LiFe5O3F5 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(3), one F(3), two equivalent F(1), and two equivalent F(2) atoms to form LiOF5 octahedra that share corners with three equivalent Fe(4)O2F2 tetrahedra, corners with three equivalent Fe(2)OF3 tetrahedra, edges with two equivalent Fe(3)O2F4 octahedra, and edges with four equivalent Fe(1)O3F3 octahedra. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one F(1), one F(2), and one F(3) atom to form FeO3F3 octahedra that share corners with three equivalent Fe(4)O2F2 tetrahedra, corners with three equivalent Fe(2)OF3 tetrahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Fe(3)O2F4 octahedra, and edges with two equivalent Fe(1)O3F3 octahedra. In the second Fe site, Fe(2) is bonded to one O(2), one F(3), and two equivalent F(2) atoms to form FeOF3 tetrahedra that share corners with three equivalent Li(1)OF5 octahedra, corners with three equivalent Fe(3)O2F4 octahedra, and corners with six equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 51-67°. In the third Fe site, Fe(3) is bonded to one O(1), one O(2), two equivalent F(1), and two equivalent F(2) atoms to form FeO2F4 octahedra that share corners with three equivalent Fe(4)O2F2 tetrahedra, corners with three equivalent Fe(2)OF3 tetrahedra, edges with two equivalent Li(1)OF5 octahedra, and edges with four equivalent Fe(1)O3F3 octahedra. In the fourth Fe site, Fe(4) is bonded to one O(1), one O(3), and two equivalent F(1) atoms to form FeO2F2 tetrahedra that share corners with three equivalent Li(1)OF5 octahedra, corners with three equivalent Fe(3)O2F4 octahedra, and corners with six equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-68°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Fe(3), one Fe(4), and two equivalent Fe(1) atoms to form distorted corner-sharing OFe4 tetrahedra. In the second O site, O(2) is bonded to one Fe(2), one Fe(3), and two equivalent Fe(1) atoms to form corner-sharing OFe4 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(4), and two equivalent Fe(1) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(1), one Fe(3), and one Fe(4) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(1), one Fe(2), and one Fe(3) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(2), and two equivalent Fe(1) atoms.
LiFe5O3F5 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(3), one F(3), two equivalent F(1), and two equivalent F(2) atoms to form LiOF5 octahedra that share corners with three equivalent Fe(4)O2F2 tetrahedra, corners with three equivalent Fe(2)OF3 tetrahedra, edges with two equivalent Fe(3)O2F4 octahedra, and edges with four equivalent Fe(1)O3F3 octahedra. The Li(1)-O(3) bond length is 2.00 Å. The Li(1)-F(3) bond length is 2.17 Å. Both Li(1)-F(1) bond lengths are 2.19 Å. Both Li(1)-F(2) bond lengths are 2.15 Å. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one F(1), one F(2), and one F(3) atom to form FeO3F3 octahedra that share corners with three equivalent Fe(4)O2F2 tetrahedra, corners with three equivalent Fe(2)OF3 tetrahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Fe(3)O2F4 octahedra, and edges with two equivalent Fe(1)O3F3 octahedra. The Fe(1)-O(1) bond length is 2.13 Å. The Fe(1)-O(2) bond length is 2.09 Å. The Fe(1)-O(3) bond length is 2.03 Å. The Fe(1)-F(1) bond length is 2.26 Å. The Fe(1)-F(2) bond length is 2.24 Å. The Fe(1)-F(3) bond length is 2.29 Å. In the second Fe site, Fe(2) is bonded to one O(2), one F(3), and two equivalent F(2) atoms to form FeOF3 tetrahedra that share corners with three equivalent Li(1)OF5 octahedra, corners with three equivalent Fe(3)O2F4 octahedra, and corners with six equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 51-67°. The Fe(2)-O(2) bond length is 1.95 Å. The Fe(2)-F(3) bond length is 2.08 Å. Both Fe(2)-F(2) bond lengths are 2.10 Å. In the third Fe site, Fe(3) is bonded to one O(1), one O(2), two equivalent F(1), and two equivalent F(2) atoms to form FeO2F4 octahedra that share corners with three equivalent Fe(4)O2F2 tetrahedra, corners with three equivalent Fe(2)OF3 tetrahedra, edges with two equivalent Li(1)OF5 octahedra, and edges with four equivalent Fe(1)O3F3 octahedra. The Fe(3)-O(1) bond length is 1.99 Å. The Fe(3)-O(2) bond length is 2.00 Å. Both Fe(3)-F(1) bond lengths are 2.25 Å. Both Fe(3)-F(2) bond lengths are 2.29 Å. In the fourth Fe site, Fe(4) is bonded to one O(1), one O(3), and two equivalent F(1) atoms to form FeO2F2 tetrahedra that share corners with three equivalent Li(1)OF5 octahedra, corners with three equivalent Fe(3)O2F4 octahedra, and corners with six equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-68°. The Fe(4)-O(1) bond length is 1.97 Å. The Fe(4)-O(3) bond length is 1.96 Å. Both Fe(4)-F(1) bond lengths are 2.15 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Fe(3), one Fe(4), and two equivalent Fe(1) atoms to form distorted corner-sharing OFe4 tetrahedra. In the second O site, O(2) is bonded to one Fe(2), one Fe(3), and two equivalent Fe(1) atoms to form corner-sharing OFe4 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(4), and two equivalent Fe(1) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(1), one Fe(3), and one Fe(4) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(1), one Fe(2), and one Fe(3) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(2), and two equivalent Fe(1) atoms.