Li3Fe8O3F13 crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one F(2), two equivalent F(1), and two equivalent F(9) atoms to form LiOF5 octahedra that share  an edgeedge with one Fe(3)OF5 octahedra,  an edgeedge with one Fe(5)OF5 octahedra, edges with two equivalent Fe(4)O2F4 octahedra, edges with two equivalent Fe(2)OF5 octahedra, and edges with four equivalent Fe(1)O3F3 octahedra. In the second Li site, Li(2) is bonded to one F(5), one F(8), and two equivalent F(3) atoms to form LiF4 tetrahedra that share  a cornercorner with one Fe(5)OF5 octahedra, corners with two equivalent Fe(4)O2F4 octahedra, corners with two equivalent Fe(3)OF5 octahedra, and corners with four equivalent Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 52-59°. In the third Li site, Li(3) is bonded to one F(4), one F(6), and two equivalent F(7) atoms to form LiF4 tetrahedra that share  a cornercorner with one Fe(3)OF5 octahedra, corners with two equivalent Fe(2)OF5 octahedra, corners with two equivalent Fe(5)OF5 octahedra, and corners with four equivalent Fe(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 53-64°. There are five inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one F(1), one F(2), and one F(9) atom to form FeO3F3 octahedra that share corners with three equivalent Fe(4)O2F4 octahedra, corners with three equivalent Fe(2)OF5 octahedra,  an edgeedge with one Fe(4)O2F4 octahedra,  an edgeedge with one Fe(2)OF5 octahedra,  an edgeedge with one Fe(3)OF5 octahedra,  an edgeedge with one Fe(5)OF5 octahedra, edges with two equivalent Li(1)OF5 octahedra, and edges with two equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 7-12°. 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(5) atom to form FeOF5 octahedra that share corners with three equivalent Fe(1)O3F3 octahedra,  a cornercorner with one Li(3)F4 tetrahedra, corners with two equivalent Li(2)F4 tetrahedra,  an edgeedge with one Li(1)OF5 octahedra,  an edgeedge with one Fe(1)O3F3 octahedra, edges with two equivalent Fe(2)OF5 octahedra, and edges with two equivalent Fe(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 7-12°. In the third Fe site, Fe(3) is bonded to one O(1), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form FeOF5 octahedra that share  a cornercorner with one Li(3)F4 tetrahedra, corners with two equivalent Li(2)F4 tetrahedra,  an edgeedge with one Li(1)OF5 octahedra, edges with two equivalent Fe(1)O3F3 octahedra, and edges with four equivalent Fe(2)OF5 octahedra. In the fourth Fe site, Fe(4) is bonded to one O(2), one O(3), one F(6), one F(7), one F(8), and one F(9) atom to form FeO2F4 octahedra that share corners with three equivalent Fe(1)O3F3 octahedra,  a cornercorner with one Li(2)F4 tetrahedra, corners with two equivalent Li(3)F4 tetrahedra,  an edgeedge with one Li(1)OF5 octahedra,  an edgeedge with one Fe(1)O3F3 octahedra, edges with two equivalent Fe(4)O2F4 octahedra, and edges with two equivalent Fe(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. In the fifth Fe site, Fe(5) is bonded to one O(3), one F(8), two equivalent F(7), and two equivalent F(9) atoms to form FeOF5 octahedra that share  a cornercorner with one Li(2)F4 tetrahedra, corners with two equivalent Li(3)F4 tetrahedra,  an edgeedge with one Li(1)OF5 octahedra, edges with two equivalent Fe(1)O3F3 octahedra, and edges with four equivalent Fe(4)O2F4 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Fe(3), two equivalent Fe(1), and two equivalent Fe(2) atoms to form OFe5 square pyramids that share corners with two equivalent O(3)Fe5 square pyramids,  an edgeedge with one O(2)LiFe4 square pyramid, and edges with two equivalent F(2)LiFe4 square pyramids. In the second O site, O(2) is bonded to one Li(1), two equivalent Fe(1), and two equivalent Fe(4) atoms to form OLiFe4 square pyramids that share corners with three equivalent F(2)LiFe4 square pyramids,  an edgeedge with one O(1)Fe5 square pyramid, and edges with two equivalent O(3)Fe5 square pyramids. In the third O site, O(3) is bonded to one Fe(5), two equivalent Fe(1), and two equivalent Fe(4) atoms to form OFe5 square pyramids that share corners with two equivalent O(1)Fe5 square pyramids,  an edgeedge with one F(2)LiFe4 square pyramid, and edges with two equivalent O(2)LiFe4 square pyramids. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(1), one Fe(2), and one Fe(3) atom. In the second F site, F(2) is bonded to one Li(1), two equivalent Fe(1), and two equivalent Fe(2) atoms to form FLiFe4 square pyramids that share corners with three equivalent O(2)LiFe4 square pyramids,  an edgeedge with one O(3)Fe5 square pyramid, and edges with two equivalent O(1)Fe5 square pyramids. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(2), one Fe(2), and one Fe(3) atom. In the fourth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Fe(3), and two equivalent Fe(2) atoms. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Fe(2) atoms. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(3) and two equivalent Fe(4) atoms. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(3), one Fe(4), and one Fe(5) atom. In the eighth F site, F(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Fe(5), and two equivalent Fe(4) atoms. In the ninth F site, F(9) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(1), one Fe(4), and one Fe(5) atom.
Li3Fe8O3F13 crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one F(2), two equivalent F(1), and two equivalent F(9) atoms to form LiOF5 octahedra that share  an edgeedge with one Fe(3)OF5 octahedra,  an edgeedge with one Fe(5)OF5 octahedra, edges with two equivalent Fe(4)O2F4 octahedra, edges with two equivalent Fe(2)OF5 octahedra, and edges with four equivalent Fe(1)O3F3 octahedra. The Li(1)-O(2) bond length is 1.98 Å. The Li(1)-F(2) bond length is 2.11 Å. Both Li(1)-F(1) bond lengths are 2.14 Å. Both Li(1)-F(9) bond lengths are 1.99 Å. In the second Li site, Li(2) is bonded to one F(5), one F(8), and two equivalent F(3) atoms to form LiF4 tetrahedra that share  a cornercorner with one Fe(5)OF5 octahedra, corners with two equivalent Fe(4)O2F4 octahedra, corners with two equivalent Fe(3)OF5 octahedra, and corners with four equivalent Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 52-59°. The Li(2)-F(5) bond length is 1.97 Å. The Li(2)-F(8) bond length is 1.93 Å. Both Li(2)-F(3) bond lengths are 1.94 Å. In the third Li site, Li(3) is bonded to one F(4), one F(6), and two equivalent F(7) atoms to form LiF4 tetrahedra that share  a cornercorner with one Fe(3)OF5 octahedra, corners with two equivalent Fe(2)OF5 octahedra, corners with two equivalent Fe(5)OF5 octahedra, and corners with four equivalent Fe(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 53-64°. The Li(3)-F(4) bond length is 1.99 Å. The Li(3)-F(6) bond length is 1.96 Å. Both Li(3)-F(7) bond lengths are 1.88 Å. There are five inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one F(1), one F(2), and one F(9) atom to form FeO3F3 octahedra that share corners with three equivalent Fe(4)O2F4 octahedra, corners with three equivalent Fe(2)OF5 octahedra,  an edgeedge with one Fe(4)O2F4 octahedra,  an edgeedge with one Fe(2)OF5 octahedra,  an edgeedge with one Fe(3)OF5 octahedra,  an edgeedge with one Fe(5)OF5 octahedra, edges with two equivalent Li(1)OF5 octahedra, and edges with two equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 7-12°. The Fe(1)-O(1) bond length is 2.13 Å. The Fe(1)-O(2) bond length is 2.16 Å. The Fe(1)-O(3) bond length is 2.06 Å. The Fe(1)-F(1) bond length is 2.35 Å. The Fe(1)-F(2) bond length is 2.33 Å. The Fe(1)-F(9) bond length is 2.23 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(5) atom to form FeOF5 octahedra that share corners with three equivalent Fe(1)O3F3 octahedra,  a cornercorner with one Li(3)F4 tetrahedra, corners with two equivalent Li(2)F4 tetrahedra,  an edgeedge with one Li(1)OF5 octahedra,  an edgeedge with one Fe(1)O3F3 octahedra, edges with two equivalent Fe(2)OF5 octahedra, and edges with two equivalent Fe(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 