LiMn2O3F crystallizes in the orthorhombic Imm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), one F(1), and one F(2) atom to form LiO2F2 tetrahedra that share  a cornercorner with one Mn(4)O5F octahedra, corners with two equivalent Mn(1)O5F octahedra, corners with three equivalent Mn(2)O5F octahedra, corners with four equivalent Mn(3)O5F octahedra, and  a cornercorner with one Li(1)O2F2 tetrahedra. The corner-sharing octahedral tilt angles range from 51-67°. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(5), and one F(3) atom to form LiO3F tetrahedra that share  a cornercorner with one Mn(1)O5F octahedra, corners with two equivalent Mn(4)O5F octahedra, corners with three equivalent Mn(2)O5F octahedra, corners with four equivalent Mn(3)O5F octahedra, and  a cornercorner with one Li(2)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 54-62°. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), four equivalent O(1), and one F(3) atom to form distorted MnO5F octahedra that share corners with two equivalent Li(2)O3F tetrahedra, corners with four equivalent Li(1)O2F2 tetrahedra, edges with two equivalent Mn(2)O5F octahedra, and edges with four equivalent Mn(3)O5F octahedra. In the second Mn site, Mn(2) is bonded to one O(3), two equivalent O(1), two equivalent O(5), and one F(2) atom to form MnO5F octahedra that share corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra,  an edgeedge with one Mn(1)O5F octahedra,  an edgeedge with one Mn(4)O5F octahedra, and edges with four equivalent Mn(3)O5F octahedra. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(2) atom to form MnO5F octahedra that share corners with two equivalent Mn(3)O5F octahedra, corners with two equivalent Li(1)O2F2 tetrahedra, corners with two equivalent Li(2)O3F tetrahedra,  an edgeedge with one Mn(1)O5F octahedra,  an edgeedge with one Mn(4)O5F octahedra, edges with two equivalent Mn(2)O5F octahedra, and edges with three equivalent Mn(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 2-3°. In the fourth Mn site, Mn(4) is bonded to one O(4), four equivalent O(5), and one F(1) atom to form distorted MnO5F octahedra that share corners with two equivalent Li(1)O2F2 tetrahedra, corners with four equivalent Li(2)O3F tetrahedra, edges with two equivalent Mn(2)O5F octahedra, and edges with four equivalent Mn(3)O5F octahedra. There are five inequivalent O sites. In the first O site, O(5) is bonded to one Li(2), one Mn(2), one Mn(3), and one Mn(4) atom to form OLiMn3 tetrahedra that share  a cornercorner with one O(2)Mn5 square pyramid, corners with three equivalent O(1)LiMn3 tetrahedra, corners with three equivalent O(5)LiMn3 tetrahedra,  an edgeedge with one O(4)Mn5 square pyramid, and  an edgeedge with one O(5)LiMn3 tetrahedra. In the second O site, O(1) is bonded to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom to form OLiMn3 tetrahedra that share  a cornercorner with one O(4)Mn5 square pyramid, corners with three equivalent O(1)LiMn3 tetrahedra, corners with three equivalent O(5)LiMn3 tetrahedra,  an edgeedge with one O(2)Mn5 square pyramid, and  an edgeedge with one O(1)LiMn3 tetrahedra. In the third O site, O(2) is bonded to one Mn(1) and four equivalent Mn(3) atoms to form OMn5 square pyramids that share corners with four equivalent O(5)LiMn3 tetrahedra, edges with two equivalent O(4)Mn5 square pyramids, and edges with four equivalent O(1)LiMn3 tetrahedra. In the fourth O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Mn(2), and two equivalent Mn(3) atoms. In the fifth O site, O(4) is bonded to one Mn(4) and four equivalent Mn(3) atoms to form OMn5 square pyramids that share corners with four equivalent O(1)LiMn3 tetrahedra, edges with two equivalent O(2)Mn5 square pyramids, and edges with four equivalent O(5)LiMn3 tetrahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Mn(4) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(2), and two equivalent Mn(3) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(2) and one Mn(1) atom.
