Li5VO4F crystallizes in the monoclinic Cc space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one F(1) atom. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), and one F(1) atom to form distorted LiO4F square pyramids that share  a cornercorner with one Li(4)O4F square pyramid, corners with four equivalent V(1)O4 tetrahedra,  a cornercorner with one Li(3)O4F trigonal bipyramid, edges with two equivalent Li(4)O4F square pyramids, 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), one O(3), one O(4), and one F(1) atom to form LiO4F trigonal bipyramids that share  a cornercorner with one Li(2)O4F square pyramid,  a cornercorner with one Li(4)O4F square pyramid, corners with two equivalent V(1)O4 tetrahedra, edges with two equivalent Li(2)O4F square pyramids, edges with two equivalent Li(4)O4F square pyramids, and  an edgeedge with one V(1)O4 tetrahedra. 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(1) atom to form distorted LiO4F square pyramids that share  a cornercorner with one Li(2)O4F square pyramid, corners with two equivalent V(1)O4 tetrahedra,  a cornercorner with one Li(3)O4F trigonal bipyramid, edges with two equivalent Li(2)O4F square pyramids,  an edgeedge with one V(1)O4 tetrahedra, and edges with two equivalent Li(3)O4F trigonal bipyramids. In the fifth Li site, Li(5) is bonded in a rectangular see-saw-like geometry to one O(2), one O(3), one O(4), and one F(1) atom. V(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted VO4 tetrahedra that share corners with two equivalent Li(4)O4F square pyramids, corners with four equivalent Li(2)O4F square pyramids, corners with two equivalent Li(3)O4F trigonal bipyramids,  an edgeedge with one Li(4)O4F square pyramid, and  an edgeedge with one Li(3)O4F trigonal bipyramid. 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), and one V(1) atom to form OLi4V trigonal bipyramids that share  a cornercorner with one O(2)Li5V octahedra,  a cornercorner with one O(3)Li5V octahedra, corners with two equivalent O(4)Li4V trigonal bipyramids, edges with two equivalent O(2)Li5V octahedra, edges with two equivalent O(3)Li5V octahedra, and  an edgeedge with one O(4)Li4V trigonal bipyramid. The corner-sharing octahedral tilt angles range from 71-72°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one V(1) atom to form OLi5V octahedra that share corners with two equivalent O(3)Li5V octahedra,  a cornercorner with one O(1)Li4V trigonal bipyramid,  a cornercorner with one O(4)Li4V trigonal bipyramid, edges with two equivalent O(3)Li5V octahedra, edges with two equivalent O(1)Li4V trigonal bipyramids, and edges with two equivalent O(4)Li4V trigonal bipyramids. The corner-sharing octahedral tilt angles range from 15-27°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one V(1) atom to form distorted OLi5V octahedra that share corners with two equivalent O(2)Li5V octahedra,  a cornercorner with one O(1)Li4V trigonal bipyramid,  a cornercorner with one O(4)Li4V trigonal bipyramid, edges with two equivalent O(2)Li5V octahedra, edges with two equivalent O(1)Li4V trigonal bipyramids, and edges with two equivalent O(4)Li4V trigonal bipyramids. The corner-sharing octahedral tilt angles range from 15-27°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), and one V(1) atom to form OLi4V trigonal bipyramids that share  a cornercorner with one O(2)Li5V octahedra,  a cornercorner with one O(3)Li5V octahedra, corners with two equivalent O(1)Li4V trigonal bipyramids, edges with two equivalent O(2)Li5V octahedra, edges with two equivalent O(3)Li5V octahedra, and  an edgeedge with one O(1)Li4V trigonal bipyramid. The corner-sharing octahedral tilt angles range from 23-73°. F(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one Li(5) atom.
