LiFe2OF3 is Spinel-derived structured and crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(1), one F(1), one F(2), and one F(3) atom to form distorted LiOF3 tetrahedra that share  a cornercorner with one Fe(1)O2F4 octahedra,  a cornercorner with one Fe(3)O2F4 octahedra,  a cornercorner with one Fe(4)O2F4 octahedra, corners with three equivalent Fe(2)F6 octahedra,  an edgeedge with one Fe(1)O2F4 octahedra,  an edgeedge with one Fe(3)O2F4 octahedra, and  an edgeedge with one Fe(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 62-65°. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms to form FeO2F4 octahedra that share corners with four equivalent Fe(2)F6 octahedra, corners with two equivalent Li(1)OF3 tetrahedra, edges with two equivalent Fe(3)O2F4 octahedra, edges with two equivalent Fe(4)O2F4 octahedra, and edges with two equivalent Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. In the second Fe site, Fe(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form FeF6 octahedra that share corners with four equivalent Fe(1)O2F4 octahedra, corners with four equivalent Fe(3)O2F4 octahedra, corners with four equivalent Fe(4)O2F4 octahedra, and corners with six equivalent Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 48-50°. In the third Fe site, Fe(3) 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 four equivalent Fe(2)F6 octahedra, corners with two equivalent Li(1)OF3 tetrahedra, edges with two equivalent Fe(1)O2F4 octahedra, edges with two equivalent Fe(4)O2F4 octahedra, and edges with two equivalent Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 48-50°. In the fourth Fe site, Fe(4) 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 four equivalent Fe(2)F6 octahedra, corners with two equivalent Li(1)OF3 tetrahedra, edges with two equivalent Fe(1)O2F4 octahedra, edges with two equivalent Fe(3)O2F4 octahedra, and edges with two equivalent Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. O(1) is bonded to one Li(1), one Fe(1), one Fe(3), and one Fe(4) atom to form 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(2), 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(1), one Fe(2), and one Fe(4) atom.
LiFe2OF3 is Spinel-derived structured and crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(1), one F(1), one F(2), and one F(3) atom to form distorted LiOF3 tetrahedra that share  a cornercorner with one Fe(1)O2F4 octahedra,  a cornercorner with one Fe(3)O2F4 octahedra,  a cornercorner with one Fe(4)O2F4 octahedra, corners with three equivalent Fe(2)F6 octahedra,  an edgeedge with one Fe(1)O2F4 octahedra,  an edgeedge with one Fe(3)O2F4 octahedra, and  an edgeedge with one Fe(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 62-65°. The Li(1)-O(1) bond length is 1.89 Å. The Li(1)-F(1) bond length is 1.97 Å. The Li(1)-F(2) bond length is 2.00 Å. The Li(1)-F(3) bond length is 1.98 Å. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms to form FeO2F4 octahedra that share corners with four equivalent Fe(2)F6 octahedra, corners with two equivalent Li(1)OF3 tetrahedra, edges with two equivalent Fe(3)O2F4 octahedra, edges with two equivalent Fe(4)O2F4 octahedra, and edges with two equivalent Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. Both Fe(1)-O(1) bond lengths are 1.96 Å. Both Fe(1)-F(2) bond lengths are 2.31 Å. Both Fe(1)-F(3) bond lengths are 2.29 Å. In the second Fe site, Fe(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form FeF6 octahedra that share corners with four equivalent Fe(1)O2F4 octahedra, corners with four equivalent Fe(3)O2F4 octahedra, corners with four equivalent Fe(4)O2F4 octahedra, and corners with six equivalent Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 48-50°. Both Fe(2)-F(1) bond lengths are 2.18 Å. Both Fe(2)-F(2) bond lengths are 2.10 Å. Both Fe(2)-F(3) bond lengths are 2.15 Å. In the third Fe site, Fe(3) 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 four equivalent Fe(2)F6 octahedra, corners with two equivalent Li(1)OF3 tetrahedra, edges with two equivalent Fe(1)O2F4 octahedra, edges with two equivalent Fe(4)O2F4 octahedra, and edges with two equivalent Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 48-50°. Both Fe(3)-O(1) bond lengths are 1.97 Å. Both Fe(3)-F(1) bond lengths are 2.26 Å. Both Fe(3)-F(2) bond lengths are 2.30 Å. In the fourth Fe site, Fe(4) 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 four equivalent Fe(2)F6 octahedra, corners with two equivalent Li(1)OF3 tetrahedra, edges with two equivalent Fe(1)O2F4 octahedra, edges with two equivalent Fe(3)O2F4 octahedra, and edges with two equivalent Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. Both Fe(4)-O(1) bond lengths are 1.97 Å. Both Fe(4)-F(1) bond lengths are 2.27 Å. Both Fe(4)-F(3) bond lengths are 2.28 Å. O(1) is bonded to one Li(1), one Fe(1), one Fe(3), and one Fe(4) atom to form 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(2), 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(1), one Fe(2), and one Fe(4) atom.