Na3Li4Mn5O9 crystallizes in the triclinic P1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form distorted NaO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one Mn(1)O4 tetrahedra,  a cornercorner with one Mn(2)O4 tetrahedra,  a cornercorner with one Mn(3)O4 tetrahedra,  a cornercorner with one Mn(4)O4 tetrahedra,  a cornercorner with one Mn(5)O4 tetrahedra, edges with three equivalent Na(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra,  an edgeedge with one Mn(1)O4 tetrahedra,  an edgeedge with one Mn(2)O4 tetrahedra,  an edgeedge with one Mn(3)O4 tetrahedra,  an edgeedge with one Mn(4)O4 tetrahedra, and  an edgeedge with one Mn(5)O4 tetrahedra. In the second Na site, Na(2) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form distorted NaO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one Mn(1)O4 tetrahedra,  a cornercorner with one Mn(2)O4 tetrahedra,  a cornercorner with one Mn(3)O4 tetrahedra,  a cornercorner with one Mn(4)O4 tetrahedra,  a cornercorner with one Mn(5)O4 tetrahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Na(3)O6 octahedra,  an edgeedge with one Mn(1)O4 tetrahedra,  an edgeedge with one Mn(2)O4 tetrahedra,  an edgeedge with one Mn(3)O4 tetrahedra,  an edgeedge with one Mn(4)O4 tetrahedra, and  an edgeedge with one Mn(5)O4 tetrahedra. In the third Na site, Na(3) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form distorted NaO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one Mn(1)O4 tetrahedra,  a cornercorner with one Mn(2)O4 tetrahedra,  a cornercorner with one Mn(3)O4 tetrahedra,  a cornercorner with one Mn(4)O4 tetrahedra,  a cornercorner with one Mn(5)O4 tetrahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra,  an edgeedge with one Mn(1)O4 tetrahedra,  an edgeedge with one Mn(2)O4 tetrahedra,  an edgeedge with one Mn(3)O4 tetrahedra,  an edgeedge with one Mn(4)O4 tetrahedra, and  an edgeedge with one Mn(5)O4 tetrahedra. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(9) atom. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(5), and one O(9) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(4), and one O(9) atom. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(7), and one O(9) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one Mn(1)O4 tetrahedra,  a cornercorner with one Mn(2)O4 tetrahedra,  an edgeedge with one Mn(3)O4 tetrahedra,  an edgeedge with one Mn(4)O4 tetrahedra, and  an edgeedge with one Mn(5)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-50°. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form MnO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one Mn(5)O4 tetrahedra, corners with three equivalent Mn(2)O4 tetrahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra, and  an edgeedge with one Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-27°. In the second Mn site, Mn(2) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form MnO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one Mn(4)O4 tetrahedra, corners with three equivalent Mn(1)O4 tetrahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra, and  an edgeedge with one Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-28°. In the third Mn site, Mn(3) is bonded to one O(6), one O(7), one O(8), and one O(9) atom to form MnO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra, corners with three equivalent Mn(4)O4 tetrahedra, corners with three equivalent Mn(5)O4 tetrahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one Na(3)O6 octahedra, and  an edgeedge with one Li(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 18-32°. In the fourth Mn site, Mn(4) is bonded to one O(2), one O(6), one O(7), and one O(8) atom to form MnO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one Mn(2)O4 tetrahedra, corners with