Li4Mn3O5F3 crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), two equivalent O(4), one F(2), and two equivalent F(3) atoms to form LiO3F3 octahedra that share  a cornercorner with one Mn(2)O5F octahedra, corners with two equivalent Mn(1)O3F3 octahedra, corners with two equivalent Mn(3)O6 octahedra,  an edgeedge with one Mn(1)O3F3 octahedra,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent Mn(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 9-18°. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(5), one F(1), and one F(3) atom. In the third Li site, Li(3) is bonded to one O(3), one O(5), two equivalent O(2), and two equivalent F(1) atoms to form distorted LiO4F2 octahedra that share  a cornercorner with one Mn(1)O3F3 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(2)O5F octahedra,  an edgeedge with one Mn(2)O5F octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent Mn(1)O3F3 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. In the fourth Li site, Li(4) is bonded to one O(2), one O(4), two equivalent O(3), and two equivalent F(2) atoms to form distorted LiO4F2 octahedra that share  a cornercorner with one Mn(2)O5F octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(1)O3F3 octahedra,  an edgeedge with one Mn(1)O3F3 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent Mn(2)O5F octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-14°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(5), two equivalent O(3), one F(1), and two equivalent F(3) atoms to form distorted MnO3F3 octahedra that share  a cornercorner with one Li(3)O4F2 octahedra, corners with two equivalent Li(1)O3F3 octahedra, corners with two equivalent Li(4)O4F2 octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(4)O4F2 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Mn(1)O3F3 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-13°. In the second Mn site, Mn(2) is bonded to one O(4), two equivalent O(1), two equivalent O(2), and one F(2) atom to form distorted MnO5F octahedra that share  a cornercorner with one Li(1)O3F3 octahedra,  a cornercorner with one Li(4)O4F2 octahedra, corners with two equivalent Li(3)O4F2 octahedra,  an edgeedge with one Li(3)O4F2 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent Mn(2)O5F octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-18°. In the third Mn site, Mn(3) is bonded to one O(2), one O(3), two equivalent O(4), and two equivalent O(5) atoms to form MnO6 octahedra that share  a cornercorner with one Li(3)O4F2 octahedra,  a cornercorner with one Li(4)O4F2 octahedra, corners with two equivalent Li(1)O3F3 octahedra,  an edgeedge with one Li(1)O3F3 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent Mn(1)O3F3 octahedra, edges with two equivalent Mn(2)O5F octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-14°. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), and two equivalent Mn(2) atoms to form OLi3Mn2 square pyramids that share corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(5)Li3Mn3 octahedra, corners with two equivalent F(1)Li3Mn trigonal pyramids,  an edgeedge with one O(2)Li3Mn3 octahedra,  an edgeedge with one O(5)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(1)Li3Mn2 square pyramids, and edges with two equivalent F(3)Li3Mn2 square pyramids. The corner-sharing octahedral tilt angles range from 10-14°. In the second O site, O(2) is bonded to one Li(4), two equivalent Li(3), one Mn(3), and two equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(4)Li3Mn3 octahedra, corners with two equivalent O(1)Li3Mn2 square pyramids, corners with two equivalent F(1)Li3Mn trigonal pyramids, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra,  an edgeedge with one O(1)Li3Mn2 square pyramid, and  an edgeedge with one F(1)Li3Mn trigonal pyramid. The corner-sharing octahedral tilt angles range from 2-3°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(4), one Mn(3), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra,  a cornercorner with one O(5)Li3Mn3 octahedra, corners with two equivalent F(3)Li3Mn2 square pyramids, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra,  an edgeedge with one F(3)Li3Mn2 square pyramid, and edges with two equivalent F(1)Li3Mn trigonal pyramids. The corner-sharing octahedral tilt angles range from 0-3°. In the fourth O site, O(4) is bonded to one Li(4), two equivalent Li(1), one Mn(2), and two equivalent Mn(3) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra, corners with two equivalent O(5)Li3Mn3 octahedra, corners with two equivalent F(3)Li3Mn2 square pyramids,  an edgeedge with one O(5)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra,  an edgeedge with one F(3)Li3Mn2 square pyramid, and edges with two equivalent O(1)Li3Mn2 square pyramids. The corner-sharing octahedral tilt angles are 2°. In the fifth O site, O(5) is bonded to one Li(3), two equivalent Li(2), one Mn(1), and two equivalent Mn(3) atoms to form distorted OLi3Mn3 octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra, corners with two equivalent O(4)Li3Mn3 octahedra, corners with two equivalent O(1)Li3Mn2 square pyramids,  a cornercorner with one F(1)Li3Mn trigonal pyramid,  an edgeedge with one O(4)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra,  an edgeedge with one O(1)Li3Mn2 square pyramid, edges with two equivalent F(3)Li3Mn2 square pyramids, and edges with two equivalent F(1)Li3Mn trigonal pyramids. The corner-sharing octahedral tilt angles range from 0-2°. