Li3Fe4O3F5 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one F(1), one F(2), one F(4), and one F(5) atom to form distorted LiO2F4 octahedra that share corners with six equivalent Fe(3)O2F4 octahedra, edges with two equivalent Li(2)O3F3 octahedra, and edges with two equivalent Fe(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 6-25°. In the second Li site, Li(2) 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 LiO3F3 octahedra that share corners with six equivalent Fe(2)O3F3 octahedra, edges with two equivalent Li(1)O2F4 octahedra, and edges with two equivalent Fe(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 1-19°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one F(1), one F(3), and one F(5) atom. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in a 5-coordinate geometry to one O(2), one F(1), one F(2), one F(3), and one F(4) atom. In the second Fe site, Fe(2) 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 six equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(1)O2F4 octahedra, and edges with two equivalent Fe(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 1-19°. In the third Fe site, Fe(3) is bonded to one O(1), one O(3), one F(1), one F(2), one F(4), and one F(5) atom to form distorted FeO2F4 octahedra that share corners with six equivalent Li(1)O2F4 octahedra, edges with two equivalent Li(2)O3F3 octahedra, and edges with two equivalent Fe(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 6-25°. In the fourth Fe site, Fe(4) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(2), one F(3), one F(4), and one F(5) atom. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Fe(2), and one Fe(3) atom to form OLi3Fe2 square pyramids that share  a cornercorner with one O(2)Li2Fe3 square pyramid,  a cornercorner with one F(3)Li2Fe3 square pyramid, corners with five equivalent O(3)Li3Fe2 square pyramids, edges with two equivalent F(2)Li2Fe4 octahedra,  an edgeedge with one O(2)Li2Fe3 square pyramid, and  an edgeedge with one F(3)Li2Fe3 square pyramid. In the second O site, O(2) is bonded to one Li(2), one Li(3), one Fe(1), one Fe(2), and one Fe(4) atom to form distorted OLi2Fe3 square pyramids that share  a cornercorner with one O(1)Li3Fe2 square pyramid,  a cornercorner with one O(3)Li3Fe2 square pyramid, corners with five equivalent F(3)Li2Fe3 square pyramids, edges with two equivalent F(2)Li2Fe4 octahedra,  an edgeedge with one O(1)Li3Fe2 square pyramid, and  an edgeedge with one O(3)Li3Fe2 square pyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Fe(2), and one Fe(3) atom to form OLi3Fe2 square pyramids that share  a cornercorner with one O(2)Li2Fe3 square pyramid,  a cornercorner with one F(3)Li2Fe3 square pyramid, corners with five equivalent O(1)Li3Fe2 square pyramids, edges with two equivalent F(2)Li2Fe4 octahedra,  an edgeedge with one O(2)Li2Fe3 square pyramid, and  an edgeedge with one F(3)Li2Fe3 square pyramid. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(3), one Fe(1), one Fe(3), and one Fe(4) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Fe(1), one Fe(2), one Fe(3), and one Fe(4) atom to form distorted FLi2Fe4 octahedra that share edges with two equivalent O(2)Li2Fe3 square pyramids, edges with two equivalent O(1)Li3Fe2 square pyramids, edges with two equivalent O(3)Li3Fe2 square pyramids, and edges with two equivalent F(3)Li2Fe3 square pyramids. In the third F site, F(3) is bonded to one Li(2), one Li(3), one Fe(1), one Fe(2), and one Fe(4) atom to form FLi2Fe3 square pyramids that share  a cornercorner with one O(1)Li3Fe2 square pyramid,  a cornercorner with one O(3)Li3Fe2 square pyramid, corners with five equivalent O(2)Li2Fe3 square pyramids, edges with two equivalent F(2)Li2Fe4 octahedra,  an edgeedge with one O(1)Li3Fe2 square pyramid, and  an edgeedge with one O(3)Li3Fe2 square pyramid. In the fourth F site, F(4) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Fe(1), one Fe(2), one Fe(3), and one Fe(4) atom. In the fifth F site, F(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one Fe(3), and one Fe(4) atom.
