LiFe8(O3F)4 crystallizes in the monoclinic Pm space group. Li(1) is bonded in a 4-coordinate geometry to one O(6), two equivalent O(5), and one F(2) atom. There are eight inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(6), two equivalent O(2), and one F(1) atom to form distorted FeO4F trigonal bipyramids that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(5)O4F2 octahedra, corners with two equivalent Fe(4)O4F2 octahedra, corners with two equivalent Fe(3)O5 square pyramids, and  an edgeedge with one Fe(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 55-71°. In the second Fe site, Fe(2) is bonded to one O(1), one O(6), two equivalent O(3), one F(1), and one F(2) atom to form FeO4F2 octahedra that share corners with two equivalent Fe(4)O4F2 octahedra, corners with two equivalent Fe(5)O4F2 octahedra, corners with two equivalent Fe(3)O5 square pyramids,  a cornercorner with one Fe(1)O4F trigonal bipyramid, and  an edgeedge with one Fe(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 34-51°. In the third Fe site, Fe(3) is bonded to one O(7), two equivalent O(2), and two equivalent O(3) atoms to form distorted FeO5 square pyramids that share  a cornercorner with one Fe(7)O4F2 octahedra,  a cornercorner with one Fe(8)O4F2 octahedra, corners with two equivalent Fe(2)O4F2 octahedra, corners with two equivalent Fe(1)O4F trigonal bipyramids, and edges with two equivalent Fe(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 49-53°. In the fourth Fe site, Fe(4) is bonded to two equivalent O(2), two equivalent O(3), one F(3), and one F(4) atom to form distorted FeO4F2 octahedra that share corners with two equivalent Fe(2)O4F2 octahedra, corners with two equivalent Fe(7)O4F2 octahedra, corners with two equivalent Fe(8)O4F2 octahedra, corners with two equivalent Fe(1)O4F trigonal bipyramids, and edges with two equivalent Fe(3)O5 square pyramids. The corner-sharing octahedral tilt angles range from 43-51°. In the fifth Fe site, Fe(5) is bonded to two equivalent O(4), two equivalent O(5), one F(1), and one F(2) atom to form FeO4F2 octahedra that share corners with two equivalent Fe(2)O4F2 octahedra, corners with two equivalent Fe(7)O4F2 octahedra, corners with two equivalent Fe(8)O4F2 octahedra, and  a cornercorner with one Fe(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 34-56°. In the sixth Fe site, Fe(6) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(4), and two equivalent O(5) atoms. In the seventh Fe site, Fe(7) is bonded to one O(7), one O(8), two equivalent O(4), one F(3), and one F(4) atom to form FeO4F2 octahedra that share corners with two equivalent Fe(4)O4F2 octahedra, corners with two equivalent Fe(5)O4F2 octahedra,  a cornercorner with one Fe(3)O5 square pyramid, and edges with two equivalent Fe(8)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. In the eighth Fe site, Fe(8) is bonded to one O(7), one O(8), two equivalent O(5), one F(3), and one F(4) atom to form FeO4F2 octahedra that share corners with two equivalent Fe(4)O4F2 octahedra, corners with two equivalent Fe(5)O4F2 octahedra,  a cornercorner with one Fe(3)O5 square pyramid, and edges with two equivalent Fe(7)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(6) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Fe(1), one Fe(3), and one Fe(4) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Fe(2), one Fe(3), and one Fe(4) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Fe(5), one Fe(6), and one Fe(7) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Fe(5), one Fe(6), and one Fe(8) atom. In the sixth O site, O(6) is bonded in a T-shaped geometry to one Li(1), one Fe(1), and one Fe(2) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Fe(3), one Fe(7), and one Fe(8) atom. In the eighth O site, O(8) is bonded in a water-like geometry to one Fe(7) and one Fe(8) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(2), and one Fe(5) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Li(1), one Fe(2), and one Fe(5) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Fe(4), one Fe(7), and one Fe(8) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Fe(4), one Fe(7), and one Fe(8) atom.
