Li4Mn5O9F crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form distorted LiO6 octahedra that share  a cornercorner with one Mn(2)O5F octahedra,  a cornercorner with one Mn(4)O5F octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(5)O5F octahedra,  an edgeedge with one Li(4)O5F octahedra,  an edgeedge with one Mn(2)O5F octahedra,  an edgeedge with one Mn(4)O5F octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Li(2)O4F square pyramids. The corner-sharing octahedral tilt angles range from 5-13°. In the second Li site, Li(2) is bonded to one O(2), one O(3), one O(6), one O(7), and one F(1) atom to form distorted LiO4F square pyramids that share  a cornercorner with one Li(4)O5F octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(2)O5F octahedra, corners with two equivalent Mn(4)O5F octahedra, corners with two equivalent Mn(1)O6 octahedra,  an edgeedge with one Mn(4)O5F octahedra,  an edgeedge with one Mn(5)O5F octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra, and edges with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-90°. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(7), one O(8), and one F(1) atom. In the fourth Li site, Li(4) is bonded to one O(1), one O(4), one O(5), one O(8), one O(9), and one F(1) atom to form LiO5F octahedra that share  a cornercorner with one Mn(2)O5F octahedra,  a cornercorner with one Mn(4)O5F octahedra,  a cornercorner with one Mn(5)O5F octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Li(2)O4F square pyramid,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Mn(4)O5F octahedra,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Mn(2)O5F octahedra, and edges with two equivalent Mn(5)O5F octahedra. The corner-sharing octahedral tilt angles range from 13-19°. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(4)O5F octahedra, corners with two equivalent Li(2)O4F square pyramids,  an edgeedge with one Mn(2)O5F octahedra,  an edgeedge with one Mn(5)O5F octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(4)O5F octahedra, edges with two equivalent Mn(3)O6 octahedra, and  an edgeedge with one Li(2)O4F square pyramid. The corner-sharing octahedral tilt angles range from 10-19°. In the second Mn site, Mn(2) is bonded to one O(1), one O(4), one O(5), one O(6), one O(9), and one F(1) atom to form distorted MnO5F octahedra that share  a cornercorner with one Li(4)O5F octahedra,  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(2)O4F square pyramids,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Mn(4)O5F octahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Mn(5)O5F octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-16°. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(7) atom to form MnO6 octahedra that share  a cornercorner with one Li(4)O5F octahedra,  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O4F square pyramid,  an edgeedge with one Li(4)O5F octahedra,  an edgeedge with one Mn(4)O5F octahedra,  an edgeedge with one Mn(5)O5F octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(2)O5F octahedra, edges with two equivalent Mn(1)O6 octahedra, and  an edgeedge with one Li(2)O4F square pyramid. The corner-sharing octahedral tilt angles range from 8-13°. In the fourth Mn site, Mn(4) is bonded to one O(2), one O(3), one O(7), one O(8), one O(9), and one F(1) atom to form distorted MnO5F octahedra that share  a cornercorner with one Li(4)O5F octahedra,  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(2)O4F square pyramids,  an edgeedge with one Li(4)O5F octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Mn(2)O5F octahedra,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Mn(5)O5F octahedra, edges with two