Li4V2OF7 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(5) atoms to form LiF6 octahedra that share corners with three equivalent Li(4)F4 tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with two equivalent Li(2)OF5 octahedra, and edges with four equivalent V(1)OF5 octahedra. In the second Li site, Li(2) is bonded to one O(1), one F(2), two equivalent F(1), and two equivalent F(5) atoms to form LiOF5 octahedra that share corners with three equivalent Li(4)F4 tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with two equivalent Li(1)F6 octahedra, and edges with four equivalent V(1)OF5 octahedra. In the third Li site, Li(3) is bonded to one O(1), one F(4), and two equivalent F(5) atoms to form LiOF3 tetrahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)OF5 octahedra, and corners with six equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 54-63°. In the fourth Li site, Li(4) is bonded to one F(2), one F(3), and two equivalent F(1) atoms to form LiF4 tetrahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)OF5 octahedra, and corners with six equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 55-61°. V(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form VOF5 octahedra that share corners with three equivalent Li(4)F4 tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(2)OF5 octahedra, and edges with two equivalent V(1)OF5 octahedra. O(1) is bonded to one Li(2), one Li(3), and two equivalent V(1) atoms to form distorted OLi2V2 trigonal pyramids that share corners with two equivalent F(3)Li2V2 trigonal pyramids and corners with three equivalent F(2)Li2V2 trigonal pyramids. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one V(1) atom. In the second F site, F(2) is bonded to one Li(2), one Li(4), and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share  a cornercorner with one F(3)Li2V2 trigonal pyramid, corners with three equivalent O(1)Li2V2 trigonal pyramids, and  an edgeedge with one F(3)Li2V2 trigonal pyramid. In the third F site, F(3) is bonded to one Li(1), one Li(4), and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share  a cornercorner with one F(2)Li2V2 trigonal pyramid, corners with two equivalent O(1)Li2V2 trigonal pyramids, and  an edgeedge with one F(2)Li2V2 trigonal pyramid. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), and two equivalent V(1) atoms. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom.
Li4V2OF7 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(5) atoms to form LiF6 octahedra that share corners with three equivalent Li(4)F4 tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with two equivalent Li(2)OF5 octahedra, and edges with four equivalent V(1)OF5 octahedra. The Li(1)-F(3) bond length is 2.07 Å. The Li(1)-F(4) bond length is 2.04 Å. Both Li(1)-F(1) bond lengths are 2.07 Å. Both Li(1)-F(5) bond lengths are 2.07 Å. In the second Li site, Li(2) is bonded to one O(1), one F(2), two equivalent F(1), and two equivalent F(5) atoms to form LiOF5 octahedra that share corners with three equivalent Li(4)F4 tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with two equivalent Li(1)F6 octahedra, and edges with four equivalent V(1)OF5 octahedra. The Li(2)-O(1) bond length is 2.05 Å. The Li(2)-F(2) bond length is 2.12 Å. Both Li(2)-F(1) bond lengths are 2.05 Å. Both Li(2)-F(5) bond lengths are 2.12 Å. In the third Li site, Li(3) is bonded to one O(1), one F(4), and two equivalent F(5) atoms to form LiOF3 tetrahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)OF5 octahedra, and corners with six equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 54-63°. The Li(3)-O(1) bond length is 1.94 Å. The Li(3)-F(4) bond length is 1.97 Å. Both Li(3)-F(5) bond lengths are 1.97 Å. In the fourth Li site, Li(4) is bonded to one F(2), one F(3), and two equivalent F(1) atoms to form LiF4 tetrahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)OF5 octahedra, and corners with six equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 55-61°. The Li(4)-F(2) bond length is 1.97 Å. The Li(4)-F(3) bond length is 1.95 Å. Both Li(4)-F(1) bond lengths are 1.97 Å. V(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form VOF5 octahedra that share corners with three equivalent Li(4)F4 tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(2)OF5 octahedra, and edges with two equivalent V(1)OF5 octahedra. The V(1)-O(1) bond length is 1.89 Å. The V(1)-F(1) bond length is 2.04 Å. The V(1)-F(2) bond length is 2.14 Å. The V(1)-F(3) bond length is 2.09 Å. The V(1)-F(4) bond length is 2.12 Å. The V(1)-F(5) bond length is 2.03 Å. O(1) is bonded to one Li(2), one Li(3), and two equivalent V(1) atoms to form distorted OLi2V2 trigonal pyramids that share corners with two equivalent F(3)Li2V2 trigonal pyramids and corners with three equivalent F(2)Li2V2 trigonal pyramids. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one V(1) atom. In the second F site, F(2) is bonded to one Li(2), one Li(4), and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share  a cornercorner with one F(3)Li2V2 trigonal pyramid, corners with three equivalent O(1)Li2V2 trigonal pyramids, and  an edgeedge with one F(3)Li2V2 trigonal pyramid. In the third F site, F(3) is bonded to one Li(1), one Li(4), and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share  a cornercorner with one F(2)Li2V2 trigonal pyramid, corners with two equivalent O(1)Li2V2 trigonal pyramids, and  an edgeedge with one F(2)Li2V2 trigonal pyramid. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), and two equivalent V(1) atoms. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom.