Li3Fe3OF7 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form LiOF5 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Fe(1)OF3 tetrahedra, edges with two equivalent Li(3)F6 octahedra, and edges with four equivalent Fe(2)OF5 octahedra. In the second Li site, Li(2) is bonded to one F(2), one F(4), and two equivalent F(3) atoms to form LiF4 tetrahedra that share corners with three equivalent Li(3)F6 octahedra, corners with three equivalent Li(1)OF5 octahedra, and corners with six equivalent Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 54-60°. In the third Li site, Li(3) is bonded to one F(2), one F(5), two equivalent F(1), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Fe(1)OF3 tetrahedra, edges with two equivalent Li(1)OF5 octahedra, and edges with four equivalent Fe(2)OF5 octahedra. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one F(5), and two equivalent F(1) atoms to form FeOF3 tetrahedra that share corners with three equivalent Li(3)F6 octahedra, corners with three equivalent Li(1)OF5 octahedra, and corners with six equivalent Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 50-68°. In the second Fe site, Fe(2) 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 FeOF5 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Fe(1)OF3 tetrahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(1)OF5 octahedra, and edges with two equivalent Fe(2)OF5 octahedra. O(1) is bonded to one Li(1), one Fe(1), and two equivalent Fe(2) atoms to form distorted OLiFe3 trigonal pyramids that share corners with two equivalent F(1)Li2Fe2 tetrahedra and edges with two equivalent F(1)Li2Fe2 tetrahedra. There are five inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(3), one Fe(1), and one Fe(2) atom to form distorted FLi2Fe2 tetrahedra that share  a cornercorner with one F(1)Li2Fe2 tetrahedra,  a cornercorner with one O(1)LiFe3 trigonal pyramid,  an edgeedge with one F(1)Li2Fe2 tetrahedra, and  an edgeedge with one O(1)LiFe3 trigonal pyramid. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), and two equivalent Fe(2) atoms. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Fe(2) atom. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent Fe(2) atoms. In the fifth F site, F(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Fe(1), and two equivalent Fe(2) atoms.
Li3Fe3OF7 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form LiOF5 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Fe(1)OF3 tetrahedra, edges with two equivalent Li(3)F6 octahedra, and edges with four equivalent Fe(2)OF5 octahedra. The Li(1)-O(1) bond length is 1.98 Å. The Li(1)-F(4) bond length is 2.24 Å. Both Li(1)-F(1) bond lengths are 2.18 Å. Both Li(1)-F(3) bond lengths are 2.05 Å. In the second Li site, Li(2) is bonded to one F(2), one F(4), and two equivalent F(3) atoms to form LiF4 tetrahedra that share corners with three equivalent Li(3)F6 octahedra, corners with three equivalent Li(1)OF5 octahedra, and corners with six equivalent Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 54-60°. The Li(2)-F(2) bond length is 1.99 Å. The Li(2)-F(4) bond length is 2.11 Å. Both Li(2)-F(3) bond lengths are 1.97 Å. In the third Li site, Li(3) is bonded to one F(2), one F(5), two equivalent F(1), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Fe(1)OF3 tetrahedra, edges with two equivalent Li(1)OF5 octahedra, and edges with four equivalent Fe(2)OF5 octahedra. The Li(3)-F(2) bond length is 2.07 Å. The Li(3)-F(5) bond length is 2.12 Å. Both Li(3)-F(1) bond lengths are 2.12 Å. Both Li(3)-F(3) bond lengths are 2.06 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one F(5), and two equivalent F(1) atoms to form FeOF3 tetrahedra that share corners with three equivalent Li(3)F6 octahedra, corners with three equivalent Li(1)OF5 octahedra, and corners with six equivalent Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 50-68°. The Fe(1)-O(1) bond length is 1.91 Å. The Fe(1)-F(5) bond length is 2.08 Å. Both Fe(1)-F(1) bond lengths are 2.02 Å. In the second Fe site, Fe(2) 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 FeOF5 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Fe(1)OF3 tetrahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(1)OF5 octahedra, and edges with two equivalent Fe(2)OF5 octahedra. The Fe(2)-O(1) bond length is 1.95 Å. The Fe(2)-F(1) bond length is 2.15 Å. The Fe(2)-F(2) bond length is 2.21 Å. The Fe(2)-F(3) bond length is 2.07 Å. The Fe(2)-F(4) bond length is 2.18 Å. The Fe(2)-F(5) bond length is 2.16 Å. O(1) is bonded to one Li(1), one Fe(1), and two equivalent Fe(2) atoms to form distorted OLiFe3 trigonal pyramids that share corners with two equivalent F(1)Li2Fe2 tetrahedra and edges with two equivalent F(1)Li2Fe2 tetrahedra. There are five inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(3), one Fe(1), and one Fe(2) atom to form distorted FLi2Fe2 tetrahedra that share  a cornercorner with one F(1)Li2Fe2 tetrahedra,  a cornercorner with one O(1)LiFe3 trigonal pyramid,  an edgeedge with one F(1)Li2Fe2 tetrahedra, and  an edgeedge with one O(1)LiFe3 trigonal pyramid. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), and two equivalent Fe(2) atoms. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Fe(2) atom. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent Fe(2) atoms. In the fifth F site, F(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Fe(1), and two equivalent Fe(2) atoms.