equivalent Mn(1)O6 octahedra, and  an edgeedge with one Li(2)O4F square pyramid. The corner-sharing octahedral tilt angles range from 10-14°. In the fifth Mn site, Mn(5) is bonded to one O(3), one O(4), one O(5), one O(8), one O(9), and one F(1) atom to form MnO5F octahedra that share  a cornercorner with one Li(4)O5F octahedra, corners with two equivalent Li(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Mn(2)O5F octahedra, edges with two equivalent Mn(4)O5F octahedra, and  an edgeedge with one Li(2)O4F square pyramid. The corner-sharing octahedral tilt angles range from 5-19°. There are nine inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(4), one Mn(1), one Mn(2), and one Mn(3) atom to form distorted OLi2Mn3 square pyramids that share  a cornercorner with one O(7)Li3Mn3 octahedra,  a cornercorner with one O(2)Li2Mn3 square pyramid,  a cornercorner with one O(4)Li2Mn3 square pyramid, corners with two equivalent O(6)Li2Mn3 square pyramids, corners with two equivalent O(8)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(3)Li3Mn3 octahedra,  an edgeedge with one O(7)Li3Mn3 octahedra,  an edgeedge with one O(2)Li2Mn3 square pyramid,  an edgeedge with one O(4)Li2Mn3 square pyramid,  an edgeedge with one O(6)Li2Mn3 square pyramid, and edges with two equivalent O(5)Li2Mn3 square pyramids. The corner-sharing octahedral tilt angles are 2°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Mn(1), one Mn(3), and one Mn(4) atom to form OLi2Mn3 square pyramids that share  a cornercorner with one O(7)Li3Mn3 octahedra,  a cornercorner with one O(1)Li2Mn3 square pyramid,  a cornercorner with one O(4)Li2Mn3 square pyramid, corners with two equivalent O(5)Li2Mn3 square pyramids, corners with two equivalent O(6)Li2Mn3 square pyramids, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(7)Li3Mn3 octahedra,  an edgeedge with one O(1)Li2Mn3 square pyramid,  an edgeedge with one O(6)Li2Mn3 square pyramid, and  an edgeedge with one O(8)Li2Mn3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 5°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Mn(1), one Mn(4), and one Mn(5) atom to form OLi3Mn3 octahedra that share  a cornercorner with one O(7)Li3Mn3 octahedra,  a cornercorner with one O(6)Li2Mn3 square pyramid, corners with two equivalent O(5)Li2Mn3 square pyramids, corners with two equivalent O(8)Li2Mn3 trigonal bipyramids, edges with two equivalent O(7)Li3Mn3 octahedra,  an edgeedge with one O(1)Li2Mn3 square pyramid,  an edgeedge with one O(4)Li2Mn3 square pyramid,  an edgeedge with one O(6)Li2Mn3 square pyramid, edges with two equivalent O(2)Li2Mn3 square pyramids, and  an edgeedge with one O(8)Li2Mn3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 13°. In the fourth O site, O(4) is bonded to one Li(3), one Li(4), one Mn(2), one Mn(3), and one Mn(5) atom to form OLi2Mn3 square pyramids that share corners with two equivalent O(7)Li3Mn3 octahedra,  a cornercorner with one O(1)Li2Mn3 square pyramid,  a cornercorner with one O(2)Li2Mn3 square pyramid, corners with two equivalent O(5)Li2Mn3 square pyramids,  a cornercorner with one O(8)Li2Mn3 trigonal bipyramid,  an edgeedge with one O(3)Li3Mn3 octahedra,  an edgeedge with one O(1)Li2Mn3 square pyramid,  an edgeedge with one O(5)Li2Mn3 square pyramid,  an edgeedge with one O(6)Li2Mn3 square pyramid, and  an edgeedge with one O(8)Li2Mn3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 3-5°. In the fifth O site, O(5) is bonded to one Li(1), one Li(4), one Mn(2), one Mn(3), and one Mn(5) atom to form OLi2Mn3 square pyramids that share corners with two equivalent O(3)Li3Mn3 octahedra,  a cornercorner with one O(6)Li2Mn3 square pyramid, corners with two equivalent O(2)Li2Mn3 square pyramids, corners with two equivalent O(4)Li2Mn3 square pyramids,  an edgeedge with one O(7)Li3Mn3 octahedra,  an edgeedge with one O(4)Li2Mn3 square pyramid,  an edgeedge with one O(6)Li2Mn3 square pyramid, edges with two equivalent O(1)Li2Mn3 square pyramids, and  an edgeedge with one O(8)Li2Mn3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 3-5°. