LiFe2OF3 crystallizes in the orthorhombic Imm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one F(1), and two equivalent F(2) atoms to form LiOF3 tetrahedra that share  a cornercorner with one Fe(4)OF5 octahedra, corners with two equivalent Fe(1)OF5 octahedra, corners with three equivalent Fe(2)OF5 octahedra, corners with four equivalent Fe(3)O3F3 octahedra, and  a cornercorner with one Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 50-64°. In the second Li site, Li(2) is bonded to one F(3), one F(5), and two equivalent F(4) atoms to form LiF4 tetrahedra that share  a cornercorner with one Fe(1)OF5 octahedra, corners with two equivalent Fe(4)OF5 octahedra, corners with three equivalent Fe(2)OF5 octahedra, corners with four equivalent Fe(3)O3F3 octahedra, and  a cornercorner with one Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-61°. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one F(5), and four equivalent F(2) atoms to form FeOF5 octahedra that share corners with two equivalent Li(2)F4 tetrahedra, corners with four equivalent Li(1)OF3 tetrahedra, edges with two equivalent Fe(2)OF5 octahedra, and edges with four equivalent Fe(3)O3F3 octahedra. In the second Fe site, Fe(2) is bonded to one O(2), one F(3), two equivalent F(2), and two equivalent F(4) atoms to form FeOF5 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Li(1)OF3 tetrahedra,  an edgeedge with one Fe(1)OF5 octahedra,  an edgeedge with one Fe(4)OF5 octahedra, and edges with four equivalent Fe(3)O3F3 octahedra. In the third Fe site, Fe(3) is bonded to one O(1), one O(2), one O(3), one F(2), one F(3), and one F(4) atom to form FeO3F3 octahedra that share corners with two equivalent Fe(3)O3F3 octahedra, corners with two equivalent Li(2)F4 tetrahedra, corners with two equivalent Li(1)OF3 tetrahedra,  an edgeedge with one Fe(1)OF5 octahedra,  an edgeedge with one Fe(4)OF5 octahedra, edges with two equivalent Fe(2)OF5 octahedra, and edges with three equivalent Fe(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 15-20°. In the fourth Fe site, Fe(4) is bonded to one O(3), one F(1), and four equivalent F(4) atoms to form FeOF5 octahedra that share corners with two equivalent Li(1)OF3 tetrahedra, corners with four equivalent Li(2)F4 tetrahedra, edges with two equivalent Fe(2)OF5 octahedra, and edges with four equivalent Fe(3)O3F3 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Fe(1) and four equivalent Fe(3) atoms to form OFe5 square pyramids that share edges with two equivalent O(3)Fe5 square pyramids and edges with two equivalent O(2)LiFe3 tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Fe(2), and two equivalent Fe(3) atoms to form a mixture of distorted edge and corner-sharing OLiFe3 tetrahedra. In the third O site, O(3) is bonded to one Fe(4) and four equivalent Fe(3) atoms to form OFe5 square pyramids that share corners with four equivalent O(2)LiFe3 tetrahedra and edges with two equivalent O(1)Fe5 square pyramids. There are five inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) 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 distorted rectangular see-saw-like geometry to one Li(2), one Fe(2), 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(2), one Fe(3), and one Fe(4) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to two equivalent Li(2) and one Fe(1) atom.
