Li5MnO3F is Corundum-derived structured and crystallizes in the monoclinic P2_1/m space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(2) and two equivalent F(1) atoms. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to two equivalent O(3) and two equivalent F(1) atoms. In the third Li site, Li(3) is bonded to one O(1), two equivalent O(3), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO3F trigonal pyramids. In the fourth Li site, Li(4) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO3F tetrahedra. In the fifth Li site, Li(5) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO3F trigonal pyramids. In the sixth Li site, Li(6) is bonded to one O(1), two equivalent O(3), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO3F trigonal pyramids. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(3) atoms. In the second Mn site, Mn(2) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Li(4), one Li(5), one Li(6), one Mn(1), and one Mn(2) atom to form distorted OLi4Mn2 octahedra that share corners with two equivalent O(2)Li5Mn octahedra, corners with two equivalent O(3)Li5Mn octahedra,  an edgeedge with one O(1)Li4Mn2 octahedra, edges with two equivalent O(2)Li5Mn octahedra, edges with two equivalent O(3)Li5Mn octahedra, and edges with two equivalent F(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-39°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(4), two equivalent Li(5), and one Mn(2) atom to form distorted OLi5Mn octahedra that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent F(1)Li6 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with three equivalent O(2)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 9-41°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(3), two equivalent Li(6), and one Mn(1) atom to form OLi5Mn octahedra that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent F(1)Li6 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with three equivalent O(3)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 2-39°. F(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Li(6) atom to form distorted FLi6 octahedra that share corners with two equivalent O(2)Li5Mn octahedra, corners with two equivalent O(3)Li5Mn octahedra,  an edgeedge with one F(1)Li6 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent O(2)Li5Mn octahedra, and edges with two equivalent O(3)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 7-41°.
Li5MnO3F is Corundum-derived structured and crystallizes in the monoclinic P2_1/m space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(2) and two equivalent F(1) atoms. Both Li(1)-O(2) bond lengths are 1.95 Å. Both Li(1)-F(1) bond lengths are 2.20 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to two equivalent O(3) and two equivalent F(1) atoms. Both Li(2)-O(3) bond lengths are 1.96 Å. Both Li(2)-F(1) bond lengths are 2.11 Å. In the third Li site, Li(3) is bonded to one O(1), two equivalent O(3), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO3F trigonal pyramids. The Li(3)-O(1) bond length is 1.96 Å. There is one shorter (1.95 Å) and one longer (1.97 Å) Li(3)-O(3) bond length. The Li(3)-F(1) bond length is 2.01 Å. In the fourth Li site, Li(4) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO3F tetrahedra. The Li(4)-O(1) bond length is 2.04 Å. There is one shorter (1.91 Å) and one longer (1.95 Å) Li(4)-O(2) bond length. The Li(4)-F(1) bond length is 2.01 Å. In the fifth Li site, Li(5) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO3F trigonal pyramids. The Li(5)-O(1) bond length is 1.97 Å. There is one shorter (1.92 Å) and one longer (1.93 Å) Li(5)-O(2) bond length. The Li(5)-F(1) bond length is 2.07 Å. In the sixth Li site, Li(6) is bonded to one O(1), two equivalent O(3), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO3F trigonal pyramids. The Li(6)-O(1) bond length is 1.96 Å. There is one shorter (1.95 Å) and one longer (1.99 Å) Li(6)-O(3) bond length. The Li(6)-F(1) bond length is 2.06 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(3) atoms. Both Mn(1)-O(1) bond lengths are 1.99 Å. Both Mn(1)-O(3) bond lengths are 1.95 Å. In the second Mn site, Mn(2) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Mn(2)-O(1) bond lengths are 2.15 Å. Both Mn(2)-O(2) bond lengths are 2.08 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Li(4), one Li(5), one Li(6), one Mn(1), and one Mn(2) atom to form distorted OLi4Mn2 octahedra that share corners with two equivalent O(2)Li5Mn octahedra, corners with two equivalent O(3)Li5Mn octahedra,  an edgeedge with one O(1)Li4Mn2 octahedra, edges with two equivalent O(2)Li5Mn octahedra, edges with two equivalent O(3)Li5Mn octahedra, and edges with two equivalent F(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-39°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(4), two equivalent Li(5), and one Mn(2) atom to form distorted OLi5Mn octahedra that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent F(1)Li6 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with three equivalent O(2)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 9-41°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(3), two equivalent Li(6), and one Mn(1) atom to form OLi5Mn octahedra that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent F(1)Li6 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with three equivalent O(3)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 2-39°. F(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Li(6) atom to form distorted FLi6 octahedra that share corners with two equivalent O(2)Li5Mn octahedra, corners with two equivalent O(3)Li5Mn octahedra,  an edgeedge with one F(1)Li6 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent O(2)Li5Mn octahedra, and edges with two equivalent O(3)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 7-41°.