LiFe2OF3 is Spinel-derived structured and crystallizes in the orthorhombic P222_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with six equivalent Fe(2)OF3 tetrahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Fe(1)O2F4 octahedra, and edges with two equivalent Fe(3)O2F4 octahedra. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms to form LiO2F4 octahedra that share corners with six equivalent Fe(2)OF3 tetrahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Fe(1)O2F4 octahedra, and edges with two equivalent Fe(3)O2F4 octahedra. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form FeO2F4 octahedra that share corners with six equivalent Fe(2)OF3 tetrahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(2)O2F4 octahedra, and edges with two equivalent Fe(3)O2F4 octahedra. In the second Fe site, Fe(2) is bonded to one O(1), one F(1), one F(2), and one F(3) atom to form FeOF3 tetrahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)O2F4 octahedra, corners with three equivalent Fe(1)O2F4 octahedra, and corners with three equivalent Fe(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 46-69°. In the third Fe site, Fe(3) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(3) atoms to form FeO2F4 octahedra that share corners with six equivalent Fe(2)OF3 tetrahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(2)O2F4 octahedra, and edges with two equivalent Fe(1)O2F4 octahedra. O(1) is bonded to one Li(2), one Fe(1), one Fe(2), and one Fe(3) atom to form distorted corner-sharing OLiFe3 tetrahedra. 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(2), and one Fe(3) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Fe(1), and one Fe(2) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Fe(2), and one Fe(3) atom.
LiFe2OF3 is Spinel-derived structured and crystallizes in the orthorhombic P222_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with six equivalent Fe(2)OF3 tetrahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Fe(1)O2F4 octahedra, and edges with two equivalent Fe(3)O2F4 octahedra. Both Li(1)-F(1) bond lengths are 2.06 Å. Both Li(1)-F(2) bond lengths are 2.08 Å. Both Li(1)-F(3) bond lengths are 2.04 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms to form LiO2F4 octahedra that share corners with six equivalent Fe(2)OF3 tetrahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Fe(1)O2F4 octahedra, and edges with two equivalent Fe(3)O2F4 octahedra. Both Li(2)-O(1) bond lengths are 2.05 Å. Both Li(2)-F(2) bond lengths are 2.20 Å. Both Li(2)-F(3) bond lengths are 2.10 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form FeO2F4 octahedra that share corners with six equivalent Fe(2)OF3 tetrahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(2)O2F4 octahedra, and edges with two equivalent Fe(3)O2F4 octahedra. Both Fe(1)-O(1) bond lengths are 2.06 Å. Both Fe(1)-F(1) bond lengths are 2.21 Å. Both Fe(1)-F(2) bond lengths are 2.15 Å. In the second Fe site, Fe(2) is bonded to one O(1), one F(1), one F(2), and one F(3) atom to form FeOF3 tetrahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)O2F4 octahedra, corners with three equivalent Fe(1)O2F4 octahedra, and corners with three equivalent Fe(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 46-69°. The Fe(2)-O(1) bond length is 1.92 Å. The Fe(2)-F(1) bond length is 2.10 Å. The Fe(2)-F(2) bond length is 2.08 Å. The Fe(2)-F(3) bond length is 2.01 Å. In the third Fe site, Fe(3) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(3) atoms to form FeO2F4 octahedra that share corners with six equivalent Fe(2)OF3 tetrahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(2)O2F4 octahedra, and edges with two equivalent Fe(1)O2F4 octahedra. Both Fe(3)-O(1) bond lengths are 1.99 Å. Both Fe(3)-F(1) bond lengths are 2.26 Å. Both Fe(3)-F(3) bond lengths are 2.24 Å. O(1) is bonded to one Li(2), one Fe(1), one Fe(2), and one Fe(3) atom to form distorted corner-sharing OLiFe3 tetrahedra. 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(2), and one Fe(3) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Fe(1), and one Fe(2) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Fe(2), and one Fe(3) atom.