with two equivalent O(1)Li3V2 trigonal bipyramids. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Li(4), and one V(1) atom.
Li2VO3F crystallizes in the monoclinic Cc space group. There are four inequivalent Li sites. In the first Li site, Li(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 LiO4F2 octahedra that share  a cornercorner with one Li(3)O4F2 octahedra,  a cornercorner with one Li(2)O5F octahedra, corners with four equivalent V(2)O5F octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent Li(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 5-17°. The Li(1)-O(1) bond length is 2.26 Å. The Li(1)-O(2) bond length is 2.14 Å. The Li(1)-O(3) bond length is 2.06 Å. The Li(1)-O(4) bond length is 2.20 Å. The Li(1)-F(1) bond length is 2.16 Å. The Li(1)-F(2) bond length is 1.95 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(1) atom to form distorted LiO5F octahedra that share  a cornercorner with one Li(1)O4F2 octahedra,  a cornercorner with one V(2)O5F octahedra, corners with four equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 4-20°. The Li(2)-O(1) bond length is 2.00 Å. The Li(2)-O(2) bond length is 2.12 Å. The Li(2)-O(3) bond length is 2.18 Å. The Li(2)-O(4) bond length is 2.06 Å. The Li(2)-O(5) bond length is 2.39 Å. The Li(2)-F(1) bond length is 1.98 Å. In the third Li site, Li(3) is bonded to one O(1), one O(3), one O(4), one O(6), one F(1), and one F(2) atom to form LiO4F2 octahedra that share  a cornercorner with one Li(1)O4F2 octahedra,  a cornercorner with one V(2)O5F octahedra, corners with four equivalent Li(2)O5F octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 7-20°. The Li(3)-O(1) bond length is 2.05 Å. The Li(3)-O(3) bond length is 2.09 Å. The Li(3)-O(4) bond length is 2.05 Å. The Li(3)-O(6) bond length is 2.19 Å. The Li(3)-F(1) bond length is 2.06 Å. The Li(3)-F(2) bond length is 2.34 Å. In the fourth Li site, Li(4) is bonded to one O(2), one O(4), one O(5), one O(6), one F(1), and one F(2) atom to form LiO4F2 octahedra that share edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(2)O5F octahedra, and edges with two equivalent V(2)O5F octahedra. The Li(4)-O(2) bond length is 2.08 Å. The Li(4)-O(4) bond length is 2.00 Å. The Li(4)-O(5) bond length is 2.22 Å. The Li(4)-O(6) bond length is 2.27 Å. The Li(4)-F(1) bond length is 1.97 Å. The Li(4)-F(2) bond length is 2.10 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), and one F(2) atom. The V(1)-O(1) bond length is 1.81 Å. The V(1)-O(2) bond length is 1.69 Å. The V(1)-O(3) bond length is 2.05 Å. The V(1)-O(5) bond length is 1.75 Å. The V(1)-O(6) bond length is 2.28 Å. The V(1)-F(2) bond length is 2.05 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one F(1) atom to form distorted VO5F octahedra that share  a cornercorner with one Li(3)O4F2 octahedra,  a cornercorner with one Li(2)O5F octahedra, corners with four equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent Li(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 4-17°. The V(2)-O(1) bond length is 2.15 Å. The V(2)-O(3) bond length is 1.82 Å. The V(2)-O(4) bond length is 1.74 Å. The V(2)-O(5) bond length is 2.16 Å. The V(2)-O(6) bond length is 1.72 Å. The V(2)-F(1) bond length is 2.11 Å. There are six inequivalent O sites. In the first O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(4), one V(1), and one V(2) atom. In the second O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one V(1), and one V(2) atom to form OLi3V2 trigonal bipyramids that share  a cornercorner with one O(3)Li3V2 square pyramid, corners with four equivalent O(4)Li4V square pyramids, edges with two equivalent O(3)Li3V2 square pyramids, and edges with two equivalent F(1)Li4V square pyramids. In the third O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one V(1) atom. In the fourth O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(1), and one V(2) atom to form OLi3V2 square pyramids that share corners with four equivalent F(1)Li4V square pyramids,  a cornercorner with one O(1)Li3V2 trigonal bipyramid, edges with two equivalent O(4)Li4V square pyramids, and edges with two equivalent O(1)Li3V2 trigonal bipyramids. In the fifth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one V(2) atom to form OLi4V square pyramids that share  a cornercorner with one F(1)Li4V square pyramid, corners with four equivalent O(1)Li3V2 trigonal bipyramids, edges with two equivalent O(3)Li3V2 square pyramids, and edges with two equivalent F(1)Li4V square pyramids. In the sixth O site, O(5) is bonded in a distorted square co-planar geometry to one Li(2), one Li(4), one V(1), and one V(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one V(2) atom to form FLi4V square pyramids that share  a cornercorner with one O(4)Li4V square pyramid, corners with four equivalent O(3)Li3V2 square pyramids, edges with two equivalent O(4)Li4V square pyramids, and edges with two equivalent O(1)Li3V2 trigonal bipyramids. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Li(4), and one V(1) atom.