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), two equivalent Li(3), and one Mn(1) atom to form distorted FLi3Mn trigonal pyramids that share  a cornercorner with one O(5)Li3Mn3 octahedra, corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(1)Li3Mn2 square pyramids, corners with three equivalent F(3)Li3Mn2 square pyramids, corners with two equivalent F(1)Li3Mn trigonal pyramids,  an edgeedge with one O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, and edges with two equivalent O(5)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 8-20°. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Li(4), and one Mn(2) atom. In the third F site, F(3) is bonded to one Li(2), two equivalent Li(1), and two equivalent Mn(1) atoms to form FLi3Mn2 square pyramids that share corners with two equivalent O(3)Li3Mn3 octahedra, corners with two equivalent O(4)Li3Mn3 octahedra, corners with three equivalent F(1)Li3Mn trigonal pyramids,  an edgeedge with one O(3)Li3Mn3 octahedra,  an edgeedge with one O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(1)Li3Mn2 square pyramids, and edges with two equivalent F(3)Li3Mn2 square pyramids. The corner-sharing octahedral tilt angles range from 9-15°.
Li4Mn3O5F3 crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), two equivalent O(4), one F(2), and two equivalent F(3) atoms to form LiO3F3 octahedra that share  a cornercorner with one Mn(2)O5F octahedra, corners with two equivalent Mn(1)O3F3 octahedra, corners with two equivalent Mn(3)O6 octahedra,  an edgeedge with one Mn(1)O3F3 octahedra,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent Mn(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 9-18°. The Li(1)-O(1) bond length is 2.17 Å. Both Li(1)-O(4) bond lengths are 2.27 Å. The Li(1)-F(2) bond length is 1.95 Å. Both Li(1)-F(3) bond lengths are 2.07 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(5), one F(1), and one F(3) atom. Both Li(2)-O(1) bond lengths are 2.07 Å. Both Li(2)-O(5) bond lengths are 2.51 Å. The Li(2)-F(1) bond length is 1.90 Å. The Li(2)-F(3) bond length is 2.19 Å. In the third Li site, Li(3) is bonded to one O(3), one O(5), two equivalent O(2), and two equivalent F(1) atoms to form distorted LiO4F2 octahedra that share  a cornercorner with one Mn(1)O3F3 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(2)O5F octahedra,  an edgeedge with one Mn(2)O5F octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent Mn(1)O3F3 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. The Li(3)-O(3) bond length is 2.35 Å. The Li(3)-O(5) bond length is 2.04 Å. Both Li(3)-O(2) bond lengths are 2.24 Å. Both Li(3)-F(1) bond lengths are 1.95 Å. In the fourth Li site, Li(4) is bonded to one O(2), one O(4), two equivalent O(3), and two equivalent F(2) atoms to form distorted LiO4F2 octahedra that share  a cornercorner with one Mn(2)O5F octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(1)O3F3 octahedra,  an edgeedge with one Mn(1)O3F3 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent Mn(2)O5F octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-14°. The Li(4)-O(2) bond length is 2.33 Å. The Li(4)-O(4) bond length is 2.04 Å. Both Li(4)-O(3) bond lengths are 2.16 Å. Both Li(4)-F(2) bond lengths are 1.96 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(5), two equivalent O(3), one F(1), and two equivalent F(3) atoms to form distorted MnO3F3 octahedra that share  a cornercorner with one Li(3)O4F2 octahedra, corners with two equivalent Li(1)O3F3 octahedra, corners with two equivalent Li(4)O4F2 octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(4)O4F2 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Mn(1)O3F3 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-13°. The Mn(1)-O(5) bond length is 2.27 Å. Both Mn(1)-O(3) bond lengths are 2.12 Å. The Mn(1)-F(1) bond length is 2.10 Å. Both Mn(1)-F(3) bond lengths are 2.19 Å. In the second Mn site, Mn(2) is bonded to one O(4), two equivalent O(1), two equivalent O(2), and one F(2) atom to form distorted MnO5F octahedra that share  a cornercorner with one Li(1)O3F3 octahedra,  a cornercorner with one Li(4)O4F2 octahedra, corners with two equivalent Li(3)O4F2 octahedra,  