7-12°. The Fe(2)-O(1) bond length is 2.22 Å. The Fe(2)-F(1) bond length is 2.08 Å. The Fe(2)-F(2) bond length is 2.20 Å. The Fe(2)-F(3) bond length is 2.07 Å. The Fe(2)-F(4) bond length is 2.18 Å. The Fe(2)-F(5) bond length is 2.08 Å. In the third Fe site, Fe(3) is bonded to one O(1), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form FeOF5 octahedra that share  a cornercorner with one Li(3)F4 tetrahedra, corners with two equivalent Li(2)F4 tetrahedra,  an edgeedge with one Li(1)OF5 octahedra, edges with two equivalent Fe(1)O3F3 octahedra, and edges with four equivalent Fe(2)OF5 octahedra. The Fe(3)-O(1) bond length is 2.14 Å. The Fe(3)-F(4) bond length is 2.13 Å. Both Fe(3)-F(1) bond lengths are 2.14 Å. Both Fe(3)-F(3) bond lengths are 2.09 Å. In the fourth Fe site, Fe(4) is bonded to one O(2), one O(3), one F(6), one F(7), one F(8), and one F(9) atom to form FeO2F4 octahedra that share corners with three equivalent Fe(1)O3F3 octahedra,  a cornercorner with one Li(2)F4 tetrahedra, corners with two equivalent Li(3)F4 tetrahedra,  an edgeedge with one Li(1)OF5 octahedra,  an edgeedge with one Fe(1)O3F3 octahedra, edges with two equivalent Fe(4)O2F4 octahedra, and edges with two equivalent Fe(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. The Fe(4)-O(2) bond length is 2.05 Å. The Fe(4)-O(3) bond length is 2.27 Å. The Fe(4)-F(6) bond length is 2.11 Å. The Fe(4)-F(7) bond length is 2.14 Å. The Fe(4)-F(8) bond length is 2.18 Å. The Fe(4)-F(9) bond length is 2.24 Å. In the fifth Fe site, Fe(5) is bonded to one O(3), one F(8), two equivalent F(7), and two equivalent F(9) atoms to form FeOF5 octahedra that share  a cornercorner with one Li(2)F4 tetrahedra, corners with two equivalent Li(3)F4 tetrahedra,  an edgeedge with one Li(1)OF5 octahedra, edges with two equivalent Fe(1)O3F3 octahedra, and edges with four equivalent Fe(4)O2F4 octahedra. The Fe(5)-O(3) bond length is 2.15 Å. The Fe(5)-F(8) bond length is 2.17 Å. Both Fe(5)-F(7) bond lengths are 2.07 Å. Both Fe(5)-F(9) bond lengths are 2.13 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Fe(3), two equivalent Fe(1), and two equivalent Fe(2) atoms to form OFe5 square pyramids that share corners with two equivalent O(3)Fe5 square pyramids,  an edgeedge with one O(2)LiFe4 square pyramid, and edges with two equivalent F(2)LiFe4 square pyramids. In the second O site, O(2) is bonded to one Li(1), two equivalent Fe(1), and two equivalent Fe(4) atoms to form OLiFe4 square pyramids that share corners with three equivalent F(2)LiFe4 square pyramids,  an edgeedge with one O(1)Fe5 square pyramid, and edges with two equivalent O(3)Fe5 square pyramids. In the third O site, O(3) is bonded to one Fe(5), two equivalent Fe(1), and two equivalent Fe(4) atoms to form OFe5 square pyramids that share corners with two equivalent O(1)Fe5 square pyramids,  an edgeedge with one F(2)LiFe4 square pyramid, and edges with two equivalent O(2)LiFe4 square pyramids. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(1), one Fe(2), and one Fe(3) atom. In the second F site, F(2) is bonded to one Li(1), two equivalent Fe(1), and two equivalent Fe(2) atoms to form FLiFe4 square pyramids that share corners with three equivalent O(2)LiFe4 square pyramids,  an edgeedge with one O(3)Fe5 square pyramid, and edges with two equivalent O(1)Fe5 square pyramids. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(2), one Fe(2), and one Fe(3) atom. In the fourth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Fe(3), and two equivalent Fe(2) atoms. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Fe(2) atoms. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(3) and two equivalent Fe(4) atoms. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(3), one Fe(4), and one Fe(5) atom. In the eighth F site, F(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Fe(5), and two equivalent Fe(4) atoms. In the ninth F site, F(9) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(1), one Fe(4), and one Fe(5) atom.