Li4Fe2OF8 is Corundum-derived structured and crystallizes in the monoclinic Cc 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(6) atom to form distorted LiOF5 octahedra that share corners with three equivalent Li(4)F6 octahedra, corners with three equivalent Li(3)OF5 octahedra, corners with three equivalent Fe(1)OF5 octahedra, edges with three equivalent Fe(2)OF5 octahedra, and  a faceface with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-69°. In the second Li site, Li(2) is bonded to one F(2), one F(3), one F(4), one F(5), one F(7), and one F(8) atom to form LiF6 octahedra that share corners with three equivalent Li(3)OF5 octahedra, corners with three equivalent Fe(1)OF5 octahedra, corners with three equivalent Fe(2)OF5 octahedra, edges with three equivalent Li(4)F6 octahedra, and  a faceface with one Li(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-59°. In the third Li site, Li(3) is bonded to one O(1), one F(1), one F(5), one F(6), one F(7), and one F(8) atom to form distorted LiOF5 octahedra that share corners with three equivalent Li(2)F6 octahedra, corners with three equivalent Li(1)OF5 octahedra, corners with three equivalent Fe(2)OF5 octahedra, edges with three equivalent Fe(1)OF5 octahedra, and  a faceface with one Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-69°. In the fourth Li site, Li(4) is bonded to one F(2), one F(3), one F(4), one F(5), one F(7), and one F(8) atom to form LiF6 octahedra that share corners with three equivalent Li(1)OF5 octahedra, corners with three equivalent Fe(1)OF5 octahedra, corners with three equivalent Fe(2)OF5 octahedra, edges with three equivalent Li(2)F6 octahedra, and  a faceface with one Li(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-60°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one F(1), one F(5), one F(6), one F(7), and one F(8) atom to form distorted FeOF5 octahedra that share corners with three equivalent Li(2)F6 octahedra, corners with three equivalent Li(4)F6 octahedra, corners with three equivalent Li(1)OF5 octahedra, edges with three equivalent Li(3)OF5 octahedra, and  a faceface with one Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-59°. In the second Fe site, Fe(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(6) atom to form distorted FeOF5 octahedra that share corners with three equivalent Li(2)F6 octahedra, corners with three equivalent Li(4)F6 octahedra, corners with three equivalent Li(3)OF5 octahedra, edges with three equivalent Li(1)OF5 octahedra, and  a faceface with one Fe(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-60°. O(1) is bonded to one Li(1), one Li(3), one Fe(1), and one Fe(2) atom to form distorted OLi2Fe2 trigonal pyramids that share corners with two equivalent F(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(6)Li2Fe2 trigonal pyramids, corners with two equivalent F(2)Li3Fe trigonal pyramids, corners with two equivalent F(8)Li3Fe trigonal pyramids,  an edgeedge with one F(1)Li2Fe2 trigonal pyramid,  an edgeedge with one F(6)Li2Fe2 trigonal pyramid,  an edgeedge with one F(4)Li3Fe trigonal pyramid, and  an edgeedge with one F(7)Li3Fe trigonal pyramid. There are eight inequivalent F sites. In the first F site, F(5) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one Fe(1) atom. In the second F site, F(6) is bonded to one Li(1), one Li(3), one Fe(1), and one Fe(2) atom to form distorted FLi2Fe2 trigonal pyramids that share corners with two equivalent O(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(4)Li3Fe trigonal pyramids, corners with two equivalent F(7)Li3Fe trigonal pyramids, corners with two equivalent F(8)Li3Fe trigonal pyramids,  an edgeedge with one O(1)Li2Fe2 trigonal pyramid,  an edgeedge with one F(1)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(2)Li3Fe trigonal pyramid. In the third F site, F(7) is bonded to one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form distorted FLi3Fe trigonal pyramids that share corners with two equivalent F(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(6)Li2Fe2 trigonal pyramids, corners with two equivalent F(2)Li3Fe trigonal pyramids, corners with two equivalent F(4)Li3Fe trigonal pyramids, corners with two equivalent F(8)Li3Fe trigonal pyramids,  an edgeedge with one O(1)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(8)Li3Fe trigonal pyramid. In the fourth F site, F(8) is bonded to one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form distorted FLi3Fe trigonal pyramids that share corners with two equivalent O(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(6)Li2Fe2 trigonal pyramids, corners with two equivalent F(2)Li3Fe trigonal pyramids, corners with two equivalent F(7)Li3Fe trigonal pyramids,  an edgeedge