Li4FeOF5 crystallizes in the trigonal P3_1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiOF5 octahedra that share corners with two equivalent Li(3)OF5 octahedra, corners with two equivalent Fe(1)OF5 octahedra, edges with two equivalent Li(3)OF5 octahedra, edges with two equivalent Fe(1)OF5 octahedra, edges with three equivalent Li(2)OF5 octahedra, and edges with three equivalent Li(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. In the second Li site, Li(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiOF5 octahedra that share corners with two equivalent Li(3)OF5 octahedra, corners with two equivalent Fe(1)OF5 octahedra, edges with two equivalent Li(3)OF5 octahedra, edges with two equivalent Fe(1)OF5 octahedra, edges with three equivalent Li(1)OF5 octahedra, and edges with three equivalent Li(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 6-13°. In the third Li site, Li(3) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent Li(4)OF5 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Li(2)OF5 octahedra, edges with two equivalent Li(4)OF5 octahedra, and edges with three equivalent Fe(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. In the fourth Li site, Li(4) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form distorted LiOF5 octahedra that share corners with two equivalent Li(3)OF5 octahedra, corners with two equivalent Fe(1)OF5 octahedra, edges with two equivalent Li(3)OF5 octahedra, edges with two equivalent Fe(1)OF5 octahedra, edges with three equivalent Li(1)OF5 octahedra, and edges with three equivalent Li(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. Fe(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form FeOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent Li(4)OF5 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Li(2)OF5 octahedra, edges with two equivalent Li(4)OF5 octahedra, and edges with three equivalent Li(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form OLi4Fe square pyramids that share  a cornercorner with one F(1)Li4Fe square pyramid,  a cornercorner with one F(2)Li4Fe square pyramid,  a cornercorner with one F(5)Li4Fe square pyramid, corners with three equivalent F(3)Li4Fe square pyramids, corners with three equivalent F(4)Li4Fe square pyramids,  an edgeedge with one F(3)Li4Fe square pyramid,  an edgeedge with one F(4)Li4Fe square pyramid, edges with two equivalent F(1)Li4Fe square pyramids, edges with two equivalent F(2)Li4Fe square pyramids, and edges with two equivalent F(5)Li4Fe square pyramids. There are five inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form FLi4Fe square pyramids that share  a cornercorner with one O(1)Li4Fe square pyramid,  a cornercorner with one F(3)Li4Fe square pyramid,  a cornercorner with one F(4)Li4Fe square pyramid, corners with three equivalent F(2)Li4Fe square pyramids, corners with three equivalent F(5)Li4Fe square pyramids,  an edgeedge with one F(2)Li4Fe square pyramid,  an edgeedge with one F(5)Li4Fe square pyramid, edges with two equivalent O(1)Li4Fe square pyramids, edges with two equivalent F(3)Li4Fe square pyramids, and edges with two equivalent F(4)Li4Fe square pyramids. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form FLi4Fe square pyramids that share  a cornercorner with one O(1)Li4Fe square pyramid,  a cornercorner with one F(3)Li4Fe square pyramid,  a cornercorner with one F(5)Li4Fe square pyramid, corners with three equivalent F(1)Li4Fe square pyramids, corners with three equivalent F(4)Li4Fe square pyramids,  an edgeedge with one F(1)Li4Fe square pyramid,  an edgeedge with one F(4)Li4Fe square pyramid, edges with two equivalent O(1)Li4Fe square pyramids, edges with two equivalent F(3)Li4Fe square pyramids, and edges with two equivalent F(5)Li4Fe square pyramids. In the third F site, F(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form distorted FLi4Fe square pyramids that share  a cornercorner with one F(1)Li4Fe square pyramid,  a cornercorner with one F(2)Li4Fe square pyramid,  a cornercorner with one F(4)Li4Fe square pyramid, corners with three equivalent O(1)Li4Fe square pyramids, corners with three equivalent F(5)Li4Fe square pyramids,  an edgeedge with one O(1)Li4Fe square pyramid,  an edgeedge with one F(5)Li4Fe square pyramid, edges with two equivalent F(1)Li4Fe square pyramids, edges with two equivalent F(2)Li4Fe square pyramids, and edges with two equivalent F(4)Li4Fe square pyramids. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form FLi4Fe square pyramids that share  a cornercorner with one F(1)Li4Fe square pyramid,  a cornercorner with one F(3)Li4Fe square pyramid,  a cornercorner with one F(5)Li4Fe square pyramid, corners with three equivalent O(1)Li4Fe square pyramids, corners with three equivalent F(2)Li4Fe square pyramids,  an edgeedge with one O(1)Li4Fe square pyramid,  an edgeedge with one F(2)Li4Fe square pyramid, edges with two equivalent F(1)Li4Fe square pyramids, edges with two equivalent F(3)Li4Fe square pyramids, and edges with two equivalent F(5)Li4Fe square pyramids. In the fifth F site, F(5) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form FLi4Fe square pyramids that share  a cornercorner with one O(1)Li4Fe square pyramid,  a cornercorner with one F(2)Li4Fe square pyramid,  a cornercorner with one F(4)Li4Fe square pyramid, corners with three equivalent F(1)Li4Fe square pyramids, corners with three equivalent F(3)Li4Fe square pyramids,  an edgeedge with one F(1)Li4Fe square pyramid,  an edgeedge with one F(3)Li4Fe square pyramid, edges with two equivalent O(1)Li4Fe square pyramids, edges with two equivalent F(2)Li4Fe square pyramids, and edges with two equivalent F(4)Li4Fe square pyramids.
Li4FeOF5 crystallizes in the trigonal P3_1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiOF5 octahedra that share corners with two equivalent Li(3)OF5 octahedra, corners with two equivalent Fe(1)OF5 octahedra, edges with two equivalent Li(3)OF5 octahedra, edges with two equivalent Fe(1)OF5 octahedra, edges with three equivalent Li(2)OF5 octahedra, and edges with three equivalent Li(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. The Li(1)-O(1) bond length is 2.02 Å. The Li(1)-F(1) bond length is 2.10 Å. The Li(1)-F(2) bond length is 2.09 Å. The Li(1)-F(3) bond length is 2.01 Å. The Li(1)-F(4) bond length is 2.08 Å. The Li(1)-F(5) bond length is 2.22 Å. In the second Li site, Li(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiOF5 octahedra that share corners with two equivalent Li(3)OF5 octahedra, corners with two equivalent Fe(1)OF5 octahedra, edges with two equivalent Li(3)OF5 octahedra, edges with two equivalent Fe(1)OF5 octahedra, edges with three equivalent Li(1)OF5 octahedra, and edges with three equivalent Li(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 6-13°. The Li(2)-O(1) bond length is 2.08 Å. The Li(2)-F(1) bond length is 1.94 Å. The Li(2)-F(2) bond length is 1.95 Å. The Li(2)-F(3) bond length is 2.28 Å. The Li(2)-F(4) bond length is 2.33 Å. The Li(2)-F(5) bond length is 2.09 Å. In the third Li site, Li(3) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent Li(4)OF5 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Li(2)OF5 octahedra, edges with two equivalent Li(4)OF5 octahedra, and edges with three equivalent Fe(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. The Li(3)-O(1) bond length is 2.04 Å. The Li(3)-F(1) bond length is 2.13 Å. The Li(3)-F(2) bond length is 2.22 Å. The Li(3)-F(3) bond length is 2.05 Å. The Li(3)-F(4) bond length is 2.01 Å. The Li(3)-F(5) bond length is 2.02 Å. In the fourth Li site, Li(4) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form distorted LiOF5 octahedra that share corners with two equivalent Li(3)OF5 octahedra, corners with two equivalent Fe(1)OF5 octahedra, edges with two equivalent Li(3)OF5 octahedra, edges with two equivalent Fe(1)OF5 octahedra, edges with three equivalent Li(1)OF5 octahedra, and edges with three equivalent Li(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. The Li(4)-O(1) bond length is 2.03 Å. The Li(4)-F(1) bond length is 2.04 Å. The Li(4)-F(2) bond length is 2.05 Å. The Li(4)-F(3) bond length is 2.44 Å. The Li(4)-F(4) bond length is 2.00 Å. The Li(4)-F(5) bond length is 2.00 Å. Fe(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form FeOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent Li(4)OF5 