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Mn(1), one Mn(2), and one Mn(3) atom to form OLi2Mn3 square pyramids that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(5)Li2Mn3 square pyramid, corners with two equivalent O(1)Li2Mn3 square pyramids, corners with two equivalent O(2)Li2Mn3 square pyramids,  a cornercorner with one O(8)Li2Mn3 trigonal bipyramid,  an edgeedge with one O(3)Li3Mn3 octahedra, edges with two equivalent O(7)Li3Mn3 octahedra,  an edgeedge with one O(1)Li2Mn3 square pyramid,  an edgeedge with one O(2)Li2Mn3 square pyramid,  an edgeedge with one O(4)Li2Mn3 square pyramid, and  an edgeedge with one O(5)Li2Mn3 square pyramid. The corner-sharing octahedral tilt angles are 7°. In the seventh O site, O(7) is bonded to one Li(1), one Li(2), one Li(3), one Mn(1), one Mn(3), and one Mn(4) atom to form OLi3Mn3 octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(1)Li2Mn3 square pyramid,  a cornercorner with one O(2)Li2Mn3 square pyramid, corners with two equivalent O(4)Li2Mn3 square pyramids,  a cornercorner with one O(8)Li2Mn3 trigonal bipyramid, edges with two equivalent O(3)Li3Mn3 octahedra,  an edgeedge with one O(1)Li2Mn3 square pyramid,  an edgeedge with one O(5)Li2Mn3 square pyramid, edges with two equivalent O(2)Li2Mn3 square pyramids, edges with two equivalent O(6)Li2Mn3 square pyramids, and  an edgeedge with one O(8)Li2Mn3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 13°. In the eighth O site, O(8) is bonded to one Li(3), one Li(4), one Mn(1), one Mn(4), and one Mn(5) atom to form distorted OLi2Mn3 trigonal bipyramids that share  a cornercorner with one O(7)Li3Mn3 octahedra, corners with two equivalent O(3)Li3Mn3 octahedra,  a cornercorner with one O(4)Li2Mn3 square pyramid,  a cornercorner with one O(6)Li2Mn3 square pyramid, corners with two equivalent O(1)Li2Mn3 square pyramids,  an edgeedge with one O(3)Li3Mn3 octahedra,  an edgeedge with one O(7)Li3Mn3 octahedra,  an edgeedge with one O(2)Li2Mn3 square pyramid,  an edgeedge with one O(4)Li2Mn3 square pyramid, and  an edgeedge with one O(5)Li2Mn3 square pyramid. The corner-sharing octahedral tilt angles range from 11-76°. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Li(4), one Mn(2), one Mn(4), and one Mn(5) atom. F(1) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), one Li(4), one Mn(2), one Mn(4), and one Mn(5) atom.
Li4Mn5O9F crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form distorted LiO6 octahedra that share  a cornercorner with one Mn(2)O5F octahedra,  a cornercorner with one Mn(4)O5F octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(5)O5F octahedra,  an edgeedge with one Li(4)O5F octahedra,  an edgeedge with one Mn(2)O5F octahedra,  an edgeedge with one Mn(4)O5F octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Li(2)O4F square pyramids. The corner-sharing octahedral tilt angles range from 5-13°. The Li(1)-O(1) bond length is 2.56 Å. The Li(1)-O(2) bond length is 2.15 Å. The Li(1)-O(3) bond length is 2.20 Å. The Li(1)-O(5) bond length is 2.23 Å. The Li(1)-O(6) bond length is 2.22 Å. The Li(1)-O(7) bond length is 2.21 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), one O(6), one O(7), and one F(1) atom to form distorted LiO4F square pyramids that share  a cornercorner with one Li(4)O5F octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(2)O5F