Li3Fe3(OF)4 crystallizes in the monoclinic Pm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form distorted LiF6 octahedra that share corners with four equivalent Fe(2)O3F3 octahedra, corners with three equivalent Li(2)OF3 trigonal pyramids, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Fe(3)O3F3 octahedra, and  an edgeedge with one Li(2)OF3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 48-54°. In the second Li site, Li(2) is bonded to one O(1), one F(3), and two equivalent F(1) atoms to form distorted LiOF3 trigonal pyramids that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Fe(3)O3F3 octahedra, corners with three equivalent Li(1)F6 octahedra, corners with two equivalent Li(2)OF3 trigonal pyramids,  an edgeedge with one Li(1)F6 octahedra, and edges with two equivalent Fe(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 19-76°. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(2), one O(3), and two equivalent O(4) atoms. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form FeO6 octahedra that share corners with four equivalent Fe(3)O3F3 octahedra,  a cornercorner with one Li(2)OF3 trigonal pyramid, edges with two equivalent Fe(2)O3F3 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. In the second Fe site, Fe(2) is bonded to one O(2), two equivalent O(4), one F(4), and two equivalent F(2) atoms to form FeO3F3 octahedra that share corners with four equivalent Li(1)F6 octahedra, edges with two equivalent Fe(2)O3F3 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. In the third Fe site, Fe(3) is bonded to one O(3), two equivalent O(1), one F(1), and two equivalent F(3) atoms to form distorted FeO3F3 octahedra that share corners with four equivalent Fe(1)O6 octahedra, corners with two equivalent Li(2)OF3 trigonal pyramids, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Fe(3)O3F3 octahedra, and edges with two equivalent Li(2)OF3 trigonal pyramids. The corner-sharing octahedral tilt angles range from 48-53°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Fe(1), and two equivalent Fe(3) atoms to form OLiFe3 trigonal pyramids that share  a cornercorner with one O(4)Li2Fe3 square pyramid, corners with two equivalent O(2)LiFe3 tetrahedra, corners with three equivalent F(3)Li2Fe2 tetrahedra, corners with two equivalent O(1)LiFe3 trigonal pyramids, edges with two equivalent F(1)Li4Fe square pyramids, and  an edgeedge with one F(3)Li2Fe2 tetrahedra. In the second O site, O(2) is bonded to one Li(3), one Fe(2), and two equivalent Fe(1) atoms to form distorted OLiFe3 tetrahedra that share corners with two equivalent O(4)Li2Fe3 square pyramids, corners with two equivalent O(2)LiFe3 tetrahedra, corners with two equivalent O(1)LiFe3 trigonal pyramids, and edges with two equivalent O(4)Li2Fe3 square pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(3), one Fe(3), and two equivalent Fe(1) atoms. In the fourth O site, O(4) is bonded to two equivalent Li(3), one Fe(1), and two equivalent Fe(2) atoms to form OLi2Fe3 square pyramids that share corners with two equivalent O(2)LiFe3 tetrahedra,  a cornercorner with one O(1)LiFe3 trigonal pyramid, edges with two equivalent O(4)Li2Fe3 square pyramids, and edges with two equivalent O(2)LiFe3 tetrahedra. There are four inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one Fe(3) atom to form distorted FLi4Fe square pyramids that share corners with two equivalent F(3)Li2Fe2 tetrahedra, edges with two equivalent F(1)Li4Fe square pyramids, edges with two equivalent F(3)Li2Fe2 tetrahedra, and edges with two equivalent O(1)LiFe3 trigonal pyramids. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Fe(2) atoms. In the third F site, F(3) is bonded to one Li(1), one Li(2), and two equivalent Fe(3) atoms to form distorted FLi2Fe2 tetrahedra that share corners with two equivalent F(1)Li4Fe square pyramids, corners with two equivalent F(3)Li2Fe2 tetrahedra, corners with three equivalent O(1)LiFe3 trigonal pyramids, edges with two equivalent F(1)Li4Fe square pyramids, and  an edgeedge with one O(1)LiFe3 trigonal pyramid. In the fourth F site, F(4) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Fe(2) atom.