three equivalent Mn(3)O4 tetrahedra, corners with three equivalent Mn(5)O4 tetrahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one Na(3)O6 octahedra, and  an edgeedge with one Li(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 13-26°. In the fifth Mn site, Mn(5) is bonded to one O(1), one O(6), one O(7), and one O(8) atom to form MnO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one Mn(1)O4 tetrahedra, corners with three equivalent Mn(3)O4 tetrahedra, corners with three equivalent Mn(4)O4 tetrahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one Na(3)O6 octahedra, and  an edgeedge with one Li(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 13-25°. There are nine inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(1), and one Mn(5) atom to form distorted OLi4Mn2 octahedra that share  a cornercorner with one O(6)Na3Mn3 octahedra,  a cornercorner with one O(8)Na3Mn3 octahedra, corners with two equivalent O(2)Li4Mn2 octahedra, corners with two equivalent O(9)Li4Mn trigonal bipyramids,  an edgeedge with one O(2)Li4Mn2 octahedra,  an edgeedge with one O(3)Na3LiMn2 pentagonal pyramid,  an edgeedge with one O(4)Na3LiMn2 pentagonal pyramid,  an edgeedge with one O(5)Na3LiMn2 pentagonal pyramid, and  an edgeedge with one O(9)Li4Mn trigonal bipyramid. The corner-sharing octahedral tilt angles range from 60-68°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(2), and one Mn(4) atom to form distorted OLi4Mn2 octahedra that share  a cornercorner with one O(6)Na3Mn3 octahedra,  a cornercorner with one O(8)Na3Mn3 octahedra, corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent O(9)Li4Mn trigonal bipyramids,  an edgeedge with one O(1)Li4Mn2 octahedra,  an edgeedge with one O(3)Na3LiMn2 pentagonal pyramid,  an edgeedge with one O(4)Na3LiMn2 pentagonal pyramid,  an edgeedge with one O(5)Na3LiMn2 pentagonal pyramid, and  an edgeedge with one O(9)Li4Mn trigonal bipyramid. The corner-sharing octahedral tilt angles range from 60-68°. In the third O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), one Li(1), one Mn(1), and one Mn(2) atom to form distorted ONa3LiMn2 pentagonal pyramids that share  a cornercorner with one O(6)Na3Mn3 octahedra,  a cornercorner with one O(8)Na3Mn3 octahedra,  a cornercorner with one O(4)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(5)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(9)Li4Mn trigonal bipyramid,  an edgeedge with one O(1)Li4Mn2 octahedra,  an edgeedge with one O(2)Li4Mn2 octahedra,  an edgeedge with one O(6)Na3Mn3 octahedra,  an edgeedge with one O(8)Na3Mn3 octahedra, edges with two equivalent O(4)Na3LiMn2 pentagonal pyramids, and edges with two equivalent O(5)Na3LiMn2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 2-11°. In the fourth O site, O(4) is bonded to one Na(1), one Na(2), one Na(3), one Li(3), one Mn(1), and one Mn(2) atom to form distorted ONa3LiMn2 pentagonal pyramids that share  a cornercorner with one O(6)Na3Mn3 octahedra,  a cornercorner with one O(8)Na3Mn3 octahedra,  a cornercorner with one O(3)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(5)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(9)Li4Mn trigonal bipyramid,  an edgeedge with one O(1)Li4Mn2 octahedra,  an edgeedge with one O(2)Li4Mn2 octahedra,  an edgeedge with one O(6)Na3Mn3 octahedra,  an edgeedge with one O(8)Na3Mn3 octahedra, edges with two equivalent O(3)Na3LiMn2 pentagonal pyramids, and edges with two equivalent O(5)Na3LiMn2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 0-11°. In the fifth O site, O(5) is bonded to one Na(1), one Na(2), one Na(3), one Li(2), one Mn(1), and one Mn(2) atom to form distorted ONa3LiMn2 pentagonal pyramids that share  a cornercorner with one O(6)Na3Mn3 octahedra,  a cornercorner with one O(8)Na3Mn3 