LiFe2OF3 is Spinel-derived structured and crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one O(1), one F(2), and two equivalent F(1) atoms to form distorted LiOF3 tetrahedra that share corners with two equivalent Fe(1)O2F4 octahedra, corners with four equivalent Fe(2)OF5 octahedra,  an edgeedge with one Fe(2)OF5 octahedra, and edges with two equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 49-71°. There are two 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 four equivalent Fe(2)OF5 octahedra, corners with two equivalent Li(1)OF3 tetrahedra, edges with two equivalent Fe(1)O2F4 octahedra, edges with two equivalent Fe(2)OF5 octahedra, and edges with two equivalent Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 54-58°. In the second Fe site, Fe(2) is bonded to one O(1), one F(2), and four equivalent F(1) atoms to form distorted FeOF5 octahedra that share corners with four equivalent Fe(1)O2F4 octahedra, corners with four equivalent Fe(2)OF5 octahedra, corners with four equivalent Li(1)OF3 tetrahedra, edges with two equivalent Fe(1)O2F4 octahedra, and  an edgeedge with one Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 47-58°. O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(2), and two equivalent Fe(1) atoms. There are two 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), and two equivalent Fe(2) atoms. In the second F site, F(2) is bonded to one Li(1), one Fe(2), and two equivalent Fe(1) atoms to form distorted corner-sharing FLiFe3 tetrahedra.
LiFe2OF3 is Spinel-derived structured and crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one O(1), one F(2), and two equivalent F(1) atoms to form distorted LiOF3 tetrahedra that share corners with two equivalent Fe(1)O2F4 octahedra, corners with four equivalent Fe(2)OF5 octahedra,  an edgeedge with one Fe(2)OF5 octahedra, and edges with two equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 49-71°. The Li(1)-O(1) bond length is 1.96 Å. The Li(1)-F(2) bond length is 1.86 Å. Both Li(1)-F(1) bond lengths are 1.91 Å. There are two 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 four equivalent Fe(2)OF5 octahedra, corners with two equivalent Li(1)OF3 tetrahedra, edges with two equivalent Fe(1)O2F4 octahedra, edges with two equivalent Fe(2)OF5 octahedra, and edges with two equivalent Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 54-58°. Both Fe(1)-O(1) bond lengths are 2.03 Å. Both Fe(1)-F(1) bond lengths are 2.26 Å. Both Fe(1)-F(2) bond lengths are 2.21 Å. In the second Fe site, Fe(2) is bonded to one O(1), one F(2), and four equivalent F(1) atoms to form distorted FeOF5 octahedra that share corners with four equivalent Fe(1)O2F4 octahedra, corners with four equivalent Fe(2)OF5 octahedra, corners with four equivalent Li(1)OF3 tetrahedra, edges with two equivalent Fe(1)O2F4 octahedra, and  an edgeedge with one Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 47-58°. The Fe(2)-O(1) bond length is 1.98 Å. The Fe(2)-F(2) bond length is 2.17 Å. There are two shorter (2.17 Å) and two longer (2.26 Å) Fe(2)-F(1) bond lengths. O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(2), and two equivalent Fe(1) atoms. There are two 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), and two equivalent Fe(2) atoms. In the second F site, F(2) is bonded to one Li(1), one Fe(2), and two equivalent Fe(1) atoms to form distorted corner-sharing FLiFe3 tetrahedra.