octahedra, corners with two equivalent Mn(4)O5F octahedra, corners with two equivalent Mn(1)O6 octahedra,  an edgeedge with one Mn(4)O5F octahedra,  an edgeedge with one Mn(5)O5F octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra, and edges with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-90°. The Li(2)-O(2) bond length is 2.05 Å. The Li(2)-O(3) bond length is 2.25 Å. The Li(2)-O(6) bond length is 1.96 Å. The Li(2)-O(7) bond length is 2.23 Å. The Li(2)-F(1) bond length is 2.04 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(7), one O(8), and one F(1) atom. The Li(3)-O(3) bond length is 2.12 Å. The Li(3)-O(4) bond length is 2.25 Å. The Li(3)-O(7) bond length is 2.19 Å. The Li(3)-O(8) bond length is 2.13 Å. The Li(3)-F(1) bond length is 2.01 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(4), one O(5), one O(8), one O(9), and one F(1) atom to form LiO5F octahedra that share  a cornercorner with one Mn(2)O5F octahedra,  a cornercorner with one Mn(4)O5F octahedra,  a cornercorner with one Mn(5)O5F octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Li(2)O4F square pyramid,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Mn(4)O5F octahedra,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Mn(2)O5F octahedra, and edges with two equivalent Mn(5)O5F octahedra. The corner-sharing octahedral tilt angles range from 13-19°. The Li(4)-O(1) bond length is 2.10 Å. The Li(4)-O(4) bond length is 2.24 Å. The Li(4)-O(5) bond length is 2.12 Å. The Li(4)-O(8) bond length is 2.33 Å. The Li(4)-O(9) bond length is 2.01 Å. The Li(4)-F(1) bond length is 2.16 Å. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(4)O5F octahedra, corners with two equivalent Li(2)O4F square pyramids,  an edgeedge with one Mn(2)O5F octahedra,  an edgeedge with one Mn(5)O5F octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(4)O5F octahedra, edges with two equivalent Mn(3)O6 octahedra, and  an edgeedge with one Li(2)O4F square pyramid. The corner-sharing octahedral tilt angles range from 10-19°. The Mn(1)-O(1) bond length is 2.00 Å. The Mn(1)-O(2) bond length is 1.97 Å. The Mn(1)-O(3) bond length is 2.34 Å. The Mn(1)-O(6) bond length is 2.14 Å. The Mn(1)-O(7) bond length is 1.97 Å. The Mn(1)-O(8) bond length is 2.03 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(4), one O(5), one O(6), one O(9), and one F(1) atom to form distorted MnO5F octahedra that share  a cornercorner with one Li(4)O5F octahedra,  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(2)O4F square pyramids,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Mn(4)O5F octahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Mn(5)O5F octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-16°. The Mn(2)-O(1) bond length is 2.09 Å. The Mn(2)-O(4) bond length is 1.99 Å. The Mn(2)-O(5) bond length is 1.91 Å. The Mn(2)-O(6) bond length is 2.11 Å. The Mn(2)-O(9) bond length is 1.98 Å. The Mn(2)-F(1) bond length is 2.39 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(7) atom to form MnO6 octahedra that share  a cornercorner with one Li(4)O5F octahedra,  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O4F square pyramid,  an edgeedge with one Li(4)O5F octahedra,  an edgeedge with one Mn(4)O5F octahedra,  an edgeedge with one Mn(5)O5F octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(2)O5F octahedra, edges with two equivalent Mn(1)O6 octahedra, and  an edgeedge with one Li(2)O4F square pyramid. The corner-sharing octahedral tilt angles range from 8-13°. The Mn(3)-O(1) bond length is 1.97 Å. The Mn(3)-O(2) bond length is 2.35 Å. The Mn(3)-O(4) bond length is 2.00 Å. The Mn(3)-O(5) bond length is 2.28 Å. The Mn(3)-O(6) bond