octahedra,  a cornercorner with one O(3)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(4)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(9)Li4Mn trigonal bipyramid,  an edgeedge with one O(1)Li4Mn2 octahedra,  an edgeedge with one O(2)Li4Mn2 octahedra,  an edgeedge with one O(6)Na3Mn3 octahedra,  an edgeedge with one O(8)Na3Mn3 octahedra, edges with two equivalent O(3)Na3LiMn2 pentagonal pyramids, and edges with two equivalent O(4)Na3LiMn2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 1-9°. In the sixth O site, O(6) is bonded to one Na(1), one Na(2), one Na(3), one Mn(3), one Mn(4), and one Mn(5) atom to form distorted ONa3Mn3 octahedra that share  a cornercorner with one O(1)Li4Mn2 octahedra,  a cornercorner with one O(2)Li4Mn2 octahedra,  a cornercorner with one O(3)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(4)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(5)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(9)Li4Mn trigonal bipyramid, edges with three equivalent O(8)Na3Mn3 octahedra,  an edgeedge with one O(3)Na3LiMn2 pentagonal pyramid,  an edgeedge with one O(4)Na3LiMn2 pentagonal pyramid, and  an edgeedge with one O(5)Na3LiMn2 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 60-64°. In the seventh O site, O(7) is bonded in a 7-coordinate geometry to one Na(1), one Na(2), one Na(3), one Li(4), one Mn(3), one Mn(4), and one Mn(5) atom. In the eighth O site, O(8) is bonded to one Na(1), one Na(2), one Na(3), one Mn(3), one Mn(4), and one Mn(5) atom to form ONa3Mn3 octahedra that share  a cornercorner with one O(1)Li4Mn2 octahedra,  a cornercorner with one O(2)Li4Mn2 octahedra,  a cornercorner with one O(3)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(4)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(5)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(9)Li4Mn trigonal bipyramid, edges with three equivalent O(6)Na3Mn3 octahedra,  an edgeedge with one O(3)Na3LiMn2 pentagonal pyramid,  an edgeedge with one O(4)Na3LiMn2 pentagonal pyramid, and  an edgeedge with one O(5)Na3LiMn2 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 60-64°. In the ninth O site, O(9) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Mn(3) atom to form distorted OLi4Mn trigonal bipyramids that share  a cornercorner with one O(6)Na3Mn3 octahedra,  a cornercorner with one O(8)Na3Mn3 octahedra, corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent O(2)Li4Mn2 octahedra,  a cornercorner with one O(3)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(4)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(5)Na3LiMn2 pentagonal pyramid,  an edgeedge with one O(1)Li4Mn2 octahedra, and  an edgeedge with one O(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 48-68°.
Na3Li4Mn5O9 crystallizes in the triclinic P1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form distorted NaO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one Mn(1)O4 tetrahedra,  a cornercorner with one Mn(2)O4 tetrahedra,  a cornercorner with one Mn(3)O4 tetrahedra,  a cornercorner with one Mn(4)O4 tetrahedra,  a cornercorner with one Mn(5)O4 tetrahedra, edges with three equivalent Na(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra,  an edgeedge with one Mn(1)O4 tetrahedra,  an edgeedge with one Mn(2)O4 tetrahedra,  an edgeedge with one Mn(3)O4 tetrahedra,  an edgeedge with one Mn(4)O4 tetrahedra, and  an edgeedge with one Mn(5)O4 tetrahedra. The Na(1)-O(3) bond length is 2.59 Å. The Na(1)-O(4) bond length is 2.42 Å. The Na(1)-O(5) bond length is 2.55 Å. The Na(1)-O(6) bond length is 2.67 Å. The Na(1)-O(7) bond length is 2.72 Å. The Na(1)-O(8) bond length is 2.45 Å. In the second Na site, Na(2) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form distorted