Li3Fe3(OF)4 crystallizes in the monoclinic Pm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form distorted LiF6 octahedra that share corners with four equivalent Fe(2)O3F3 octahedra, corners with three equivalent Li(2)OF3 trigonal pyramids, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Fe(3)O3F3 octahedra, and  an edgeedge with one Li(2)OF3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 48-54°. The Li(1)-F(2) bond length is 2.04 Å. The Li(1)-F(3) bond length is 2.23 Å. Both Li(1)-F(1) bond lengths are 2.30 Å. Both Li(1)-F(4) bond lengths are 1.92 Å. In the second Li site, Li(2) is bonded to one O(1), one F(3), and two equivalent F(1) atoms to form distorted LiOF3 trigonal pyramids that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Fe(3)O3F3 octahedra, corners with three equivalent Li(1)F6 octahedra, corners with two equivalent Li(2)OF3 trigonal pyramids,  an edgeedge with one Li(1)F6 octahedra, and edges with two equivalent Fe(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 19-76°. The Li(2)-O(1) bond length is 2.06 Å. The Li(2)-F(3) bond length is 1.88 Å. Both Li(2)-F(1) bond lengths are 1.91 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(2), one O(3), and two equivalent O(4) atoms. The Li(3)-O(2) bond length is 1.86 Å. The Li(3)-O(3) bond length is 2.09 Å. Both Li(3)-O(4) bond lengths are 2.02 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form FeO6 octahedra that share corners with four equivalent Fe(3)O3F3 octahedra,  a cornercorner with one Li(2)OF3 trigonal pyramid, edges with two equivalent Fe(2)O3F3 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. The Fe(1)-O(1) bond length is 2.04 Å. The Fe(1)-O(4) bond length is 2.10 Å. Both Fe(1)-O(2) bond lengths are 2.03 Å. Both Fe(1)-O(3) bond lengths are 2.06 Å. In the second Fe site, Fe(2) is bonded to one O(2), two equivalent O(4), one F(4), and two equivalent F(2) atoms to form FeO3F3 octahedra that share corners with four equivalent Li(1)F6 octahedra, edges with two equivalent Fe(2)O3F3 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. The Fe(2)-O(2) bond length is 1.99 Å. Both Fe(2)-O(4) bond lengths are 2.02 Å. The Fe(2)-F(4) bond length is 1.98 Å. Both Fe(2)-F(2) bond lengths are 2.07 Å. In the third Fe site, Fe(3) is bonded to one O(3), two equivalent O(1), one F(1), and two equivalent F(3) atoms to form distorted FeO3F3 octahedra that share corners with four equivalent Fe(1)O6 octahedra, corners with two equivalent Li(2)OF3 trigonal pyramids, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Fe(3)O3F3 octahedra, and edges with two equivalent Li(2)OF3 trigonal pyramids. The corner-sharing octahedral tilt angles range from 48-53°. The Fe(3)-O(3) bond length is 1.91 Å. Both Fe(3)-O(1) bond lengths are 1.96 Å. The Fe(3)-F(1) bond length is 2.12 Å. Both Fe(3)-F(3) bond lengths are 2.13 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Fe(1), and two equivalent Fe(3) atoms to form OLiFe3 trigonal pyramids that share  a cornercorner with one O(4)Li2Fe3 square pyramid, corners with two equivalent O(2)LiFe3 tetrahedra, corners with three equivalent F(3)Li2Fe2 tetrahedra, corners with two equivalent O(1)LiFe3 trigonal pyramids, edges with two equivalent F(1)Li4Fe square pyramids, and  an edgeedge with one F(3)Li2Fe2 tetrahedra. In the second O site, O(2) is bonded to one Li(3), one Fe(2), and two equivalent Fe(1) atoms to form distorted OLiFe3 tetrahedra that share corners with two equivalent O(4)Li2Fe3 square pyramids, corners with two equivalent O(2)LiFe3 tetrahedra, corners with two equivalent O(1)LiFe3 trigonal pyramids, and edges with two equivalent O(4)Li2Fe3 square pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(3), one Fe(3), and two equivalent Fe(1) atoms. In the fourth O site, O(4) is bonded to two equivalent Li(3), one Fe(1), and two equivalent Fe(2) atoms to form OLi2Fe3 square pyramids that share corners with two equivalent O(2)LiFe3 tetrahedra,  a cornercorner with one O(1)LiFe3 trigonal pyramid, edges with two equivalent O(4)Li2Fe3 square pyramids, and edges with two equivalent O(2)LiFe3 tetrahedra. There are four inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one Fe(3) atom to form distorted FLi4Fe square pyramids that share corners with two equivalent F(3)Li2Fe2 tetrahedra, edges with two equivalent F(1)Li4Fe square pyramids, edges with two equivalent F(3)Li2Fe2 tetrahedra, and edges with two equivalent O(1)LiFe3 trigonal pyramids. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Fe(2) atoms. In the third F site, F(3) is bonded to one Li(1), one Li(2), and two equivalent Fe(3) atoms to form distorted FLi2Fe2 tetrahedra that share corners with two equivalent F(1)Li4Fe square pyramids, corners with two equivalent F(3)Li2Fe2 tetrahedra, corners with three equivalent O(1)LiFe3 trigonal pyramids, edges with two equivalent F(1)Li4Fe square pyramids, and  an edgeedge with one O(1)LiFe3 trigonal pyramid. In the fourth F site, F(4) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Fe(2) atom.