LiFe8(O3F)4 crystallizes in the monoclinic Pm space group. Li(1) is bonded in a 4-coordinate geometry to one O(6), two equivalent O(5), and one F(2) atom. The Li(1)-O(6) bond length is 1.78 Å. Both Li(1)-O(5) bond lengths are 1.98 Å. The Li(1)-F(2) bond length is 1.85 Å. There are eight inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(6), two equivalent O(2), and one F(1) atom to form distorted FeO4F trigonal bipyramids that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(5)O4F2 octahedra, corners with two equivalent Fe(4)O4F2 octahedra, corners with two equivalent Fe(3)O5 square pyramids, and  an edgeedge with one Fe(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 55-71°. The Fe(1)-O(1) bond length is 1.90 Å. The Fe(1)-O(6) bond length is 1.88 Å. Both Fe(1)-O(2) bond lengths are 1.96 Å. The Fe(1)-F(1) bond length is 1.96 Å. In the second Fe site, Fe(2) is bonded to one O(1), one O(6), two equivalent O(3), one F(1), and one F(2) atom to form FeO4F2 octahedra that share corners with two equivalent Fe(4)O4F2 octahedra, corners with two equivalent Fe(5)O4F2 octahedra, corners with two equivalent Fe(3)O5 square pyramids,  a cornercorner with one Fe(1)O4F trigonal bipyramid, and  an edgeedge with one Fe(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 34-51°. The Fe(2)-O(1) bond length is 1.95 Å. The Fe(2)-O(6) bond length is 1.86 Å. Both Fe(2)-O(3) bond lengths are 1.95 Å. The Fe(2)-F(1) bond length is 2.31 Å. The Fe(2)-F(2) bond length is 2.03 Å. In the third Fe site, Fe(3) is bonded to one O(7), two equivalent O(2), and two equivalent O(3) atoms to form distorted FeO5 square pyramids that share  a cornercorner with one Fe(7)O4F2 octahedra,  a cornercorner with one Fe(8)O4F2 octahedra, corners with two equivalent Fe(2)O4F2 octahedra, corners with two equivalent Fe(1)O4F trigonal bipyramids, and edges with two equivalent Fe(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 49-53°. The Fe(3)-O(7) bond length is 1.97 Å. Both Fe(3)-O(2) bond lengths are 1.98 Å. Both Fe(3)-O(3) bond lengths are 1.97 Å. In the fourth Fe site, Fe(4) is bonded to two equivalent O(2), two equivalent O(3), one F(3), and one F(4) atom to form distorted FeO4F2 octahedra that share corners with two equivalent Fe(2)O4F2 octahedra, corners with two equivalent Fe(7)O4F2 octahedra, corners with two equivalent Fe(8)O4F2 octahedra, corners with two equivalent Fe(1)O4F trigonal bipyramids, and edges with two equivalent Fe(3)O5 square pyramids. The corner-sharing octahedral tilt angles range from 43-51°. Both Fe(4)-O(2) bond lengths are 1.98 Å. Both Fe(4)-O(3) bond lengths are 1.97 Å. The Fe(4)-F(3) bond length is 2.39 Å. The Fe(4)-F(4) bond length is 2.11 Å. In the fifth Fe site, Fe(5) is bonded to two equivalent O(4), two equivalent O(5), one F(1), and one F(2) atom to form FeO4F2 octahedra that share corners with two equivalent Fe(2)O4F2 octahedra, corners with two equivalent Fe(7)O4F2 octahedra, corners with two equivalent Fe(8)O4F2 octahedra, and  a cornercorner with one Fe(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 34-56°. Both Fe(5)-O(4) bond lengths are 1.93 Å. Both Fe(5)-O(5) bond lengths are 2.02 Å. The Fe(5)-F(1) bond length is 2.07 Å. The Fe(5)-F(2) bond length is 2.18 Å. In the sixth Fe site, Fe(6) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(4), and two equivalent O(5) atoms. The Fe(6)-O(1) bond length is 1.90 Å. Both Fe(6)-O(4) bond lengths are 1.98 Å. Both Fe(6)-O(5) bond lengths are 2.00 Å. In the seventh Fe site, Fe(7) is bonded to one O(7), one O(8), two equivalent O(4), one F(3), and one F(4) atom to form FeO4F2 octahedra that share corners with two equivalent Fe(4)O4F2 octahedra, corners with two equivalent Fe(5)O4F2 octahedra,  a cornercorner with one Fe(3)O5 square pyramid, and edges with two equivalent Fe(8)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. The Fe(7)-O(7) bond length is 1.97 Å. The Fe(7)-O(8) bond length is 1.88 Å. Both Fe(7)-O(4) bond lengths are 1.94 Å. The Fe(7)-F(3) bond length is 2.11 Å. The Fe(7)-F(4) bond length is 2.20 Å. In the eighth Fe site, Fe(8) is bonded to one O(7), one O(8), two equivalent O(5), one F(3), and one F(4) atom to form FeO4F2 octahedra that share corners with two equivalent Fe(4)O4F2 octahedra, corners with two equivalent Fe(5)O4F2 octahedra,  a cornercorner with one Fe(3)O5 square pyramid, and edges with two equivalent Fe(7)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. The Fe(8)-O(7) bond length is 1.96 Å. The Fe(8)-O(8) bond length is 1.86 Å. Both Fe(8)-O(5) bond lengths are 1.97 Å. The Fe(8)-F(3) bond length is 2.08 Å. The Fe(8)-F(4) bond length is 2.21 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(6) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Fe(1), one Fe(3), and one Fe(4) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Fe(2), one Fe(3), and one Fe(4) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Fe(5), one Fe(6), and one Fe(7) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Fe(5), one Fe(6), and one Fe(8) atom. In the sixth O site, O(6) is bonded in a T-shaped geometry to one Li(1), one Fe(1), and one Fe(2) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Fe(3), one Fe(7), and one Fe(8) atom. In the eighth O site, O(8) is bonded in a water-like geometry to one Fe(7) and one Fe(8) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(2), and one Fe(5) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Li(1), one Fe(2), and one Fe(5) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Fe(4), one Fe(7), and one Fe(8) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Fe(4), one Fe(7), and one Fe(8) atom.