NaO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one Mn(1)O4 tetrahedra,  a cornercorner with one Mn(2)O4 tetrahedra,  a cornercorner with one Mn(3)O4 tetrahedra,  a cornercorner with one Mn(4)O4 tetrahedra,  a cornercorner with one Mn(5)O4 tetrahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Na(3)O6 octahedra,  an edgeedge with one Mn(1)O4 tetrahedra,  an edgeedge with one Mn(2)O4 tetrahedra,  an edgeedge with one Mn(3)O4 tetrahedra,  an edgeedge with one Mn(4)O4 tetrahedra, and  an edgeedge with one Mn(5)O4 tetrahedra. The Na(2)-O(3) bond length is 2.68 Å. The Na(2)-O(4) bond length is 2.65 Å. The Na(2)-O(5) bond length is 2.46 Å. The Na(2)-O(6) bond length is 2.52 Å. The Na(2)-O(7) bond length is 2.85 Å. The Na(2)-O(8) bond length is 2.40 Å. In the third Na site, Na(3) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form distorted NaO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one Mn(1)O4 tetrahedra,  a cornercorner with one Mn(2)O4 tetrahedra,  a cornercorner with one Mn(3)O4 tetrahedra,  a cornercorner with one Mn(4)O4 tetrahedra,  a cornercorner with one Mn(5)O4 tetrahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra,  an edgeedge with one Mn(1)O4 tetrahedra,  an edgeedge with one Mn(2)O4 tetrahedra,  an edgeedge with one Mn(3)O4 tetrahedra,  an edgeedge with one Mn(4)O4 tetrahedra, and  an edgeedge with one Mn(5)O4 tetrahedra. The Na(3)-O(3) bond length is 2.45 Å. The Na(3)-O(4) bond length is 2.54 Å. The Na(3)-O(5) bond length is 2.53 Å. The Na(3)-O(6) bond length is 2.61 Å. The Na(3)-O(7) bond length is 2.85 Å. The Na(3)-O(8) bond length is 2.43 Å. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(9) atom. The Li(1)-O(1) bond length is 2.26 Å. The Li(1)-O(2) bond length is 2.01 Å. The Li(1)-O(3) bond length is 2.28 Å. The Li(1)-O(9) bond length is 1.90 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(5), and one O(9) atom. The Li(2)-O(1) bond length is 2.20 Å. The Li(2)-O(2) bond length is 2.22 Å. The Li(2)-O(5) bond length is 2.28 Å. The Li(2)-O(9) bond length is 1.88 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(4), and one O(9) atom. The Li(3)-O(1) bond length is 2.00 Å. The Li(3)-O(2) bond length is 2.18 Å. The Li(3)-O(4) bond length is 2.33 Å. The Li(3)-O(9) bond length is 1.91 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(7), and one O(9) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one Mn(1)O4 tetrahedra,  a cornercorner with one Mn(2)O4 tetrahedra,  an edgeedge with one Mn(3)O4 tetrahedra,  an edgeedge with one Mn(4)O4 tetrahedra, and  an edgeedge with one Mn(5)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-50°. The Li(4)-O(1) bond length is 1.92 Å. The Li(4)-O(2) bond length is 1.92 Å. The Li(4)-O(7) bond length is 2.16 Å. The Li(4)-O(9) bond length is 1.89 Å. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form MnO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one Mn(5)O4 tetrahedra, corners with three equivalent Mn(2)O4 tetrahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra, and  an edgeedge with one Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-27°. The Mn(1)-O(1) bond length is 2.05 Å. The Mn(1)-O(3) bond length is 1.96 Å. The Mn(1)-O(4) bond length is 1.97 Å. The Mn(1)-O(5) bond length is 1.96 Å. In the second Mn site, Mn(2) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form MnO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one Mn(4)O4 tetrahedra, corners with three equivalent Mn(1)O4 tetrahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra, and  an edgeedge with one Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-28°. The Mn(2)-O(2) bond length is 2.05 Å. The Mn(2)-O(3) bond length is 1.97 Å. The Mn(2)-O(4) bond length is 1.96 Å. The Mn(2)-O(5) bond length is 1.97 Å. In the third Mn site, Mn(3) is