Li5Mn5O12 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent Li(2)O4 trigonal pyramids,  an edgeedge with one Li(3)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-62°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Li(3)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-66°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O4 trigonal pyramids, corners with two equivalent Li(2)O4 trigonal pyramids, edges with six equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O4 trigonal pyramids, and edges with two equivalent Li(2)O4 trigonal pyramids. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O4 trigonal pyramids, corners with two equivalent Li(2)O4 trigonal pyramids, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Mn(3)O6 octahedra. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O4 trigonal pyramids, corners with two equivalent Li(2)O4 trigonal pyramids, edges with three equivalent Li(3)O6 octahedra, edges with three equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O4 trigonal pyramids, and edges with two equivalent Li(2)O4 trigonal pyramids. In the third Mn site, Mn(3) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O4 trigonal pyramids, corners with two equivalent Li(2)O4 trigonal pyramids, and edges with six equivalent Mn(1)O6 octahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), and two equivalent Mn(2) atoms to form a mixture of corner and edge-sharing OLi3Mn2 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), and two equivalent Mn(2) atoms to form a mixture of corner and edge-sharing OLi3Mn2 square pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(3), and two equivalent Mn(1) atoms. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Mn(3), and two equivalent Mn(1) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Mn(3) and two equivalent Mn(1) atoms. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Li(3), and two equivalent Mn(2) atoms to form a mixture of corner and edge-sharing OLi3Mn2 square pyramids.
Li5Mn5O12 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent Li(2)O4 trigonal pyramids,  an edgeedge with one Li(3)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-62°. The Li(1)-O(1) bond length is 1.96 Å. The Li(1)-O(2) bond length is 1.96 Å. The Li(1)-O(3) bond length is 1.97 Å. The Li(1)-O(6) bond length is 2.04 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Li(3)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-66°. The Li(2)-O(1) bond length is 1.97 Å. The Li(2)-O(2) bond length is 1.96 Å. The Li(2)-O(4) bond length is 2.02 Å. The Li(2)-O(6) bond length is 2.03 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O4 trigonal pyramids, corners with two equivalent Li(2)O4 trigonal pyramids, edges with six equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O4 trigonal pyramids, and edges with two equivalent Li(2)O4 trigonal pyramids. Both Li(3)-O(1) bond lengths are 2.16 Å. Both Li(3)-O(2) bond lengths are 2.19 Å. Both Li(3)-O(6) bond lengths are 2.02 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O4 trigonal pyramids, corners with two equivalent Li(2)O4 trigonal pyramids, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Mn(3)O6 octahedra. There is one shorter (1.91 Å) and one longer (1.94 Å) Mn(1)-O(3) bond length. There is one shorter (1.95 Å) and one longer (1.98 Å) Mn(1)-O(4) bond length. There is one shorter (1.94 Å) and one longer (1.95 Å) Mn(1)-O(5) bond length. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O4 trigonal pyramids, corners with two equivalent Li(2)O4 trigonal pyramids, edges with three equivalent Li(3)O6 octahedra, edges with three equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O4 trigonal pyramids, and edges with two equivalent Li(2)O4 trigonal pyramids. There is one shorter (1.95 Å) and one longer (1.97 Å) Mn(2)-O(1) bond length. There is one shorter (1.94 Å) and one longer (1.96 Å) Mn(2)-O(2) bond length. There is one shorter (1.96 Å) and one longer (1.97 Å) Mn(2)-O(6) bond length. In the third Mn site, Mn(3) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O4 trigonal pyramids, corners with two equivalent Li(2)O4 trigonal pyramids, and edges with six equivalent Mn(1)O6 octahedra. Both Mn(3)-O(3) bond lengths are 2.16 Å. Both Mn(3)-O(4) bond lengths are 2.00 Å. Both Mn(3)-O(5) bond lengths are 1.95 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), and two equivalent Mn(2) atoms to form a mixture of corner and edge-sharing OLi3Mn2 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), and two equivalent Mn(2) atoms to form a mixture of corner and edge-sharing OLi3Mn2 square pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(3), and two equivalent Mn(1) atoms. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Mn(3), and two equivalent Mn(1) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Mn(3) and two equivalent Mn(1) atoms. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Li(3), and two equivalent Mn(2) atoms to form a mixture of corner and edge-sharing OLi3Mn2 square pyramids.