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Li(2)OF5 octahedra, edges with two equivalent Li(4)OF5 octahedra, and edges with three equivalent Li(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. The Fe(1)-O(1) bond length is 1.80 Å. The Fe(1)-F(1) bond length is 2.08 Å. The Fe(1)-F(2) bond length is 2.08 Å. The Fe(1)-F(3) bond length is 2.01 Å. The Fe(1)-F(4) bond length is 2.11 Å. The Fe(1)-F(5) bond length is 2.05 Å. O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form OLi4Fe square pyramids that share  a cornercorner with one F(1)Li4Fe square pyramid,  a cornercorner with one F(2)Li4Fe square pyramid,  a cornercorner with one F(5)Li4Fe square pyramid, corners with three equivalent F(3)Li4Fe square pyramids, corners with three equivalent F(4)Li4Fe square pyramids,  an edgeedge with one F(3)Li4Fe square pyramid,  an edgeedge with one F(4)Li4Fe square pyramid, edges with two equivalent F(1)Li4Fe square pyramids, edges with two equivalent F(2)Li4Fe square pyramids, and edges with two equivalent F(5)Li4Fe square pyramids. There are five inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form FLi4Fe square pyramids that share  a cornercorner with one O(1)Li4Fe square pyramid,  a cornercorner with one F(3)Li4Fe square pyramid,  a cornercorner with one F(4)Li4Fe square pyramid, corners with three equivalent F(2)Li4Fe square pyramids, corners with three equivalent F(5)Li4Fe square pyramids,  an edgeedge with one F(2)Li4Fe square pyramid,  an edgeedge with one F(5)Li4Fe square pyramid, edges with two equivalent O(1)Li4Fe square pyramids, edges with two equivalent F(3)Li4Fe square pyramids, and edges with two equivalent F(4)Li4Fe square pyramids. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form FLi4Fe square pyramids that share  a cornercorner with one O(1)Li4Fe square pyramid,  a cornercorner with one F(3)Li4Fe square pyramid,  a cornercorner with one F(5)Li4Fe square pyramid, corners with three equivalent F(1)Li4Fe square pyramids, corners with three equivalent F(4)Li4Fe square pyramids,  an edgeedge with one F(1)Li4Fe square pyramid,  an edgeedge with one F(4)Li4Fe square pyramid, edges with two equivalent O(1)Li4Fe square pyramids, edges with two equivalent F(3)Li4Fe square pyramids, and edges with two equivalent F(5)Li4Fe square pyramids. In the third F site, F(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form distorted FLi4Fe square pyramids that share  a cornercorner with one F(1)Li4Fe square pyramid,  a cornercorner with one F(2)Li4Fe square pyramid,  a cornercorner with one F(4)Li4Fe square pyramid, corners with three equivalent O(1)Li4Fe square pyramids, corners with three equivalent F(5)Li4Fe square pyramids,  an edgeedge with one O(1)Li4Fe square pyramid,  an edgeedge with one F(5)Li4Fe square pyramid, edges with two equivalent F(1)Li4Fe square pyramids, edges with two equivalent F(2)Li4Fe square pyramids, and edges with two equivalent F(4)Li4Fe square pyramids. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form FLi4Fe square pyramids that share  a cornercorner with one F(1)Li4Fe square pyramid,  a cornercorner with one F(3)Li4Fe square pyramid,  a cornercorner with one F(5)Li4Fe square pyramid, corners with three equivalent O(1)Li4Fe square pyramids, corners with three equivalent F(2)Li4Fe square pyramids,  an edgeedge with one O(1)Li4Fe square pyramid,  an edgeedge with one F(2)Li4Fe square pyramid, edges with two equivalent F(1)Li4Fe square pyramids, edges with two equivalent F(3)Li4Fe square pyramids, and edges with two equivalent F(5)Li4Fe square pyramids. In the fifth F site, F(5) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form FLi4Fe square pyramids that share  a cornercorner with one O(1)Li4Fe square pyramid,  a cornercorner with one F(2)Li4Fe square pyramid,  a cornercorner with one F(4)Li4Fe square pyramid, corners with three equivalent F(1)Li4Fe square pyramids, corners with three equivalent F(3)Li4Fe square pyramids,  an edgeedge with one F(1)Li4Fe square pyramid,  an edgeedge with one F(3)Li4Fe square pyramid, edges with two equivalent O(1)Li4Fe square pyramids, edges with two equivalent F(2)Li4Fe square pyramids, and edges with two equivalent F(4)Li4Fe square pyramids.