bonded to one O(6), one O(7), one O(8), and one O(9) atom to form MnO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra, corners with three equivalent Mn(4)O4 tetrahedra, corners with three equivalent Mn(5)O4 tetrahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one Na(3)O6 octahedra, and  an edgeedge with one Li(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 18-32°. The Mn(3)-O(6) bond length is 2.12 Å. The Mn(3)-O(7) bond length is 2.16 Å. The Mn(3)-O(8) bond length is 2.15 Å. The Mn(3)-O(9) bond length is 2.00 Å. In the fourth Mn site, Mn(4) is bonded to one O(2), one O(6), one O(7), and one O(8) atom to form MnO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one Mn(2)O4 tetrahedra, corners with three equivalent Mn(3)O4 tetrahedra, corners with three equivalent Mn(5)O4 tetrahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one Na(3)O6 octahedra, and  an edgeedge with one Li(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 13-26°. The Mn(4)-O(2) bond length is 2.09 Å. The Mn(4)-O(6) bond length is 2.11 Å. The Mn(4)-O(7) bond length is 2.14 Å. The Mn(4)-O(8) bond length is 2.12 Å. In the fifth Mn site, Mn(5) is bonded to one O(1), one O(6), one O(7), and one O(8) atom to form MnO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one Mn(1)O4 tetrahedra, corners with three equivalent Mn(3)O4 tetrahedra, corners with three equivalent Mn(4)O4 tetrahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one Na(3)O6 octahedra, and  an edgeedge with one Li(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 13-25°. The Mn(5)-O(1) bond length is 2.09 Å. The Mn(5)-O(6) bond length is 2.10 Å. The Mn(5)-O(7) bond length is 2.14 Å. The Mn(5)-O(8) bond length is 2.13 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(1), and one Mn(5) atom to form distorted OLi4Mn2 octahedra that share  a cornercorner with one O(6)Na3Mn3 octahedra,  a cornercorner with one O(8)Na3Mn3 octahedra, corners with two equivalent O(2)Li4Mn2 octahedra, corners with two equivalent O(9)Li4Mn trigonal bipyramids,  an edgeedge with one O(2)Li4Mn2 octahedra,  an edgeedge with one O(3)Na3LiMn2 pentagonal pyramid,  an edgeedge with one O(4)Na3LiMn2 pentagonal pyramid,  an edgeedge with one O(5)Na3LiMn2 pentagonal pyramid, and  an edgeedge with one O(9)Li4Mn trigonal bipyramid. The corner-sharing octahedral tilt angles range from 60-68°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(2), and one Mn(4) atom to form distorted OLi4Mn2 octahedra that share  a cornercorner with one O(6)Na3Mn3 octahedra,  a cornercorner with one O(8)Na3Mn3 octahedra, corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent O(9)Li4Mn trigonal bipyramids,  an edgeedge with one O(1)Li4Mn2 octahedra,  an edgeedge with one O(3)Na3LiMn2 pentagonal pyramid,  an edgeedge with one O(4)Na3LiMn2 pentagonal pyramid,  an edgeedge with one O(5)Na3LiMn2 pentagonal pyramid, and  an edgeedge with one O(9)Li4Mn trigonal bipyramid. The corner-sharing octahedral tilt angles range from 60-68°. In the third O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), one Li(1), one Mn(1), and one Mn(2) atom to form distorted ONa3LiMn2 pentagonal pyramids that share  a cornercorner with one O(6)Na3Mn3 octahedra,  a cornercorner with one O(8)Na3Mn3 octahedra,  a cornercorner with one O(4)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(5)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(9)Li4Mn trigonal bipyramid,  an edgeedge with one O(1)Li4Mn2 octahedra,  an edgeedge with one O(2)Li4Mn2 octahedra,  an edgeedge with one O(6)Na3Mn3 octahedra,  an edgeedge with one O(8)Na3Mn3 octahedra, edges with two equivalent O(4)Na3LiMn2 pentagonal pyramids, and edges with two equivalent O(5)Na3LiMn2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 2-11°. In the