length is 1.94 Å. The Mn(3)-O(7) bond length is 1.98 Å. In the fourth Mn site, Mn(4) is bonded to one O(2), one O(3), one O(7), one O(8), one O(9), and one F(1) atom to form distorted MnO5F octahedra that share  a cornercorner with one Li(4)O5F octahedra,  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(2)O4F square pyramids,  an edgeedge with one Li(4)O5F octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Mn(2)O5F octahedra,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Mn(5)O5F octahedra, edges with two equivalent Mn(1)O6 octahedra, and  an edgeedge with one Li(2)O4F square pyramid. The corner-sharing octahedral tilt angles range from 10-14°. The Mn(4)-O(2) bond length is 1.93 Å. The Mn(4)-O(3) bond length is 1.98 Å. The Mn(4)-O(7) bond length is 2.26 Å. The Mn(4)-O(8) bond length is 2.00 Å. The Mn(4)-O(9) bond length is 1.91 Å. The Mn(4)-F(1) bond length is 2.51 Å. In the fifth Mn site, Mn(5) is bonded to one O(3), one O(4), one O(5), one O(8), one O(9), and one F(1) atom to form MnO5F octahedra that share  a cornercorner with one Li(4)O5F octahedra, corners with two equivalent Li(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Mn(2)O5F octahedra, edges with two equivalent Mn(4)O5F octahedra, and  an edgeedge with one Li(2)O4F square pyramid. The corner-sharing octahedral tilt angles range from 5-19°. The Mn(5)-O(3) bond length is 2.02 Å. The Mn(5)-O(4) bond length is 1.99 Å. The Mn(5)-O(5) bond length is 1.97 Å. The Mn(5)-O(8) bond length is 1.98 Å. The Mn(5)-O(9) bond length is 2.11 Å. The Mn(5)-F(1) bond length is 2.34 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(4), one Mn(1), one Mn(2), and one Mn(3) atom to form distorted OLi2Mn3 square pyramids that share  a cornercorner with one O(7)Li3Mn3 octahedra,  a cornercorner with one O(2)Li2Mn3 square pyramid,  a cornercorner with one O(4)Li2Mn3 square pyramid, corners with two equivalent O(6)Li2Mn3 square pyramids, corners with two equivalent O(8)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(3)Li3Mn3 octahedra,  an edgeedge with one O(7)Li3Mn3 octahedra,  an edgeedge with one O(2)Li2Mn3 square pyramid,  an edgeedge with one O(4)Li2Mn3 square pyramid,  an edgeedge with one O(6)Li2Mn3 square pyramid, and edges with two equivalent O(5)Li2Mn3 square pyramids. The corner-sharing octahedral tilt angles are 2°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Mn(1), one Mn(3), and one Mn(4) atom to form OLi2Mn3 square pyramids that share  a cornercorner with one O(7)Li3Mn3 octahedra,  a cornercorner with one O(1)Li2Mn3 square pyramid,  a cornercorner with one O(4)Li2Mn3 square pyramid, corners with two equivalent O(5)Li2Mn3 square pyramids, corners with two equivalent O(6)Li2Mn3 square pyramids, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(7)Li3Mn3 octahedra,  an edgeedge with one O(1)Li2Mn3 square pyramid,  an edgeedge with one O(6)Li2Mn3 square pyramid, and  an edgeedge with one O(8)Li2Mn3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 5°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Mn(1), one Mn(4), and one Mn(5) atom to form OLi3Mn3 octahedra that share  a cornercorner with one O(7)Li3Mn3 octahedra,  a cornercorner with one O(6)Li2Mn3 square pyramid, corners with two equivalent O(5)Li2Mn3 square pyramids, corners with two equivalent O(8)Li2Mn3 trigonal bipyramids, edges with two equivalent O(7)Li3Mn3 octahedra,  an edgeedge with one O(1)Li2Mn3 square pyramid,  an edgeedge with one O(4)Li2Mn3 square pyramid,  an edgeedge with one O(6)Li2Mn3 square pyramid, edges with two equivalent O(2)Li2Mn3 square pyramids, and  an edgeedge with one O(8)Li2Mn3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 13°. In the fourth O