LiFe2OF3 is Corundum-derived structured and crystallizes in the monoclinic Pm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one F(3), and two equivalent F(1) atoms. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(2), one F(2), and two equivalent F(4) atoms. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(4), one F(6), and two equivalent F(5) atoms. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one O(3), one F(7), and two equivalent F(8) atoms. There are six inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(4), one F(2), two equivalent F(1), and two equivalent F(8) atoms to form FeOF5 octahedra that share edges with two equivalent Fe(3)O2F4 octahedra, edges with two equivalent Fe(6)O2F4 octahedra, and edges with two equivalent Fe(2)OF5 octahedra. In the second Fe site, Fe(2) is bonded to one O(1), one F(7), two equivalent F(1), and two equivalent F(8) atoms to form FeOF5 octahedra that share edges with two equivalent Fe(3)O2F4 octahedra, edges with two equivalent Fe(6)O2F4 octahedra, and edges with two equivalent Fe(1)OF5 octahedra. In the third Fe site, Fe(3) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(4) atom to form FeO2F4 octahedra that share corners with two equivalent Fe(5)OF5 octahedra,  an edgeedge with one Fe(1)OF5 octahedra,  an edgeedge with one Fe(2)OF5 octahedra,  an edgeedge with one Fe(4)OF5 octahedra, and edges with two equivalent Fe(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. In the fourth Fe site, Fe(4) is bonded to one O(2), one F(6), two equivalent F(4), and two equivalent F(5) atoms to form FeOF5 octahedra that share corners with four equivalent Fe(5)OF5 octahedra, edges with two equivalent Fe(3)O2F4 octahedra, and edges with two equivalent Fe(6)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. In the fifth Fe site, Fe(5) is bonded to one O(3), one F(3), two equivalent F(4), and two equivalent F(5) atoms to form FeOF5 octahedra that share corners with four equivalent Fe(3)O2F4 octahedra, corners with four equivalent Fe(6)O2F4 octahedra, and corners with four equivalent Fe(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. In the sixth Fe site, Fe(6) is bonded to one O(3), one O(4), one F(5), one F(6), one F(7), and one F(8) atom to form FeO2F4 octahedra that share corners with two equivalent Fe(5)OF5 octahedra,  an edgeedge with one Fe(1)OF5 octahedra,  an edgeedge with one Fe(2)OF5 octahedra,  an edgeedge with one Fe(4)OF5 octahedra, and edges with two equivalent Fe(6)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 49-53°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Fe(2), and two equivalent Fe(3) atoms to form corner-sharing OLiFe3 tetrahedra. In the second O site, O(2) is bonded to one Li(2), one Fe(4), and two equivalent Fe(3) atoms to form corner-sharing OLiFe3 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(4), one Fe(5), and two equivalent Fe(6) atoms. In the fourth O site, O(4) is bonded in a see-saw-like geometry to one Li(3), one Fe(1), and two equivalent Fe(6) atoms. There are eight 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(2), one Fe(1), and two equivalent Fe(3) atoms. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(5), and two equivalent Fe(3) atoms. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one Fe(3), one Fe(4), and one Fe(5) atom. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(3), one Fe(4), one Fe(5), and one Fe(6) atom. In the sixth F site, F(6) is bonded in a rectangular see-saw-like geometry to one Li(3), one Fe(4), and two equivalent Fe(6) atoms. In the seventh F site, F(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Fe(2), and two equivalent Fe(6) atoms. In the eighth F site, F(8) is bonded in a rectangular see-saw-like geometry to one Li(4), one Fe(1), one Fe(2), and one Fe(6) atom.