with one F(1)Li2Fe2 trigonal pyramid,  an edgeedge with one F(4)Li3Fe trigonal pyramid, and  an edgeedge with one F(7)Li3Fe trigonal pyramid. In the fifth F site, F(1) is bonded to one Li(1), one Li(3), one Fe(1), and one Fe(2) atom to form distorted FLi2Fe2 trigonal pyramids that share corners with two equivalent O(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(6)Li2Fe2 trigonal pyramids, corners with two equivalent F(2)Li3Fe trigonal pyramids, corners with two equivalent F(4)Li3Fe trigonal pyramids, corners with two equivalent F(7)Li3Fe trigonal pyramids,  an edgeedge with one O(1)Li2Fe2 trigonal pyramid,  an edgeedge with one F(6)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(8)Li3Fe trigonal pyramid. In the sixth F site, F(2) 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 corners with two equivalent O(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(4)Li3Fe trigonal pyramids, corners with two equivalent F(7)Li3Fe trigonal pyramids, corners with two equivalent F(8)Li3Fe trigonal pyramids,  an edgeedge with one F(6)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(4)Li3Fe trigonal pyramid. In the seventh F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one Fe(2) atom. In the eighth F site, F(4) 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 corners with two equivalent F(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(6)Li2Fe2 trigonal pyramids, corners with two equivalent F(2)Li3Fe trigonal pyramids, corners with two equivalent F(7)Li3Fe trigonal pyramids,  an edgeedge with one O(1)Li2Fe2 trigonal pyramid,  an edgeedge with one F(2)Li3Fe trigonal pyramid, and  an edgeedge with one F(8)Li3Fe trigonal pyramid.
Li4Fe2OF8 is Corundum-derived structured and crystallizes in the monoclinic Cc 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(6) atom to form distorted LiOF5 octahedra that share corners with three equivalent Li(4)F6 octahedra, corners with three equivalent Li(3)OF5 octahedra, corners with three equivalent Fe(1)OF5 octahedra, edges with three equivalent Fe(2)OF5 octahedra, and  a faceface with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-69°. The Li(1)-O(1) bond length is 1.98 Å. The Li(1)-F(1) bond length is 2.04 Å. The Li(1)-F(2) bond length is 2.17 Å. The Li(1)-F(3) bond length is 2.27 Å. The Li(1)-F(4) bond length is 2.18 Å. The Li(1)-F(6) bond length is 1.96 Å. In the second Li site, Li(2) is bonded to one F(2), one F(3), one F(4), one F(5), one F(7), and one F(8) atom to form LiF6 octahedra that share corners with three equivalent Li(3)OF5 octahedra, corners with three equivalent Fe(1)OF5 octahedra, corners with three equivalent Fe(2)OF5 octahedra, edges with three equivalent Li(4)F6 octahedra, and  a faceface with one Li(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-59°. The Li(2)-F(2) bond length is 2.21 Å. The Li(2)-F(3) bond length is 2.08 Å. The Li(2)-F(4) bond length is 2.14 Å. The Li(2)-F(5) bond length is 2.02 Å. The Li(2)-F(7) bond length is 1.97 Å. The Li(2)-F(8) bond length is 2.04 Å. In the third Li site, Li(3) is bonded to one O(1), one F(1), one F(5), one F(6), one F(7), and one F(8) atom to form distorted LiOF5 octahedra that share corners with three equivalent Li(2)F6 octahedra, corners with three equivalent Li(1)OF5 octahedra, corners with three equivalent Fe(2)OF5 octahedra, edges with three equivalent Fe(1)OF5 octahedra, and  a faceface with one Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-69°. The Li(3)-O(1) bond length is 1.98 Å. The Li(3)-F(1) bond length is 1.95 Å. The Li(3)-F(5) bond length is 2.31 Å. The Li(3)-F(6) bond length is 2.06 Å. The Li(3)-F(7) bond length is 2.20 Å. The Li(3)-F(8) bond length is 2.13 Å. In the fourth Li site, Li(4) is bonded to one F(2), one F(3), one F(4), one F(5), one F(7), and one F(8) atom to form LiF6 octahedra that share corners with three equivalent Li(1)OF5 octahedra, corners with three equivalent Fe(1)OF5 octahedra, corners with three equivalent Fe(2)OF5 octahedra, edges with three equivalent Li(2)F6 octahedra, and  a faceface with one Li(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-60°. The Li(4)-F(2) bond length is 2.01 Å. The Li(4)-F(3) bond length is 2.04 Å. The Li(4)-F(4) bond length is 2.01 Å. The Li(4)-F(5) bond length is 2.07 Å. The Li(4)-F(7) bond length is 2.16 Å. The Li(4)-F(8) bond length is 2.15 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one F(1), one F(5), one F(6), one F(7), and one F(8) atom to form distorted FeOF5 octahedra that share corners with three equivalent Li(2)F6 octahedra, corners with three equivalent Li(4)F6 octahedra, corners with three equivalent Li(1)OF5 octahedra, edges with three equivalent Li(3)OF5 octahedra, and  a faceface with one Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-59°. The Fe(1)-O(1) bond length is 1.92 Å. The Fe(1)-F(1) bond length is 2.18 Å. The Fe(1)-F(5) bond length is 1.94 Å. The Fe(1)-F(6) bond length is 2.12 Å. The Fe(1)-F(7) bond length is 1.95 Å. The Fe(1)-F(8) bond length is 1.98 Å. In the second Fe site, Fe(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(6) atom to form distorted FeOF5 octahedra that share corners with three equivalent Li(2)F6 octahedra, corners with three equivalent Li(4)F6 octahedra, corners with three equivalent Li(3)OF5 octahedra, edges with three equivalent Li(1)OF5 octahedra, and  a faceface with one Fe(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-60°. The Fe(2)-O(1) bond length is 1.93 Å. The Fe(2)-F(1) bond length is 2.12 Å. The Fe(2)-F(2) bond length is 1.96 Å. The Fe(2)-F(3) bond length is 1.92 Å. The Fe(2)-F(4) bond length is 1.96 Å. The Fe(2)-F(6) bond length is 2.17 Å. O(1) is bonded to one Li(1), one Li(3), one Fe(1), and one Fe(2) atom to form distorted OLi2Fe2 trigonal pyramids that share corners with two equivalent F(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(6)Li2Fe2 trigonal pyramids, corners with two equivalent F(2)Li3Fe trigonal pyramids, corners with two equivalent F(8)Li3Fe trigonal pyramids,  an edgeedge with one F(1)Li2Fe2 trigonal pyramid,  an edgeedge with one F(6)Li2Fe2 trigonal pyramid,  an edgeedge with one F(4)Li3Fe trigonal pyramid, and  an edgeedge with one F(7)Li3Fe trigonal pyramid. There are eight inequivalent F sites. In the first F site, F(5) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one Fe(1) atom. In the second F site, F(6) is bonded to one Li(1), one Li(3), one Fe(1), and one Fe(2) atom to form distorted FLi2Fe2 trigonal pyramids that share corners with two equivalent O(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(4)Li3Fe trigonal pyramids, corners with two equivalent F(7)Li3Fe trigonal pyramids, corners with two equivalent F(8)Li3Fe trigonal pyramids,  an edgeedge with one O(1)Li2Fe2 trigonal pyramid,  an edgeedge with one F(1)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(2)Li3Fe trigonal pyramid. In the third F site, F(7) is bonded to one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form distorted FLi3Fe trigonal pyramids that share corners with two equivalent F(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(6)Li2Fe2 trigonal pyramids, corners with two equivalent F(2)Li3Fe trigonal pyramids, corners with two equivalent F(4)Li3Fe trigonal pyramids, corners with two equivalent F(8)Li3Fe trigonal pyramids,  an edgeedge with one O(1)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(8)Li3Fe trigonal pyramid. In the fourth F site, F(8) is bonded to one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form distorted FLi3Fe trigonal pyramids that share corners with two equivalent O(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(6)Li2Fe2 trigonal pyramids, corners with two equivalent F(2)Li3Fe trigonal pyramids, corners with two equivalent F(7)Li3Fe trigonal pyramids,  an edgeedge with one F(1)Li2Fe2 trigonal pyramid,  an edgeedge with one F(4)Li3Fe trigonal pyramid, and  an edgeedge with one F(7)Li3Fe trigonal pyramid. In the fifth F site, F(1) is bonded to one Li(1), one Li(3), one Fe(1), and one Fe(2) atom to form distorted FLi2Fe2 trigonal pyramids that share corners with two equivalent O(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(6)Li2Fe2 trigonal pyramids, corners with two equivalent F(2)Li3Fe trigonal pyramids, corners with two equivalent F(4)Li3Fe trigonal pyramids, corners with two equivalent F(7)Li3Fe trigonal pyramids,  an edgeedge with one O(1)Li2Fe2 trigonal pyramid,  an edgeedge with one F(6)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(8)Li3Fe trigonal pyramid. In the sixth F site, F(2) 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 corners with two equivalent O(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(4)Li3Fe trigonal pyramids, corners with two equivalent F(7)Li3Fe trigonal pyramids, corners with two equivalent F(8)Li3Fe trigonal pyramids,  an edgeedge with one F(6)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(4)Li3Fe trigonal pyramid. In the seventh F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one Fe(2) atom. In the eighth F site, F(4) 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 corners with two equivalent F(1)Li2Fe2 trigonal pyramids, corners with two equivalent F(6)Li2Fe2 trigonal pyramids, corners with two equivalent F(2)Li3Fe trigonal pyramids, corners with two equivalent F(7)Li3Fe trigonal pyramids,  an edgeedge with one O(1)Li2Fe2 trigonal pyramid,  an edgeedge with one F(2)Li3Fe trigonal pyramid, and  an edgeedge with one F(8)Li3Fe trigonal pyramid.