fourth O site, O(4) is bonded to one Na(1), one Na(2), one Na(3), one Li(3), one Mn(1), and one Mn(2) atom to form distorted ONa3LiMn2 pentagonal pyramids that share  a cornercorner with one O(6)Na3Mn3 octahedra,  a cornercorner with one O(8)Na3Mn3 octahedra,  a cornercorner with one O(3)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(5)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(9)Li4Mn trigonal bipyramid,  an edgeedge with one O(1)Li4Mn2 octahedra,  an edgeedge with one O(2)Li4Mn2 octahedra,  an edgeedge with one O(6)Na3Mn3 octahedra,  an edgeedge with one O(8)Na3Mn3 octahedra, edges with two equivalent O(3)Na3LiMn2 pentagonal pyramids, and edges with two equivalent O(5)Na3LiMn2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 0-11°. In the fifth O site, O(5) is bonded to one Na(1), one Na(2), one Na(3), one Li(2), one Mn(1), and one Mn(2) atom to form distorted ONa3LiMn2 pentagonal pyramids that share  a cornercorner with one O(6)Na3Mn3 octahedra,  a cornercorner with one O(8)Na3Mn3 octahedra,  a cornercorner with one O(3)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(4)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(9)Li4Mn trigonal bipyramid,  an edgeedge with one O(1)Li4Mn2 octahedra,  an edgeedge with one O(2)Li4Mn2 octahedra,  an edgeedge with one O(6)Na3Mn3 octahedra,  an edgeedge with one O(8)Na3Mn3 octahedra, edges with two equivalent O(3)Na3LiMn2 pentagonal pyramids, and edges with two equivalent O(4)Na3LiMn2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 1-9°. In the sixth O site, O(6) is bonded to one Na(1), one Na(2), one Na(3), one Mn(3), one Mn(4), and one Mn(5) atom to form distorted ONa3Mn3 octahedra that share  a cornercorner with one O(1)Li4Mn2 octahedra,  a cornercorner with one O(2)Li4Mn2 octahedra,  a cornercorner with one O(3)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(4)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(5)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(9)Li4Mn trigonal bipyramid, edges with three equivalent O(8)Na3Mn3 octahedra,  an edgeedge with one O(3)Na3LiMn2 pentagonal pyramid,  an edgeedge with one O(4)Na3LiMn2 pentagonal pyramid, and  an edgeedge with one O(5)Na3LiMn2 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 60-64°. In the seventh O site, O(7) is bonded in a 7-coordinate geometry to one Na(1), one Na(2), one Na(3), one Li(4), one Mn(3), one Mn(4), and one Mn(5) atom. In the eighth O site, O(8) is bonded to one Na(1), one Na(2), one Na(3), one Mn(3), one Mn(4), and one Mn(5) atom to form ONa3Mn3 octahedra that share  a cornercorner with one O(1)Li4Mn2 octahedra,  a cornercorner with one O(2)Li4Mn2 octahedra,  a cornercorner with one O(3)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(4)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(5)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(9)Li4Mn trigonal bipyramid, edges with three equivalent O(6)Na3Mn3 octahedra,  an edgeedge with one O(3)Na3LiMn2 pentagonal pyramid,  an edgeedge with one O(4)Na3LiMn2 pentagonal pyramid, and  an edgeedge with one O(5)Na3LiMn2 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 60-64°. In the ninth O site, O(9) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Mn(3) atom to form distorted OLi4Mn trigonal bipyramids that share  a cornercorner with one O(6)Na3Mn3 octahedra,  a cornercorner with one O(8)Na3Mn3 octahedra, corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent O(2)Li4Mn2 octahedra,  a cornercorner with one O(3)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(4)Na3LiMn2 pentagonal pyramid,  a cornercorner with one O(5)Na3LiMn2 pentagonal pyramid,  an edgeedge with one O(1)Li4Mn2 octahedra, and  an edgeedge with one O(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 48-68°.