LiFe2OF3 is Corundum-derived structured and crystallizes in the monoclinic Pm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one F(3), and two equivalent F(1) atoms. The Li(1)-O(1) bond length is 1.89 Å. The Li(1)-F(3) bond length is 2.06 Å. Both Li(1)-F(1) bond lengths are 2.10 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(2), one F(2), and two equivalent F(4) atoms. The Li(2)-O(2) bond length is 1.88 Å. The Li(2)-F(2) bond length is 2.30 Å. Both Li(2)-F(4) bond lengths are 1.99 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(4), one F(6), and two equivalent F(5) atoms. The Li(3)-O(4) bond length is 1.94 Å. The Li(3)-F(6) bond length is 1.87 Å. Both Li(3)-F(5) bond lengths are 2.01 Å. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one O(3), one F(7), and two equivalent F(8) atoms. The Li(4)-O(3) bond length is 2.00 Å. The Li(4)-F(7) bond length is 1.86 Å. Both Li(4)-F(8) bond lengths are 1.97 Å. There are six inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(4), one F(2), two equivalent F(1), and two equivalent F(8) atoms to form FeOF5 octahedra that share edges with two equivalent Fe(3)O2F4 octahedra, edges with two equivalent Fe(6)O2F4 octahedra, and edges with two equivalent Fe(2)OF5 octahedra. The Fe(1)-O(4) bond length is 2.00 Å. The Fe(1)-F(2) bond length is 2.11 Å. Both Fe(1)-F(1) bond lengths are 2.27 Å. Both Fe(1)-F(8) bond lengths are 2.29 Å. In the second Fe site, Fe(2) is bonded to one O(1), one F(7), two equivalent F(1), and two equivalent F(8) atoms to form FeOF5 octahedra that share edges with two equivalent Fe(3)O2F4 octahedra, edges with two equivalent Fe(6)O2F4 octahedra, and edges with two equivalent Fe(1)OF5 octahedra. The Fe(2)-O(1) bond length is 2.00 Å. The Fe(2)-F(7) bond length is 2.13 Å. Both Fe(2)-F(1) bond lengths are 2.16 Å. Both Fe(2)-F(8) bond lengths are 2.15 Å. In the third Fe site, Fe(3) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(4) atom to form FeO2F4 octahedra that share corners with two equivalent Fe(5)OF5 octahedra,  an edgeedge with one Fe(1)OF5 octahedra,  an edgeedge with one Fe(2)OF5 octahedra,  an edgeedge with one Fe(4)OF5 octahedra, and edges with two equivalent Fe(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. The Fe(3)-O(1) bond length is 1.99 Å. The Fe(3)-O(2) bond length is 2.00 Å. The Fe(3)-F(1) bond length is 2.24 Å. The Fe(3)-F(2) bond length is 2.25 Å. The Fe(3)-F(3) bond length is 2.31 Å. The Fe(3)-F(4) bond length is 2.24 Å. In the fourth Fe site, Fe(4) is bonded to one O(2), one F(6), two equivalent F(4), and two equivalent F(5) atoms to form FeOF5 octahedra that share corners with four equivalent Fe(5)OF5 octahedra, edges with two equivalent Fe(3)O2F4 octahedra, and edges with two equivalent Fe(6)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. The Fe(4)-O(2) bond length is 1.97 Å. The Fe(4)-F(6) bond length is 2.07 Å. Both Fe(4)-F(4) bond lengths are 2.23 Å. Both Fe(4)-F(5) bond lengths are 2.23 Å. In the fifth Fe site, Fe(5) is bonded to one O(3), one F(3), two equivalent F(4), and two equivalent F(5) atoms to form FeOF5 octahedra that share corners with four equivalent Fe(3)O2F4 octahedra, corners with four equivalent Fe(6)O2F4 octahedra, and corners with four equivalent Fe(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. The Fe(5)-O(3) bond length is 2.02 Å. The Fe(5)-F(3) bond length is 2.13 Å. Both Fe(5)-F(4) bond lengths are 2.27 Å. Both Fe(5)-F(5) bond lengths are 2.35 Å. In the sixth Fe site, Fe(6) is bonded to one O(3), one O(4), one F(5), one F(6), one F(7), and one F(8) atom to form FeO2F4 octahedra that share corners with two equivalent Fe(5)OF5 octahedra,  an edgeedge with one Fe(1)OF5 octahedra,  an edgeedge with one Fe(2)OF5 octahedra,  an edgeedge with one Fe(4)OF5 octahedra, and edges with two equivalent Fe(6)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 49-53°. The Fe(6)-O(3) bond length is 2.02 Å. The Fe(6)-O(4) bond length is 2.03 Å. The Fe(6)-F(5) bond length is 2.19 Å. The Fe(6)-F(6) bond length is 2.22 Å. The Fe(6)-F(7) bond length is 2.23 Å. The Fe(6)-F(8) bond length is 2.23 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Fe(2), and two equivalent Fe(3) atoms to form corner-sharing OLiFe3 tetrahedra. In the second O site, O(2) is bonded to one Li(2), one Fe(4), and two equivalent Fe(3) atoms to form corner-sharing OLiFe3 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(4), one Fe(5), and two equivalent Fe(6) atoms. In the fourth O site, O(4) is bonded in a see-saw-like geometry to one Li(3), one Fe(1), and two equivalent Fe(6) atoms. There are eight 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(2), one Fe(1), and two equivalent Fe(3) atoms. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(5), and two equivalent Fe(3) atoms. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one Fe(3), one Fe(4), and one Fe(5) atom. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(3), one Fe(4), one Fe(5), and one Fe(6) atom. In the sixth F site, F(6) is bonded in a rectangular see-saw-like geometry to one Li(3), one Fe(4), and two equivalent Fe(6) atoms. In the seventh F site, F(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Fe(2), and two equivalent Fe(6) atoms. In the eighth F site, F(8) is bonded in a rectangular see-saw-like geometry to one Li(4), one Fe(1), one Fe(2), and one Fe(6) atom.