LiFe8(O7F)2 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one O(10), one O(12), and one O(6) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent Fe(1)O5F octahedra, corners with two equivalent Fe(8)O5F octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-65°. There are eight inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(12), one O(3), one O(5), one O(9), and one F(2) atom to form FeO5F octahedra that share corners with four equivalent Fe(7)O5F octahedra, corners with four equivalent Fe(5)O6 octahedra, corners with two equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Fe(4)O5F octahedra, and  an edgeedge with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. In the second Fe site, Fe(2) is bonded to one O(1), one O(10), one O(12), one O(13), one O(4), and one O(6) atom to form FeO6 octahedra that share corners with four equivalent Fe(8)O5F octahedra, corners with four equivalent Fe(5)O6 octahedra,  an edgeedge with one Fe(1)O5F octahedra,  an edgeedge with one Fe(3)O5F octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 46-54°. In the third Fe site, Fe(3) is bonded to one O(13), one O(14), one O(2), one O(4), one O(7), and one F(1) atom to form FeO5F octahedra that share corners with four equivalent Fe(6)O5F octahedra, corners with four equivalent Fe(8)O5F octahedra,  an edgeedge with one Fe(4)O5F octahedra, and  an edgeedge with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the fourth Fe site, Fe(4) is bonded to one O(11), one O(14), one O(2), one O(3), one O(8), and one F(2) atom to form a mixture of edge and corner-sharing FeO5F octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the fifth Fe site, Fe(5) is bonded to one O(1), one O(10), one O(12), one O(5), one O(6), and one O(9) atom to form FeO6 octahedra that share corners with four equivalent Fe(1)O5F octahedra, corners with four equivalent Fe(2)O6 octahedra,  an edgeedge with one Fe(7)O5F octahedra,  an edgeedge with one Fe(8)O5F octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 46-54°. In the sixth Fe site, Fe(6) is bonded to one O(11), one O(14), one O(2), one O(7), one O(8), and one F(1) atom to form a mixture of edge and corner-sharing FeO5F octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the seventh Fe site, Fe(7) is bonded to one O(11), one O(3), one O(5), one O(8), one O(9), and one F(2) atom to form FeO5F octahedra that share corners with four equivalent Fe(1)O5F octahedra, corners with four equivalent Fe(4)O5F octahedra,  an edgeedge with one Fe(6)O5F octahedra, and  an edgeedge with one Fe(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the eighth Fe site, Fe(8) is bonded to one O(10), one O(13), one O(4), one O(6), one O(7), and one F(1) atom to form FeO5F octahedra that share corners with four equivalent Fe(3)O5F octahedra, corners with four equivalent Fe(2)O6 octahedra, corners with two equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Fe(6)O5F octahedra, and  an edgeedge with one Fe(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Fe(1), one Fe(2), and one Fe(5) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Fe(3), one Fe(4), and one Fe(6) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Fe(1), one Fe(4), and one Fe(7) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Fe(2), one Fe(3), and one Fe(8) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(5), and one Fe(7) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Fe(2), one Fe(5), and one Fe(8) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Fe(3), one Fe(6), and one Fe(8) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Fe(4), one Fe(6), and one Fe(7) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(5), and one Fe(7) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Li(1), one Fe(2), one Fe(5), and one Fe(8) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Fe(4), one Fe(6), and one Fe(7) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(1), one Fe(1), one Fe(2), and one Fe(5) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Fe(2), one Fe(3), and one Fe(8) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Fe(3), one Fe(4), and one Fe(6) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Fe(3), one Fe(6), and one Fe(8) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(4), and one Fe(7) atom.
LiFe8(O7F)2 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one O(10), one O(12), and one O(6) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent Fe(1)O5F octahedra, corners with two equivalent Fe(8)O5F octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-65°. The Li(1)-O(1) bond length is 1.83 Å. The Li(1)-O(10) bond length is 1.84 Å. The Li(1)-O(12) bond length is 1.84 Å. The Li(1)-O(6) bond length is 1.83 Å. There are eight inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(12), one O(3), one O(5), one O(9), and one F(2) atom to form FeO5F octahedra that share corners with four equivalent Fe(7)O5F octahedra, corners with four equivalent Fe(5)O6 octahedra, corners with two equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Fe(4)O5F octahedra, and  an edgeedge with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. The Fe(1)-O(1) bond length is 1.97 Å. The Fe(1)-O(12) bond length is 1.97 Å. The Fe(1)-O(3) bond length is 1.93 Å. The Fe(1)-O(5) bond length is 2.06 Å. The Fe(1)-O(9) bond length is 2.07 Å. The Fe(1)-F(2) bond length is 2.06 Å. In the second Fe site, Fe(2) is bonded to one O(1), one O(10), one O(12), one O(13), one O(4), and one O(6) atom to form FeO6 octahedra that share corners with four equivalent Fe(8)O5F octahedra, corners with four equivalent Fe(5)O6 octahedra,  an edgeedge with one Fe(1)O5F octahedra,  an edgeedge with one Fe(3)O5F octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 46-54°. The Fe(2)-O(1) bond length is 1.95 Å. The Fe(2)-O(10) bond length is 2.06 Å. The Fe(2)-O(12) bond length is 1.98 Å. The Fe(2)-O(13) bond length is 1.92 Å. The Fe(2)-O(4) bond length is 1.93 Å. The Fe(2)-O(6) bond length is 2.06 Å. In the third Fe site, Fe(3) is bonded to one O(13), one O(14), one O(2), one O(4), one O(7), and one F(1) atom to form FeO5F octahedra that share corners with four equivalent Fe(6)O5F octahedra, corners with four equivalent Fe(8)O5F octahedra,  an edgeedge with one Fe(4)O5F octahedra, and  an edgeedge with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The Fe(3)-O(13) bond length is 1.97 Å. The Fe(3)-O(14) bond length is 1.94 Å. The Fe(3)-O(2) bond length is 1.93 Å. The Fe(3)-O(4) bond length is 1.97 Å. The Fe(3)-O(7) bond length is 1.99 Å. The Fe(3)-F(1) bond length is 2.14 Å. In the fourth Fe site, Fe(4) is bonded to one O(11), one O(14), one O(2), one O(3), one O(8), and one F(2) atom to form a mixture of edge and corner-sharing FeO5F octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The Fe(4)-O(11) bond length is 2.06 Å. The Fe(4)-O(14) bond length is 1.95 Å. The Fe(4)-O(2) bond length is 1.96 Å. The Fe(4)-O(3) bond length is 1.94 Å. The Fe(4)-O(8) bond length is 2.05 Å. The Fe(4)-F(2) bond length is 2.09 Å. In the fifth Fe site, Fe(5) is bonded to one O(1), one O(10), one O(12), one O(5), one O(6), and one O(9) atom to form FeO6 octahedra that share corners with four equivalent Fe(1)O5F octahedra, corners with four equivalent Fe(2)O6 octahedra,  an edgeedge with one Fe(7)O5F octahedra,  an edgeedge with one Fe(8)O5F octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 46-54°. The Fe(5)-O(1) bond length is 2.06 Å. The Fe(5)-O(10) bond length is 1.98 Å. The Fe(5)-O(12) bond length is 2.06 Å. The Fe(5)-O(5) bond length is 1.93 Å. The Fe(5)-O(6) bond length is 1.96 Å. The Fe(5)-O(9) bond length is 1.92 Å. In the sixth Fe site, Fe(6) is bonded to one O(11), one O(14), one O(2), one O(7), one O(8), and one F(1) atom to form a mixture of edge and corner-sharing FeO5F octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The Fe(6)-O(11) bond length is 1.95 Å. The Fe(6)-O(14) bond length is 2.06 Å. The Fe(6)-O(2) bond length is 2.05 Å. The Fe(6)-O(7) bond length is 1.94 Å. The Fe(6)-O(8) bond length is 1.96 Å. The Fe(6)-F(1) bond length is 2.09 Å. In the seventh Fe site, Fe(7) is bonded to one O(11), one O(3), one O(5), one O(8), one O(9), and one F(2) atom to form FeO5F octahedra that share corners with four equivalent Fe(1)O5F octahedra, corners with four equivalent Fe(4)O5F octahedra,  an edgeedge with one Fe(6)O5F octahedra, and  an edgeedge with one Fe(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The Fe(7)-O(11) bond length is 1.94 Å. The Fe(7)-O(3) bond length is 1.99 Å. The Fe(7)-O(5) bond length is 1.97 Å. The Fe(7)-O(8) bond length is 1.93 Å. The Fe(7)-O(9) bond length is 1.97 Å. The Fe(7)-F(2) bond length is 2.14 Å. In the eighth Fe site, Fe(8) is bonded to one O(10), one O(13), one O(4), one O(6), one O(7), and one F(1) atom to form FeO5F octahedra that share corners with four equivalent Fe(3)O5F octahedra, corners with four equivalent Fe(2)O6 octahedra, corners with two equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Fe(6)O5F octahedra, and  an edgeedge with one Fe(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. The Fe(8)-O(10) bond length is 1.97 Å. The Fe(8)-O(13) bond length is 2.06 Å. The Fe(8)-O(4) bond length is 2.06 Å. The Fe(8)-O(6) bond length is 1.97 Å. The Fe(8)-O(7) bond length is 1.93 Å. The Fe(8)-F(1) bond length is 2.06 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Fe(1), one Fe(2), and one Fe(5) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Fe(3), one Fe(4), and one Fe(6) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Fe(1), one Fe(4), and one Fe(7) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Fe(2), one Fe(3), and one Fe(8) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(5), and one Fe(7) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Fe(2), one Fe(5), and one Fe(8) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Fe(3), one Fe(6), and one Fe(8) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Fe(4), one Fe(6), and one Fe(7) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(5), and one Fe(7) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Li(1), one Fe(2), one Fe(5), and one Fe(8) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Fe(4), one Fe(6), and one Fe(7) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(1), one Fe(1), one Fe(2), and one Fe(5) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Fe(2), one Fe(3), and one Fe(8) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Fe(3), one Fe(4), and one Fe(6) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Fe(3), one Fe(6), and one Fe(8) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(4), and one Fe(7) atom.