Li5Fe3(OF5)2 is Ilmenite-derived structured and crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(10), one F(3), one F(4), one F(6), and one F(8) atom to form distorted LiF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with three equivalent Li(5)OF5 octahedra,  an edgeedge with one Fe(3)O2F4 octahedra, edges with two equivalent Fe(2)F6 octahedra, and  a faceface with one Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-61°. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one F(2), one F(3), and one F(5) atom. In the third Li site, Li(3) is bonded to one F(1), one F(10), one F(4), one F(6), one F(7), and one F(8) atom to form LiF6 octahedra that share  a cornercorner with one Fe(1)O2F4 octahedra, corners with two equivalent Li(1)F6 octahedra, corners with three equivalent Fe(2)F6 octahedra, corners with three equivalent Fe(3)O2F4 octahedra, edges with two equivalent Li(5)OF5 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-61°. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(1), one F(2), one F(3), one F(4), one F(6), and one F(9) atom. In the fifth Li site, Li(5) is bonded to one O(2), one F(1), one F(10), one F(5), one F(7), and one F(8) atom to form distorted LiOF5 octahedra that share  a cornercorner with one Fe(2)F6 octahedra, corners with two equivalent Fe(3)O2F4 octahedra, corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Fe(1)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, and  a faceface with one Fe(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 44-61°. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one F(2), one F(5), one F(7), and one F(9) atom to form FeO2F4 octahedra that share  a cornercorner with one Li(3)F6 octahedra, corners with three equivalent Li(5)OF5 octahedra,  an edgeedge with one Fe(2)F6 octahedra, and edges with two equivalent Fe(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 46-59°. In the second Fe site, Fe(2) is bonded to one F(2), one F(3), one F(4), one F(6), one F(8), and one F(9) atom to form FeF6 octahedra that share  a cornercorner with one Li(5)OF5 octahedra, corners with three equivalent Li(3)F6 octahedra,  an edgeedge with one Fe(1)O2F4 octahedra, and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-60°. In the third Fe site, Fe(3) is bonded to one O(1), one O(2), one F(1), one F(10), one F(5), and one F(7) atom to form FeO2F4 octahedra that share corners with two equivalent Li(5)OF5 octahedra, corners with three equivalent Li(3)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, edges with two equivalent Fe(1)O2F4 octahedra, and  a faceface with one Li(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-61°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(4), one Fe(1), and one Fe(3) atom to form OLi2Fe2 trigonal pyramids that share  a cornercorner with one F(4)Li3Fe trigonal pyramid,  a cornercorner with one F(6)Li3Fe trigonal pyramid, corners with three equivalent O(2)Li2Fe2 trigonal pyramids, corners with three equivalent F(2)Li2Fe2 trigonal pyramids, and  an edgeedge with one F(3)Li3Fe trigonal pyramid. In the second O site, O(2) is bonded to one Li(2), one Li(5), one Fe(1), and one Fe(3) atom to form distorted OLi2Fe2 trigonal pyramids that share  a cornercorner with one F(3)Li3Fe trigonal pyramid,  a cornercorner with one F(8)Li3Fe trigonal pyramid, corners with two equivalent F(2)Li2Fe2 trigonal pyramids, and corners with three equivalent O(1)Li2Fe2 trigonal pyramids. