LiFe6(OF2)4 crystallizes in the triclinic P1 space group. Li(1) is bonded to one Fe(3), one Fe(4), one Fe(6), one O(1), one O(3), one F(3), and one F(6) atom to form distorted LiFe3O2F2 tetrahedra that share corners with two equivalent Fe(5)O2F4 octahedra and corners with two equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 4-46°. There are six inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(2), one O(3), one O(4), one F(1), one F(5), and one F(6) atom to form FeO3F3 octahedra that share corners with three equivalent Fe(2)OF5 octahedra, corners with two equivalent Li(1)Fe3O2F2 tetrahedra, and  an edgeedge with one Fe(5)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. In the second Fe site, Fe(2) is bonded to one O(2), one F(1), one F(4), one F(5), one F(7), and one F(8) atom to form FeOF5 octahedra that share corners with three equivalent Fe(5)O2F4 octahedra and corners with three equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 42-57°. In the third Fe site, Fe(3) is bonded in a 7-coordinate geometry to one Li(1), one O(1), one F(2), one F(3), one F(5), one F(6), and one F(7) atom. In the fourth Fe site, Fe(4) is bonded in a 7-coordinate geometry to one Li(1), one O(1), one O(3), one O(4), one F(2), one F(4), and one F(7) atom. In the fifth Fe site, Fe(5) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(8) atom to form FeO2F4 octahedra that share corners with three equivalent Fe(2)OF5 octahedra, corners with two equivalent Li(1)Fe3O2F2 tetrahedra, and  an edgeedge with one Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 42-57°. In the sixth Fe site, Fe(6) is bonded in a 7-coordinate geometry to one Li(1), one O(3), one O(4), one F(3), one F(4), one F(6), and one F(8) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Fe(3), one Fe(4), and one Fe(5) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(5) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(1), one Fe(4), and one Fe(6) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Fe(1), one Fe(4), and one Fe(6) atom. There are eight 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(5) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Fe(3), one Fe(4), and one Fe(5) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one Fe(3), one Fe(5), and one Fe(6) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Fe(2), one Fe(4), and one Fe(6) atom. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Fe(1), one Fe(2), and one Fe(3) atom. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to one Li(1), one Fe(1), one Fe(3), and one Fe(6) atom. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Fe(2), one Fe(3), and one Fe(4) atom. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one Fe(2), one Fe(5), and one Fe(6) atom.
LiFe6(OF2)4 crystallizes in the triclinic P1 space group. Li(1) is bonded to one Fe(3), one Fe(4), one Fe(6), one O(1), one O(3), one F(3), and one F(6) atom to form distorted LiFe3O2F2 tetrahedra that share corners with two equivalent Fe(5)O2F4 octahedra and corners with two equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 4-46°. The Li(1)-Fe(3) bond length is 2.20 Å. The Li(1)-Fe(4) bond length is 2.30 Å. The Li(1)-Fe(6) bond length is 2.24 Å. The Li(1)-O(1) bond length is 1.80 Å. The Li(1)-O(3) bond length is 1.77 Å. The Li(1)-F(3) bond length is 1.89 Å. The Li(1)-F(6) bond length is 1.83 Å. There are six inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(2), one O(3), one O(4), one F(1), one F(5), and one F(6) atom to form FeO3F3 octahedra that share corners with three equivalent Fe(2)OF5 octahedra, corners with two equivalent Li(1)Fe3O2F2 tetrahedra, and  an edgeedge with one Fe(5)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. The Fe(1)-O(2) bond length is 1.94 Å. The Fe(1)-O(3) bond length is 1.95 Å. The Fe(1)-O(4) bond length is 1.93 Å. The Fe(1)-F(1) bond length is 2.11 Å. The Fe(1)-F(5) bond length is 2.15 Å. The Fe(1)-F(6) bond length is 2.19 Å. In the second Fe site, Fe(2) is bonded to one O(2), one F(1), one F(4), one F(5), one F(7), and one F(8) atom to form FeOF5 octahedra that share corners with three equivalent Fe(5)O2F4 octahedra and corners with three equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 42-57°. The Fe(2)-O(2) bond length is 1.99 Å. The Fe(2)-F(1) bond length is 2.19 Å. The Fe(2)-F(4) bond length is 2.06 Å. The Fe(2)-F(5) bond length is 2.06 Å. The Fe(2)-F(7) bond length is 2.07 Å. The Fe(2)-F(8) bond length is 2.08 Å. In the third Fe site, Fe(3) is bonded in a 7-coordinate geometry to one Li(1), one O(1), one F(2), one F(3), one F(5), one F(6), and one F(7) atom. The Fe(3)-O(1) bond length is 2.12 Å. The Fe(3)-F(2) bond length is 2.06 Å. The Fe(3)-F(3) bond length is 2.24 Å. The Fe(3)-F(5) bond length is 2.04 Å. The Fe(3)-F(6) bond length is 2.21 Å. The Fe(3)-F(7) bond length is 2.09 Å. In the fourth Fe site, Fe(4) is bonded in a 7-coordinate geometry to one Li(1), one O(1), one O(3), one O(4), one F(2), one F(4), and one F(7) atom. The Fe(4)-O(1) bond length is 2.22 Å. The Fe(4)-O(3) bond length is 2.05 Å. The Fe(4)-O(4) bond length is 1.90 Å. The Fe(4)-F(2) bond length is 2.10 Å. The Fe(4)-F(4) bond length is 2.03 Å. The Fe(4)-F(7) bond length is 2.04 Å. In the fifth Fe site, Fe(5) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(8) atom to form FeO2F4 octahedra that share corners with three equivalent Fe(2)OF5 octahedra, corners with two equivalent Li(1)Fe3O2F2 tetrahedra, and  an edgeedge with one Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 42-57°. The Fe(5)-O(1) bond length is 1.90 Å. The Fe(5)-O(2) bond length is 1.91 Å. The Fe(5)-F(1) bond length is 2.18 Å. The Fe(5)-F(2) bond length is 2.24 Å. The Fe(5)-F(3) bond length is 2.08 Å. The Fe(5)-F(8) bond length is 2.06 Å. In the sixth Fe site, Fe(6) is bonded in a 7-coordinate geometry to one Li(1), one O(3), one O(4), one F(3), one F(4), one F(6), and one F(8) atom. The Fe(6)-O(3) bond length is 2.24 Å. The Fe(6)-O(4) bond length is 1.98 Å. The Fe(6)-F(3) bond length is 2.31 Å. The Fe(6)-F(4) bond length is 2.07 Å. The Fe(6)-F(6) bond length is 2.20 Å. The Fe(6)-F(8) bond length is 2.09 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Fe(3), one Fe(4), and one Fe(5) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(5) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(1), one Fe(4), and one Fe(6) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Fe(1), one Fe(4), and one Fe(6) atom. There are eight 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(5) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Fe(3), one Fe(4), and one Fe(5) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one Fe(3), one Fe(5), and one Fe(6) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Fe(2), one Fe(4), and one Fe(6) atom. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Fe(1), one Fe(2), and one Fe(3) atom. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to one Li(1), one Fe(1), one Fe(3), and one Fe(6) atom. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Fe(2), one Fe(3), and one Fe(4) atom. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one Fe(2), one Fe(5), and one Fe(6) atom.