LiMn2O3F crystallizes in the orthorhombic Imm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), one F(1), and one F(2) atom to form LiO2F2 tetrahedra that share  a cornercorner with one Mn(4)O5F octahedra, corners with two equivalent Mn(1)O5F octahedra, corners with three equivalent Mn(2)O5F octahedra, corners with four equivalent Mn(3)O5F octahedra, and  a cornercorner with one Li(1)O2F2 tetrahedra. The corner-sharing octahedral tilt angles range from 51-67°. Both Li(1)-O(1) bond lengths are 2.04 Å. The Li(1)-F(1) bond length is 1.88 Å. The Li(1)-F(2) bond length is 1.91 Å. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(5), and one F(3) atom to form LiO3F tetrahedra that share  a cornercorner with one Mn(1)O5F octahedra, corners with two equivalent Mn(4)O5F octahedra, corners with three equivalent Mn(2)O5F octahedra, corners with four equivalent Mn(3)O5F octahedra, and  a cornercorner with one Li(2)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 54-62°. The Li(2)-O(3) bond length is 1.97 Å. Both Li(2)-O(5) bond lengths are 2.08 Å. The Li(2)-F(3) bond length is 1.89 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), four equivalent O(1), and one F(3) atom to form distorted MnO5F octahedra that share corners with two equivalent Li(2)O3F tetrahedra, corners with four equivalent Li(1)O2F2 tetrahedra, edges with two equivalent Mn(2)O5F octahedra, and edges with four equivalent Mn(3)O5F octahedra. The Mn(1)-O(2) bond length is 2.28 Å. All Mn(1)-O(1) bond lengths are 2.01 Å. The Mn(1)-F(3) bond length is 2.08 Å. In the second Mn site, Mn(2) is bonded to one O(3), two equivalent O(1), two equivalent O(5), and one F(2) atom to form MnO5F octahedra that share corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra,  an edgeedge with one Mn(1)O5F octahedra,  an edgeedge with one Mn(4)O5F octahedra, and edges with four equivalent Mn(3)O5F octahedra. The Mn(2)-O(3) bond length is 2.15 Å. Both Mn(2)-O(1) bond lengths are 1.97 Å. Both Mn(2)-O(5) bond lengths are 1.98 Å. The Mn(2)-F(2) bond length is 2.29 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(2) atom to form MnO5F octahedra that share corners with two equivalent Mn(3)O5F octahedra, corners with two equivalent Li(1)O2F2 tetrahedra, corners with two equivalent Li(2)O3F tetrahedra,  an edgeedge with one Mn(1)O5F octahedra,  an edgeedge with one Mn(4)O5F octahedra, edges with two equivalent Mn(2)O5F octahedra, and edges with three equivalent Mn(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 2-3°. The Mn(3)-O(1) bond length is 1.97 Å. The Mn(3)-O(2) bond length is 2.16 Å. The Mn(3)-O(3) bond length is 1.98 Å. The Mn(3)-O(4) bond length is 2.10 Å. The Mn(3)-O(5) bond length is 1.97 Å. The Mn(3)-F(2) bond length is 2.17 Å. In the fourth Mn site, Mn(4) is bonded to one O(4), four equivalent O(5), and one F(1) atom to form distorted MnO5F octahedra that share corners with two equivalent Li(1)O2F2 tetrahedra, corners with four equivalent Li(2)O3F tetrahedra, edges with two equivalent Mn(2)O5F octahedra, and edges with four equivalent Mn(3)O5F octahedra. The Mn(4)-O(4) bond length is 2.31 Å. All Mn(4)-O(5) bond lengths are 2.00 Å. The Mn(4)-F(1) bond length is 2.11 Å. There are five inequivalent O sites. In the first O site, O(5) is bonded to one Li(2), one Mn(2), one Mn(3), and one Mn(4) atom to form OLiMn3 tetrahedra that share  a cornercorner with one O(2)Mn5 square pyramid, corners with three equivalent O(1)LiMn3 tetrahedra, corners with three equivalent O(5)LiMn3 tetrahedra,  an edgeedge with one O(4)Mn5 square pyramid, and  an edgeedge with one O(5)LiMn3 tetrahedra. In the second O site, O(1) is bonded to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom to form OLiMn3 tetrahedra that share  a cornercorner with one O(4)Mn5 square pyramid, corners with three equivalent O(1)LiMn3 tetrahedra, corners with three equivalent O(5)LiMn3 tetrahedra,  an edgeedge with one O(2)Mn5 square pyramid, and  an edgeedge with one O(1)LiMn3 tetrahedra. In the third O site, O(2) is bonded to one Mn(1) and four equivalent Mn(3) atoms to form OMn5 square pyramids that share corners with four equivalent O(5)LiMn3 tetrahedra, edges with two equivalent O(4)Mn5 square pyramids, and edges with four equivalent O(1)LiMn3 tetrahedra. In the fourth O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Mn(2), and two equivalent Mn(3) atoms. In the fifth O site, O(4) is bonded to one Mn(4) and four equivalent Mn(3) atoms to form OMn5 square pyramids that share corners with four equivalent O(1)LiMn3 tetrahedra, edges with two equivalent O(2)Mn5 square pyramids, and edges with four equivalent O(5)LiMn3 tetrahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Mn(4) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(2), and two equivalent Mn(3) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(2) and one Mn(1) atom.