Li3Fe4O3F5 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one F(1), one F(2), one F(4), and one F(5) atom to form distorted LiO2F4 octahedra that share corners with six equivalent Fe(3)O2F4 octahedra, edges with two equivalent Li(2)O3F3 octahedra, and edges with two equivalent Fe(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 6-25°. The Li(1)-O(1) bond length is 2.13 Å. The Li(1)-O(3) bond length is 2.24 Å. The Li(1)-F(1) bond length is 2.25 Å. The Li(1)-F(2) bond length is 2.45 Å. The Li(1)-F(4) bond length is 2.45 Å. The Li(1)-F(5) bond length is 2.36 Å. In the second Li site, Li(2) 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 LiO3F3 octahedra that share corners with six equivalent Fe(2)O3F3 octahedra, edges with two equivalent Li(1)O2F4 octahedra, and edges with two equivalent Fe(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 1-19°. The Li(2)-O(1) bond length is 2.27 Å. The Li(2)-O(2) bond length is 2.18 Å. The Li(2)-O(3) bond length is 2.28 Å. The Li(2)-F(2) bond length is 2.42 Å. The Li(2)-F(3) bond length is 2.16 Å. The Li(2)-F(4) bond length is 2.41 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one F(1), one F(3), and one F(5) atom. The Li(3)-O(1) bond length is 2.17 Å. The Li(3)-O(2) bond length is 1.96 Å. The Li(3)-O(3) bond length is 2.14 Å. The Li(3)-F(1) bond length is 2.49 Å. The Li(3)-F(3) bond length is 2.09 Å. The Li(3)-F(5) bond length is 2.42 Å. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in a 5-coordinate geometry to one O(2), one F(1), one F(2), one F(3), and one F(4) atom. The Fe(1)-O(2) bond length is 2.38 Å. The Fe(1)-F(1) bond length is 2.22 Å. The Fe(1)-F(2) bond length is 2.33 Å. The Fe(1)-F(3) bond length is 2.13 Å. The Fe(1)-F(4) bond length is 2.28 Å. In the second Fe site, Fe(2) 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 six equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(1)O2F4 octahedra, and edges with two equivalent Fe(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 1-19°. The Fe(2)-O(1) bond length is 1.99 Å. The Fe(2)-O(2) bond length is 2.13 Å. The Fe(2)-O(3) bond length is 2.01 Å. The Fe(2)-F(2) bond length is 2.04 Å. The Fe(2)-F(3) bond length is 2.13 Å. The Fe(2)-F(4) bond length is 2.04 Å. In the third Fe site, Fe(3) is bonded to one O(1), one O(3), one F(1), one F(2), one F(4), and one F(5) atom to form distorted FeO2F4 octahedra that share corners with six equivalent Li(1)O2F4 octahedra, edges with two equivalent Li(2)O3F3 octahedra, and edges with two equivalent Fe(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 6-25°. The Fe(3)-O(1) bond length is 2.16 Å. The Fe(3)-O(3) bond length is 2.31 Å. The Fe(3)-F(1) bond length is 2.01 Å. The Fe(3)-F(2) bond length is 1.96 Å. The Fe(3)-F(4) bond length is 1.75 Å. The Fe(3)-F(5) bond length is 2.14 Å. In the fourth Fe site, Fe(4) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(2), one F(3), one F(4), and one F(5) atom. The Fe(4)-O(2) bond length is 2.40 Å. The Fe(4)-F(1) bond length is 1.48 Å. The Fe(4)-F(2) bond length is 2.06 Å. The Fe(4)-F(3) bond length is 2.01 Å. The Fe(4)-F(4) bond length is 2.16 Å. The Fe(4)-F(5) bond length is 2.19 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Fe(2), and one Fe(3) atom to form OLi3Fe2 square pyramids that share  a cornercorner with one O(2)Li2Fe3 square pyramid,  a cornercorner with one F(3)Li2Fe3 square pyramid, corners with five equivalent O(3)Li3Fe2 square pyramids, edges with two equivalent F(2)Li2Fe4 octahedra,  an edgeedge with one O(2)Li2Fe3 square pyramid, and  an edgeedge with one F(3)Li2Fe3 square pyramid. In the second O site, O(2) is bonded to one Li(2), one Li(3), one Fe(1), one Fe(2), and one Fe(4) atom to form distorted OLi2Fe3 square pyramids that share  a cornercorner with one O(1)Li3Fe2 square pyramid,  a cornercorner with one O(3)Li3Fe2 square pyramid, corners with five equivalent F(3)Li2Fe3 square pyramids, edges with two equivalent F(2)Li2Fe4 octahedra,  an edgeedge with one O(1)Li3Fe2 square pyramid, and  an edgeedge with one O(3)Li3Fe2 square pyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Fe(2), and one Fe(3) atom to form OLi3Fe2 square pyramids that share  a cornercorner with one O(2)Li2Fe3 square pyramid,  a cornercorner with one F(3)Li2Fe3 square pyramid, corners with five equivalent O(1)Li3Fe2 square pyramids, edges with two equivalent F(2)Li2Fe4 octahedra,  an edgeedge with one O(2)Li2Fe3 square pyramid, and  an edgeedge with one F(3)Li2Fe3 square pyramid. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(3), one Fe(1), one Fe(3), and one Fe(4) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Fe(1), one Fe(2), one Fe(3), and one Fe(4) atom to form distorted FLi2Fe4 octahedra that share edges with two equivalent O(2)Li2Fe3 square pyramids, edges with two equivalent O(1)Li3Fe2 square pyramids, edges with two equivalent O(3)Li3Fe2 square pyramids, and edges with two equivalent F(3)Li2Fe3 square pyramids. In the third F site, F(3) is bonded to one Li(2), one Li(3), one Fe(1), one Fe(2), and one Fe(4) atom to form FLi2Fe3 square pyramids that share  a cornercorner with one O(1)Li3Fe2 square pyramid,  a cornercorner with one O(3)Li3Fe2 square pyramid, corners with five equivalent O(2)Li2Fe3 square pyramids, edges with two equivalent F(2)Li2Fe4 octahedra,  an edgeedge with one O(1)Li3Fe2 square pyramid, and  an edgeedge with one O(3)Li3Fe2 square pyramid. In the fourth F site, F(4) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Fe(1), one Fe(2), one Fe(3), and one Fe(4) atom. In the fifth F site, F(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one Fe(3), and one Fe(4) atom.