Li5VO4F crystallizes in the monoclinic Cc space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one F(1) atom. The Li(1)-O(1) bond length is 1.95 Å. The Li(1)-O(2) bond length is 2.06 Å. The Li(1)-O(3) bond length is 2.03 Å. The Li(1)-F(1) bond length is 1.96 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), and one F(1) atom to form distorted LiO4F square pyramids that share  a cornercorner with one Li(4)O4F square pyramid, corners with four equivalent V(1)O4 tetrahedra,  a cornercorner with one Li(3)O4F trigonal bipyramid, edges with two equivalent Li(4)O4F square pyramids, and edges with two equivalent Li(3)O4F trigonal bipyramids. The Li(2)-O(1) bond length is 2.07 Å. The Li(2)-O(2) bond length is 2.13 Å. The Li(2)-O(3) bond length is 2.23 Å. The Li(2)-O(4) bond length is 2.02 Å. The Li(2)-F(1) bond length is 2.12 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), and one F(1) atom to form LiO4F trigonal bipyramids that share  a cornercorner with one Li(2)O4F square pyramid,  a cornercorner with one Li(4)O4F square pyramid, corners with two equivalent V(1)O4 tetrahedra, edges with two equivalent Li(2)O4F square pyramids, edges with two equivalent Li(4)O4F square pyramids, and  an edgeedge with one V(1)O4 tetrahedra. The Li(3)-O(1) bond length is 2.23 Å. The Li(3)-O(2) bond length is 2.04 Å. The Li(3)-O(3) bond length is 1.99 Å. The Li(3)-O(4) bond length is 2.08 Å. The Li(3)-F(1) bond length is 2.04 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(1) atom to form distorted LiO4F square pyramids that share  a cornercorner with one Li(2)O4F square pyramid, corners with two equivalent V(1)O4 tetrahedra,  a cornercorner with one Li(3)O4F trigonal bipyramid, edges with two equivalent Li(2)O4F square pyramids,  an edgeedge with one V(1)O4 tetrahedra, and edges with two equivalent Li(3)O4F trigonal bipyramids. The Li(4)-O(1) bond length is 1.98 Å. The Li(4)-O(2) bond length is 2.08 Å. The Li(4)-O(3) bond length is 2.32 Å. The Li(4)-O(4) bond length is 2.05 Å. The Li(4)-F(1) bond length is 2.00 Å. In the fifth Li site, Li(5) is bonded in a rectangular see-saw-like geometry to one O(2), one O(3), one O(4), and one F(1) atom. The Li(5)-O(2) bond length is 1.99 Å. The Li(5)-O(3) bond length is 1.98 Å. The Li(5)-O(4) bond length is 2.02 Å. The Li(5)-F(1) bond length is 2.05 Å. V(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted VO4 tetrahedra that share corners with two equivalent Li(4)O4F square pyramids, corners with four equivalent Li(2)O4F square pyramids, corners with two equivalent Li(3)O4F trigonal bipyramids,  an edgeedge with one Li(4)O4F square pyramid, and  an edgeedge with one Li(3)O4F trigonal bipyramid. The V(1)-O(1) bond length is 1.80 Å. The V(1)-O(2) bond length is 1.89 Å. The V(1)-O(3) bond length is 1.85 Å. The V(1)-O(4) bond length is 1.81 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), and one V(1) atom to form OLi4V trigonal bipyramids that share  a cornercorner with one O(2)Li5V octahedra,  a cornercorner with one O(3)Li5V octahedra, corners with two equivalent O(4)Li4V trigonal bipyramids, edges with two equivalent O(2)Li5V octahedra, edges with two equivalent O(3)Li5V octahedra, and  an edgeedge with one O(4)Li4V trigonal bipyramid. The corner-sharing octahedral tilt angles range from 71-72°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one V(1) atom to form OLi5V octahedra that share corners with two equivalent O(3)Li5V octahedra,  a cornercorner with one O(1)Li4V trigonal bipyramid,  a cornercorner with one O(4)Li4V trigonal bipyramid, edges with two equivalent O(3)Li5V octahedra, edges with two equivalent O(1)Li4V trigonal bipyramids, and edges with two equivalent O(4)Li4V trigonal bipyramids. The corner-sharing octahedral tilt angles range from 15-27°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one V(1) atom to form distorted OLi5V octahedra that share corners with two equivalent O(2)Li5V octahedra,  a cornercorner with one O(1)Li4V trigonal bipyramid,  a cornercorner with one O(4)Li4V trigonal bipyramid, edges with two equivalent O(2)Li5V octahedra, edges with two equivalent O(1)Li4V trigonal bipyramids, and edges with two equivalent O(4)Li4V trigonal bipyramids. The corner-sharing octahedral tilt angles range from 15-27°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), and one V(1) atom to form OLi4V trigonal bipyramids that share  a cornercorner with one O(2)Li5V octahedra,  a cornercorner with one O(3)Li5V octahedra, corners with two equivalent O(1)Li4V trigonal bipyramids, edges with two equivalent O(2)Li5V octahedra, edges with two equivalent O(3)Li5V octahedra, and  an edgeedge with one O(1)Li4V trigonal bipyramid. The corner-sharing octahedral tilt angles range from 23-73°. F(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one Li(5) atom.