an edgeedge with one Li(3)O4F2 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent Mn(2)O5F octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-18°. The Mn(2)-O(4) bond length is 2.25 Å. Both Mn(2)-O(1) bond lengths are 1.95 Å. Both Mn(2)-O(2) bond lengths are 2.03 Å. The Mn(2)-F(2) bond length is 2.15 Å. In the third Mn site, Mn(3) is bonded to one O(2), one O(3), two equivalent O(4), and two equivalent O(5) atoms to form MnO6 octahedra that share  a cornercorner with one Li(3)O4F2 octahedra,  a cornercorner with one Li(4)O4F2 octahedra, corners with two equivalent Li(1)O3F3 octahedra,  an edgeedge with one Li(1)O3F3 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent Mn(1)O3F3 octahedra, edges with two equivalent Mn(2)O5F octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-14°. The Mn(3)-O(2) bond length is 2.03 Å. The Mn(3)-O(3) bond length is 1.90 Å. Both Mn(3)-O(4) bond lengths are 1.95 Å. Both Mn(3)-O(5) bond lengths are 1.96 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), and two equivalent Mn(2) atoms to form OLi3Mn2 square pyramids that share corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(5)Li3Mn3 octahedra, corners with two equivalent F(1)Li3Mn trigonal pyramids,  an edgeedge with one O(2)Li3Mn3 octahedra,  an edgeedge with one O(5)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(1)Li3Mn2 square pyramids, and edges with two equivalent F(3)Li3Mn2 square pyramids. The corner-sharing octahedral tilt angles range from 10-14°. In the second O site, O(2) is bonded to one Li(4), two equivalent Li(3), one Mn(3), and two equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(4)Li3Mn3 octahedra, corners with two equivalent O(1)Li3Mn2 square pyramids, corners with two equivalent F(1)Li3Mn trigonal pyramids, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra,  an edgeedge with one O(1)Li3Mn2 square pyramid, and  an edgeedge with one F(1)Li3Mn trigonal pyramid. The corner-sharing octahedral tilt angles range from 2-3°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(4), one Mn(3), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra,  a cornercorner with one O(5)Li3Mn3 octahedra, corners with two equivalent F(3)Li3Mn2 square pyramids, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra,  an edgeedge with one F(3)Li3Mn2 square pyramid, and edges with two equivalent F(1)Li3Mn trigonal pyramids. The corner-sharing octahedral tilt angles range from 0-3°. In the fourth O site, O(4) is bonded to one Li(4), two equivalent Li(1), one Mn(2), and two equivalent Mn(3) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra, corners with two equivalent O(5)Li3Mn3 octahedra, corners with two equivalent F(3)Li3Mn2 square pyramids,  an edgeedge with one O(5)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra,  an edgeedge with one F(3)Li3Mn2 square pyramid, and edges with two equivalent O(1)Li3Mn2 square pyramids. The corner-sharing octahedral tilt angles are 2°. In the fifth O site, O(5) is bonded to one Li(3), two equivalent Li(2), one Mn(1), and two equivalent Mn(3) atoms to form distorted OLi3Mn3 octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra, corners with two equivalent O(4)Li3Mn3 octahedra, corners with two equivalent O(1)Li3Mn2 square pyramids,  a cornercorner with one F(1)Li3Mn trigonal pyramid,  an edgeedge with one O(4)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra,  an edgeedge with one O(1)Li3Mn2 square pyramid, edges with two equivalent F(3)Li3Mn2 square pyramids, and edges with two equivalent F(1)Li3Mn trigonal pyramids. The corner-sharing octahedral tilt angles range from 0-2°. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), two equivalent Li(3), and one Mn(1) atom to form distorted FLi3Mn trigonal pyramids that share  a cornercorner with one O(5)Li3Mn3 octahedra, corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(1)Li3Mn2 square pyramids, corners with three equivalent F(3)Li3Mn2 square pyramids, corners with two equivalent F(1)Li3Mn trigonal pyramids,  an edgeedge with one O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, and edges with two equivalent O(5)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 8-20°. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Li(4), and one Mn(2) atom. In the third F site, F(3) is bonded to one Li(2), two equivalent Li(1), and two equivalent Mn(1) atoms to form FLi3Mn2 square pyramids that share corners with two equivalent O(3)Li3Mn3 octahedra, corners with two equivalent O(4)Li3Mn3 octahedra, corners with three equivalent F(1)Li3Mn trigonal pyramids,  an edgeedge with one O(3)Li3Mn3 octahedra,  an edgeedge with one O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(1)Li3Mn2 square pyramids, and edges with two equivalent F(3)Li3Mn2 square pyramids. The corner-sharing octahedral tilt angles range from 9-15°.