LiFe2OF3 crystallizes in the orthorhombic Imm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one F(1), and two equivalent F(2) atoms to form LiOF3 tetrahedra that share  a cornercorner with one Fe(4)OF5 octahedra, corners with two equivalent Fe(1)OF5 octahedra, corners with three equivalent Fe(2)OF5 octahedra, corners with four equivalent Fe(3)O3F3 octahedra, and  a cornercorner with one Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 50-64°. The Li(1)-O(2) bond length is 1.98 Å. The Li(1)-F(1) bond length is 1.96 Å. Both Li(1)-F(2) bond lengths are 1.97 Å. In the second Li site, Li(2) is bonded to one F(3), one F(5), and two equivalent F(4) atoms to form LiF4 tetrahedra that share  a cornercorner with one Fe(1)OF5 octahedra, corners with two equivalent Fe(4)OF5 octahedra, corners with three equivalent Fe(2)OF5 octahedra, corners with four equivalent Fe(3)O3F3 octahedra, and  a cornercorner with one Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-61°. The Li(2)-F(3) bond length is 2.04 Å. The Li(2)-F(5) bond length is 1.90 Å. Both Li(2)-F(4) bond lengths are 1.96 Å. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one F(5), and four equivalent F(2) atoms to form FeOF5 octahedra that share corners with two equivalent Li(2)F4 tetrahedra, corners with four equivalent Li(1)OF3 tetrahedra, edges with two equivalent Fe(2)OF5 octahedra, and edges with four equivalent Fe(3)O3F3 octahedra. The Fe(1)-O(1) bond length is 2.06 Å. The Fe(1)-F(5) bond length is 2.01 Å. All Fe(1)-F(2) bond lengths are 2.20 Å. In the second Fe site, Fe(2) is bonded to one O(2), one F(3), two equivalent F(2), and two equivalent F(4) atoms to form FeOF5 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Li(1)OF3 tetrahedra,  an edgeedge with one Fe(1)OF5 octahedra,  an edgeedge with one Fe(4)OF5 octahedra, and edges with four equivalent Fe(3)O3F3 octahedra. The Fe(2)-O(2) bond length is 1.95 Å. The Fe(2)-F(3) bond length is 2.13 Å. Both Fe(2)-F(2) bond lengths are 2.19 Å. Both Fe(2)-F(4) bond lengths are 2.17 Å. In the third Fe site, Fe(3) is bonded to one O(1), one O(2), one O(3), one F(2), one F(3), and one F(4) atom to form FeO3F3 octahedra that share corners with two equivalent Fe(3)O3F3 octahedra, corners with two equivalent Li(2)F4 tetrahedra, corners with two equivalent Li(1)OF3 tetrahedra,  an edgeedge with one Fe(1)OF5 octahedra,  an edgeedge with one Fe(4)OF5 octahedra, edges with two equivalent Fe(2)OF5 octahedra, and edges with three equivalent Fe(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 15-20°. The Fe(3)-O(1) bond length is 2.13 Å. The Fe(3)-O(2) bond length is 2.05 Å. The Fe(3)-O(3) bond length is 2.19 Å. The Fe(3)-F(2) bond length is 2.27 Å. The Fe(3)-F(3) bond length is 2.22 Å. The Fe(3)-F(4) bond length is 2.22 Å. In the fourth Fe site, Fe(4) is bonded to one O(3), one F(1), and four equivalent F(4) atoms to form FeOF5 octahedra that share corners with two equivalent Li(1)OF3 tetrahedra, corners with four equivalent Li(2)F4 tetrahedra, edges with two equivalent Fe(2)OF5 octahedra, and edges with four equivalent Fe(3)O3F3 octahedra. The Fe(4)-O(3) bond length is 2.08 Å. The Fe(4)-F(1) bond length is 1.99 Å. All Fe(4)-F(4) bond lengths are 2.19 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Fe(1) and four equivalent Fe(3) atoms to form OFe5 square pyramids that share edges with two equivalent O(3)Fe5 square pyramids and edges with two equivalent O(2)LiFe3 tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Fe(2), and two equivalent Fe(3) atoms to form a mixture of distorted edge and corner-sharing OLiFe3 tetrahedra. In the third O site, O(3) is bonded to one Fe(4) and four equivalent Fe(3) atoms to form OFe5 square pyramids that share corners with four equivalent O(2)LiFe3 tetrahedra and edges with two equivalent O(1)Fe5 square pyramids. There are five inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) 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 distorted rectangular see-saw-like geometry to one Li(2), one Fe(2), 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(2), one Fe(3), and one Fe(4) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to two equivalent Li(2) and one Fe(1) atom.