site, O(4) is bonded to one Li(3), one Li(4), one Mn(2), one Mn(3), and one Mn(5) atom to form OLi2Mn3 square pyramids that share corners with two equivalent O(7)Li3Mn3 octahedra,  a cornercorner with one O(1)Li2Mn3 square pyramid,  a cornercorner with one O(2)Li2Mn3 square pyramid, corners with two equivalent O(5)Li2Mn3 square pyramids,  a cornercorner with one O(8)Li2Mn3 trigonal bipyramid,  an edgeedge with one O(3)Li3Mn3 octahedra,  an edgeedge with one O(1)Li2Mn3 square pyramid,  an edgeedge with one O(5)Li2Mn3 square pyramid,  an edgeedge with one O(6)Li2Mn3 square pyramid, and  an edgeedge with one O(8)Li2Mn3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 3-5°. In the fifth O site, O(5) is bonded to one Li(1), one Li(4), one Mn(2), one Mn(3), and one Mn(5) atom to form OLi2Mn3 square pyramids that share corners with two equivalent O(3)Li3Mn3 octahedra,  a cornercorner with one O(6)Li2Mn3 square pyramid, corners with two equivalent O(2)Li2Mn3 square pyramids, corners with two equivalent O(4)Li2Mn3 square pyramids,  an edgeedge with one O(7)Li3Mn3 octahedra,  an edgeedge with one O(4)Li2Mn3 square pyramid,  an edgeedge with one O(6)Li2Mn3 square pyramid, edges with two equivalent O(1)Li2Mn3 square pyramids, and  an edgeedge with one O(8)Li2Mn3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 3-5°. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Mn(1), one Mn(2), and one Mn(3) atom to form OLi2Mn3 square pyramids that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(5)Li2Mn3 square pyramid, corners with two equivalent O(1)Li2Mn3 square pyramids, corners with two equivalent O(2)Li2Mn3 square pyramids,  a cornercorner with one O(8)Li2Mn3 trigonal bipyramid,  an edgeedge with one O(3)Li3Mn3 octahedra, edges with two equivalent O(7)Li3Mn3 octahedra,  an edgeedge with one O(1)Li2Mn3 square pyramid,  an edgeedge with one O(2)Li2Mn3 square pyramid,  an edgeedge with one O(4)Li2Mn3 square pyramid, and  an edgeedge with one O(5)Li2Mn3 square pyramid. The corner-sharing octahedral tilt angles are 7°. In the seventh O site, O(7) is bonded to one Li(1), one Li(2), one Li(3), one Mn(1), one Mn(3), and one Mn(4) atom to form OLi3Mn3 octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(1)Li2Mn3 square pyramid,  a cornercorner with one O(2)Li2Mn3 square pyramid, corners with two equivalent O(4)Li2Mn3 square pyramids,  a cornercorner with one O(8)Li2Mn3 trigonal bipyramid, edges with two equivalent O(3)Li3Mn3 octahedra,  an edgeedge with one O(1)Li2Mn3 square pyramid,  an edgeedge with one O(5)Li2Mn3 square pyramid, edges with two equivalent O(2)Li2Mn3 square pyramids, edges with two equivalent O(6)Li2Mn3 square pyramids, and  an edgeedge with one O(8)Li2Mn3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 13°. In the eighth O site, O(8) is bonded to one Li(3), one Li(4), one Mn(1), one Mn(4), and one Mn(5) atom to form distorted OLi2Mn3 trigonal bipyramids that share  a cornercorner with one O(7)Li3Mn3 octahedra, corners with two equivalent O(3)Li3Mn3 octahedra,  a cornercorner with one O(4)Li2Mn3 square pyramid,  a cornercorner with one O(6)Li2Mn3 square pyramid, corners with two equivalent O(1)Li2Mn3 square pyramids,  an edgeedge with one O(3)Li3Mn3 octahedra,  an edgeedge with one O(7)Li3Mn3 octahedra,  an edgeedge with one O(2)Li2Mn3 square pyramid,  an edgeedge with one O(4)Li2Mn3 square pyramid, and  an edgeedge with one O(5)Li2Mn3 square pyramid. The corner-sharing octahedral tilt angles range from 11-76°. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Li(4), one Mn(2), one Mn(4), and one Mn(5) atom. F(1) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), one Li(4), one Mn(2), one Mn(4), and one Mn(5) atom.