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one Li(5), and one Fe(3) atom. In the second F site, F(2) is bonded to one Li(2), one Li(4), one Fe(1), and one Fe(2) atom to form distorted FLi2Fe2 trigonal pyramids that share  a cornercorner with one F(3)Li3Fe trigonal pyramid,  a cornercorner with one F(8)Li3Fe trigonal pyramid, corners with two equivalent O(2)Li2Fe2 trigonal pyramids, corners with two equivalent F(4)Li3Fe trigonal pyramids, corners with three equivalent O(1)Li2Fe2 trigonal pyramids,  an edgeedge with one F(3)Li3Fe trigonal pyramid, and  an edgeedge with one F(6)Li3Fe trigonal pyramid. In the third F site, F(3) is bonded to one Li(1), one Li(2), one Li(4), and one Fe(2) atom to form distorted FLi3Fe trigonal pyramids that share  a cornercorner with one O(2)Li2Fe2 trigonal pyramid,  a cornercorner with one F(2)Li2Fe2 trigonal pyramid,  a cornercorner with one F(6)Li3Fe trigonal pyramid, corners with three equivalent F(4)Li3Fe trigonal pyramids,  an edgeedge with one O(1)Li2Fe2 trigonal pyramid,  an edgeedge with one F(2)Li2Fe2 trigonal pyramid,  an edgeedge with one F(6)Li3Fe trigonal pyramid, and  an edgeedge with one F(8)Li3Fe trigonal pyramid. In the fourth F site, F(4) is bonded to one Li(1), one Li(3), one Li(4), and one Fe(2) atom to form distorted FLi3Fe trigonal pyramids that share  a cornercorner with one O(1)Li2Fe2 trigonal pyramid,  a cornercorner with one F(8)Li3Fe trigonal pyramid, corners with two equivalent F(2)Li2Fe2 trigonal pyramids, corners with three equivalent F(3)Li3Fe trigonal pyramids,  an edgeedge with one F(8)Li3Fe trigonal pyramid, and edges with two equivalent F(6)Li3Fe trigonal pyramids. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(5), one Fe(1), and one Fe(3) atom. In the sixth F site, F(6) is bonded to one Li(1), one Li(3), one Li(4), and one Fe(2) atom to form distorted FLi3Fe trigonal pyramids that share  a cornercorner with one O(1)Li2Fe2 trigonal pyramid,  a cornercorner with one F(3)Li3Fe trigonal pyramid, corners with three equivalent F(8)Li3Fe trigonal pyramids,  an edgeedge with one F(2)Li2Fe2 trigonal pyramid,  an edgeedge with one F(3)Li3Fe trigonal pyramid, and edges with two equivalent F(4)Li3Fe trigonal pyramids. In the seventh F site, F(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(5), one Fe(1), and one Fe(3) atom. In the eighth F site, F(8) is bonded to one Li(1), one Li(3), one Li(5), and one Fe(2) atom to form distorted FLi3Fe trigonal pyramids that share  a cornercorner with one O(2)Li2Fe2 trigonal pyramid,  a cornercorner with one F(2)Li2Fe2 trigonal pyramid,  a cornercorner with one F(4)Li3Fe trigonal pyramid, corners with three equivalent F(6)Li3Fe trigonal pyramids,  an edgeedge with one F(3)Li3Fe trigonal pyramid, and  an edgeedge with one F(4)Li3Fe trigonal pyramid. In the ninth F site, F(9) is bonded in a 3-coordinate geometry to one Li(4), one Fe(1), and one Fe(2) atom. In the tenth F site, F(10) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Li(5), and one Fe(3) atom.
Li5Fe3(OF5)2 is Ilmenite-derived structured and crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(10), one F(3), one F(4), one F(6), and one F(8) atom to form distorted LiF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with three equivalent Li(5)OF5 octahedra,  an edgeedge with one Fe(3)O2F4 octahedra, edges with two equivalent Fe(2)F6 octahedra, and  a faceface with one Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-61°. The Li(1)-F(1) bond length is 1.91 Å. The Li(1)-F(10) bond length is 2.05 Å. The Li(1)-F(3) bond length is 2.02 Å. The Li(1)-F(4) bond length is 2.22 Å. The Li(1)-F(6) bond length is 2.00 Å. The Li(1)-F(8) bond length is 2.23 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one F(2), one F(3), and one F(5) atom. The Li(2)-O(1) bond length is 2.10 Å. The Li(2)-O(2) bond length is 1.96 Å. The Li(2)-F(2) bond length is 2.24 Å. The Li(2)-F(3) bond