LiFe8(O3F)4 crystallizes in the monoclinic C2 space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(4), one O(6), one F(1), and one F(2) atom to form FeO4F2 octahedra that share corners with four equivalent Fe(4)O4F2 octahedra, corners with three equivalent Fe(3)O5 square pyramids, and edges with two equivalent Fe(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. In the second Fe site, Fe(2) is bonded to one O(1), one O(3), one O(5), one O(6), one F(1), and one F(2) atom to form FeO4F2 octahedra that share corners with four equivalent Fe(4)O4F2 octahedra, corners with three equivalent Fe(3)O5 square pyramids, and edges with two equivalent Fe(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. In the third Fe site, Fe(3) is bonded to one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form a mixture of distorted corner and edge-sharing FeO5 square pyramids. The corner-sharing octahedral tilt angles range from 51-53°. In the fourth Fe site, Fe(4) is bonded to one O(2), one O(3), one O(4), one O(5), one F(1), and one F(2) atom to form FeO4F2 octahedra that share corners with four equivalent Fe(1)O4F2 octahedra, corners with four equivalent Fe(2)O4F2 octahedra, and edges with two equivalent Fe(3)O5 square pyramids. The corner-sharing octahedral tilt angles range from 45-53°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Li(1), one Fe(1), and one Fe(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Fe(1), one Fe(3), and one Fe(4) atom. In the third O site, O(3) is bonded to one Li(1), one Fe(2), one Fe(3), and one Fe(4) atom to form distorted corner-sharing OLiFe3 trigonal pyramids. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Fe(1), one Fe(3), and one Fe(4) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Fe(2), one Fe(3), and one Fe(4) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(3) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Fe(1), one Fe(2), and one Fe(4) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Fe(1), one Fe(2), and one Fe(4) atom.
LiFe8(O3F)4 crystallizes in the monoclinic C2 space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Li(1)-O(1) bond lengths are 1.89 Å. Both Li(1)-O(2) bond lengths are 2.39 Å. Both Li(1)-O(3) bond lengths are 2.10 Å. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(4), one O(6), one F(1), and one F(2) atom to form FeO4F2 octahedra that share corners with four equivalent Fe(4)O4F2 octahedra, corners with three equivalent Fe(3)O5 square pyramids, and edges with two equivalent Fe(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. The Fe(1)-O(1) bond length is 1.88 Å. The Fe(1)-O(2) bond length is 2.00 Å. The Fe(1)-O(4) bond length is 1.97 Å. The Fe(1)-O(6) bond length is 1.94 Å. The Fe(1)-F(1) bond length is 2.10 Å. The Fe(1)-F(2) bond length is 2.10 Å. In the second Fe site, Fe(2) is bonded to one O(1), one O(3), one O(5), one O(6), one F(1), and one F(2) atom to form FeO4F2 octahedra that share corners with four equivalent Fe(4)O4F2 octahedra, corners with three equivalent Fe(3)O5 square pyramids, and edges with two equivalent Fe(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. The Fe(2)-O(1) bond length is 1.89 Å. The Fe(2)-O(3) bond length is 2.02 Å. The Fe(2)-O(5) bond length is 1.96 Å. The Fe(2)-O(6) bond length is 1.93 Å. The Fe(2)-F(1) bond length is 2.11 Å. The Fe(2)-F(2) bond length is 2.09 Å. In the third Fe site, Fe(3) is bonded to one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form a mixture of distorted corner and edge-sharing FeO5 square pyramids. The corner-sharing octahedral tilt angles range from 51-53°. The Fe(3)-O(2) bond length is 1.99 Å. The Fe(3)-O(3) bond length is 2.01 Å. The Fe(3)-O(4) bond length is 1.96 Å. The Fe(3)-O(5) bond length is 1.96 Å. The Fe(3)-O(6) bond length is 1.95 Å. In the fourth Fe site, Fe(4) is bonded to one O(2), one O(3), one O(4), one O(5), one F(1), and one F(2) atom to form FeO4F2 octahedra that share corners with four equivalent Fe(1)O4F2 octahedra, corners with four equivalent Fe(2)O4F2 octahedra, and edges with two equivalent Fe(3)O5 square pyramids. The corner-sharing octahedral tilt angles range from 45-53°. The Fe(4)-O(2) bond length is 1.96 Å. The Fe(4)-O(3) bond length is 1.97 Å. The Fe(4)-O(4) bond length is 1.95 Å. The Fe(4)-O(5) bond length is 1.95 Å. The Fe(4)-F(1) bond length is 2.14 Å. The Fe(4)-F(2) bond length is 2.16 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Li(1), one Fe(1), and one Fe(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Fe(1), one Fe(3), and one Fe(4) atom. In the third O site, O(3) is bonded to one Li(1), one Fe(2), one Fe(3), and one Fe(4) atom to form distorted corner-sharing OLiFe3 trigonal pyramids. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Fe(1), one Fe(3), and one Fe(4) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Fe(2), one Fe(3), and one Fe(4) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(3) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Fe(1), one Fe(2), and one Fe(4) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Fe(1), one Fe(2), and one Fe(4) atom.