Li5FeO3F2 crystallizes in the monoclinic Cm space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), two equivalent O(1), and one F(2) atom. In the second Li site, Li(2) is bonded to one O(2), one O(3), one F(2), and two equivalent F(1) atoms to form LiO2F3 square pyramids that share corners with two equivalent Fe(1)O4F2 octahedra, corners with two equivalent Li(2)O2F3 square pyramids,  a cornercorner with one Li(4)O2F3 trigonal bipyramid, edges with two equivalent Fe(1)O4F2 octahedra, and edges with two equivalent Li(4)O2F3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 8-10°. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(2), two equivalent O(3), and one F(1) atom. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one F(1), and two equivalent F(2) atoms to form distorted LiO2F3 trigonal bipyramids that share  a cornercorner with one Li(2)O2F3 square pyramid, corners with two equivalent Li(4)O2F3 trigonal bipyramids, edges with three equivalent Fe(1)O4F2 octahedra, and edges with two equivalent Li(2)O2F3 square pyramids. In the fifth Li site, Li(5) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(3), one F(1), and one F(2) atom. Fe(1) is bonded to one O(1), one O(3), two equivalent O(2), one F(1), and one F(2) atom to form distorted FeO4F2 octahedra that share corners with two equivalent Fe(1)O4F2 octahedra, corners with two equivalent Li(2)O2F3 square pyramids, edges with two equivalent Li(2)O2F3 square pyramids, and edges with three equivalent Li(4)O2F3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 29°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Li(4), one Li(5), two equivalent Li(1), and one Fe(1) atom to form OLi5Fe octahedra that share corners with two equivalent O(1)Li5Fe octahedra, corners with two equivalent F(2)Li5Fe octahedra, edges with two equivalent F(1)Li5Fe octahedra, edges with two equivalent F(2)Li5Fe octahedra, and edges with three equivalent O(3)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 7-23°. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and two equivalent Fe(1) atoms. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(5), two equivalent Li(3), and one Fe(1) atom to form OLi5Fe octahedra that share corners with two equivalent O(3)Li5Fe octahedra, corners with two equivalent F(1)Li5Fe octahedra, edges with two equivalent F(1)Li5Fe octahedra, edges with two equivalent F(2)Li5Fe octahedra, and edges with three equivalent O(1)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 1-26°. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(3), one Li(4), one Li(5), two equivalent Li(2), and one Fe(1) atom to form distorted FLi5Fe octahedra that share corners with two equivalent O(3)Li5Fe octahedra, corners with two equivalent F(1)Li5Fe octahedra, edges with two equivalent O(1)Li5Fe octahedra, edges with two equivalent O(3)Li5Fe octahedra, and edges with three equivalent F(2)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 1-12°. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(5), two equivalent Li(4), and one Fe(1) atom to form distorted FLi5Fe octahedra that share corners with two equivalent O(1)Li5Fe octahedra, corners with two equivalent F(2)Li5Fe octahedra, edges with two equivalent O(1)Li5Fe octahedra, edges with two equivalent O(3)Li5Fe octahedra, and edges with three equivalent F(1)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 7-25°.
Li5FeO3F2 crystallizes in the monoclinic Cm space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), two equivalent O(1), and one F(2) atom. The Li(1)-O(2) bond length is 2.55 Å. The Li(1)-O(3) bond length is 2.12 Å. Both Li(1)-O(1) bond lengths are 1.98 Å. The Li(1)-F(2) bond length is 2.09 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), one F(2), and two equivalent F(1) atoms to form LiO2F3 square pyramids that share corners with two equivalent Fe(1)O4F2 octahedra, corners with two equivalent Li(2)O2F3 square pyramids,  a cornercorner with one Li(4)O2F3 trigonal bipyramid, edges with two equivalent Fe(1)O4F2 octahedra, and edges with two equivalent Li(4)O2F3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 8-10°. The Li(2)-O(2) bond length is 2.08 Å. The Li(2)-O(3) bond length is 2.04 Å. The Li(2)-F(2) bond length is 1.99 Å. Both Li(2)-F(1) bond lengths are 1.95 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(2), two equivalent O(3), and one F(1) atom. The Li(3)-O(1) bond length is 1.96 Å. The Li(3)-O(2) bond length is 2.43 Å. Both Li(3)-O(3) bond lengths are 1.99 Å. The Li(3)-F(1) bond length is 2.00 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one F(1), and two equivalent F(2) atoms to form distorted LiO2F3 trigonal bipyramids that share  a cornercorner with one Li(2)O2F3 square pyramid, corners with two equivalent Li(4)O2F3 trigonal bipyramids, edges with three equivalent Fe(1)O4F2 octahedra, and edges with two equivalent Li(2)O2F3 square pyramids. The Li(4)-O(1) bond length is 2.00 Å. The Li(4)-O(2) bond length is 1.98 Å. The Li(4)-F(1) bond length is 2.32 Å. Both Li(4)-F(2) bond lengths are 1.99 Å. In the fifth Li site, Li(5) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(3), one F(1), and one F(2) atom. The Li(5)-O(1) bond length is 1.97 Å. The Li(5)-O(3) bond length is 2.01 Å. The Li(5)-F(1) bond length is 2.44 Å. The Li(5)-F(2) bond length is 1.96 Å. Fe(1) is bonded to one O(1), one O(3), two equivalent O(2), one F(1), and one F(2) atom to form distorted FeO4F2 octahedra that share corners with two equivalent Fe(1)O4F2 octahedra, corners with two equivalent Li(2)O2F3 square pyramids, edges with two equivalent Li(2)O2F3 square pyramids, and edges with three equivalent Li(4)O2F3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 29°. The Fe(1)-O(1) bond length is 1.93 Å. The Fe(1)-O(3) bond length is 1.92 Å. Both Fe(1)-O(2) bond lengths are 2.00 Å. The Fe(1)-F(1) bond length is 2.26 Å. The Fe(1)-F(2) bond length is 2.45 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Li(4), one Li(5), two equivalent Li(1), and one Fe(1) atom to form OLi5Fe octahedra that share corners with two equivalent O(1)Li5Fe octahedra, corners with two equivalent F(2)Li5Fe octahedra, edges with two equivalent F(1)Li5Fe octahedra, edges with two equivalent F(2)Li5Fe octahedra, and edges with three equivalent O(3)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 7-23°. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and two equivalent Fe(1) atoms. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(5), two equivalent Li(3), and one Fe(1) atom to form OLi5Fe octahedra that share corners with two equivalent O(3)Li5Fe octahedra, corners with two equivalent F(1)Li5Fe octahedra, edges with two equivalent F(1)Li5Fe octahedra, edges with two equivalent F(2)Li5Fe octahedra, and edges with three equivalent O(1)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 1-26°. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(3), one Li(4), one Li(5), two equivalent Li(2), and one Fe(1) atom to form distorted FLi5Fe octahedra that share corners with two equivalent O(3)Li5Fe octahedra, corners with two equivalent F(1)Li5Fe octahedra, edges with two equivalent O(1)Li5Fe octahedra, edges with two equivalent O(3)Li5Fe octahedra, and edges with three equivalent F(2)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 1-12°. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(5), two equivalent Li(4), and one Fe(1) atom to form distorted FLi5Fe octahedra that share corners with two equivalent O(1)Li5Fe octahedra, corners with two equivalent F(2)Li5Fe octahedra, edges with two equivalent O(1)Li5Fe octahedra, edges with two equivalent O(3)Li5Fe octahedra, and edges with three equivalent F(1)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 7-25°.