length is 2.02 Å. The Li(2)-F(5) bond length is 2.25 Å. In the third Li site, Li(3) is bonded to one F(1), one F(10), one F(4), one F(6), one F(7), and one F(8) atom to form LiF6 octahedra that share  a cornercorner with one Fe(1)O2F4 octahedra, corners with two equivalent Li(1)F6 octahedra, corners with three equivalent Fe(2)F6 octahedra, corners with three equivalent Fe(3)O2F4 octahedra, edges with two equivalent Li(5)OF5 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-61°. The Li(3)-F(1) bond length is 2.00 Å. The Li(3)-F(10) bond length is 2.17 Å. The Li(3)-F(4) bond length is 2.14 Å. The Li(3)-F(6) bond length is 2.07 Å. The Li(3)-F(7) bond length is 2.03 Å. The Li(3)-F(8) bond length is 2.24 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(1), one F(2), one F(3), one F(4), one F(6), and one F(9) atom. The Li(4)-O(1) bond length is 1.99 Å. The Li(4)-F(2) bond length is 2.30 Å. The Li(4)-F(3) bond length is 2.24 Å. The Li(4)-F(4) bond length is 2.02 Å. The Li(4)-F(6) bond length is 2.36 Å. The Li(4)-F(9) bond length is 2.08 Å. In the fifth Li site, Li(5) is bonded to one O(2), one F(1), one F(10), one F(5), one F(7), and one F(8) atom to form distorted LiOF5 octahedra that share  a cornercorner with one Fe(2)F6 octahedra, corners with two equivalent Fe(3)O2F4 octahedra, corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Fe(1)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, and  a faceface with one Fe(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 44-61°. The Li(5)-O(2) bond length is 2.17 Å. The Li(5)-F(1) bond length is 2.12 Å. The Li(5)-F(10) bond length is 1.97 Å. The Li(5)-F(5) bond length is 2.07 Å. The Li(5)-F(7) bond length is 2.26 Å. The Li(5)-F(8) bond length is 2.09 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one F(2), one F(5), one F(7), and one F(9) atom to form FeO2F4 octahedra that share  a cornercorner with one Li(3)F6 octahedra, corners with three equivalent Li(5)OF5 octahedra,  an edgeedge with one Fe(2)F6 octahedra, and edges with two equivalent Fe(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 46-59°. The Fe(1)-O(1) bond length is 1.92 Å. The Fe(1)-O(2) bond length is 1.86 Å. The Fe(1)-F(2) bond length is 2.06 Å. The Fe(1)-F(5) bond length is 2.17 Å. The Fe(1)-F(7) bond length is 2.03 Å. The Fe(1)-F(9) bond length is 2.15 Å. In the second Fe site, Fe(2) is bonded to one F(2), one F(3), one F(4), one F(6), one F(8), and one F(9) atom to form FeF6 octahedra that share  a cornercorner with one Li(5)OF5 octahedra, corners with three equivalent Li(3)F6 octahedra,  an edgeedge with one Fe(1)O2F4 octahedra, and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-60°. The Fe(2)-F(2) bond length is 2.08 Å. The Fe(2)-F(3) bond length is 1.96 Å. The Fe(2)-F(4) bond length is 1.94 Å. The Fe(2)-F(6) bond length is 1.93 Å. The Fe(2)-F(8) bond length is 1.90 Å. The Fe(2)-F(9) bond length is 1.99 Å. In the third Fe site, Fe(3) is bonded to one O(1), one O(2), one F(1), one F(10), one F(5), and one F(7) atom to form FeO2F4 octahedra that share corners with two equivalent Li(5)OF5 octahedra, corners with three equivalent Li(3)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, edges with two equivalent Fe(1)O2F4 octahedra, and  a faceface with one Li(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-61°. The Fe(3)-O(1) bond length is 1.90 Å. The Fe(3)-O(2) bond length is 1.95 Å. The Fe(3)-F(1) bond length is 2.10 Å. The Fe(3)-F(10) bond length is 2.01 Å. The Fe(3)-F(5) bond length is 2.01 Å. The Fe(3)-F(7) bond length is 2.11 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(4), one Fe(1), and one Fe(3) atom to form OLi2Fe2 trigonal pyramids that share  a cornercorner with one F(4)Li3Fe trigonal pyramid,  a cornercorner with one F(6)Li3Fe trigonal pyramid, corners with three equivalent O(2)Li2Fe2 trigonal pyramids, corners with three equivalent F(2)Li2Fe2 trigonal pyramids, and  an edgeedge with one F(3)Li3Fe trigonal pyramid. In the second O site, O(2) is bonded to one Li(2), one Li(5), one Fe(1), and one Fe(3) atom to form distorted OLi2Fe2 trigonal pyramids that share  a cornercorner with one F(3)Li3Fe trigonal pyramid,  a cornercorner with one F(8)Li3Fe trigonal pyramid, corners with two equivalent F(2)Li2Fe2 trigonal pyramids, and corners with three equivalent O(1)Li2Fe2 trigonal pyramids. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one Li(5), and one Fe(3) atom. In the second F site, F(2) is bonded to one Li(2), one Li(4), one Fe(1), and one Fe(2) atom to form distorted FLi2Fe2 trigonal pyramids that share  a cornercorner with one F(3)Li3Fe trigonal pyramid,  a cornercorner with one F(8)Li3Fe trigonal pyramid, corners with two equivalent O(2)Li2Fe2 trigonal pyramids, corners with two equivalent F(4)Li3Fe trigonal pyramids, corners with three equivalent O(1)Li2Fe2 trigonal pyramids,  an edgeedge with one F(3)Li3Fe trigonal pyramid, and  an edgeedge with one F(6)Li3Fe trigonal pyramid. In the third F site, F(3) is bonded to one Li(1), one Li(2), one Li(4), and one Fe(2) atom to form distorted FLi3Fe trigonal pyramids that share  a cornercorner with one O(2)Li2Fe2 trigonal pyramid,  a cornercorner with one F(2)Li2Fe2 trigonal pyramid,  a cornercorner with one F(6)Li3Fe trigonal pyramid, corners with three equivalent F(4)Li3Fe trigonal pyramids,  an edgeedge with one O(1)Li2Fe2 trigonal pyramid,  an edgeedge with one F(2)Li2Fe2 trigonal pyramid,  an edgeedge with one F(6)Li3Fe trigonal pyramid, and  an edgeedge with one F(8)Li3Fe trigonal pyramid. In the fourth F site, F(4) is bonded to one Li(1), one Li(3), one Li(4), and one Fe(2) atom to form distorted FLi3Fe trigonal pyramids that share  a cornercorner with one O(1)Li2Fe2 trigonal pyramid,  a cornercorner with one F(8)Li3Fe trigonal pyramid, corners with two equivalent F(2)Li2Fe2 trigonal pyramids, corners with three equivalent F(3)Li3Fe trigonal pyramids,  an edgeedge with one F(8)Li3Fe trigonal pyramid, and edges with two equivalent F(6)Li3Fe trigonal pyramids. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(5), one Fe(1), and one Fe(3) atom. In the sixth F site, F(6) is bonded to one Li(1), one Li(3), one Li(4), and one Fe(2) atom to form distorted FLi3Fe trigonal pyramids that share  a cornercorner with one O(1)Li2Fe2 trigonal pyramid,  a cornercorner with one F(3)Li3Fe trigonal pyramid, corners with three equivalent F(8)Li3Fe trigonal pyramids,  an edgeedge with one F(2)Li2Fe2 trigonal pyramid,  an edgeedge with one F(3)Li3Fe trigonal pyramid, and edges with two equivalent F(4)Li3Fe trigonal pyramids. In the seventh F site, F(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(5), one Fe(1), and one Fe(3) atom. In the eighth F site, F(8) is bonded to one Li(1), one Li(3), one Li(5), and one Fe(2) atom to form distorted FLi3Fe trigonal pyramids that share  a cornercorner with one O(2)Li2Fe2 trigonal pyramid,  a cornercorner with one F(2)Li2Fe2 trigonal pyramid,  a cornercorner with one F(4)Li3Fe trigonal pyramid, corners with three equivalent F(6)Li3Fe trigonal pyramids,  an edgeedge with one F(3)Li3Fe trigonal pyramid, and  an edgeedge with one F(4)Li3Fe trigonal pyramid. In the ninth F site, F(9) is bonded in a 3-coordinate geometry to one Li(4), one Fe(1), and one Fe(2) atom. In the tenth F site, F(10) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Li(5), and one Fe(3) atom.