Li8MnO6 crystallizes in the hexagonal P6_3cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Mn(1)O4 tetrahedra, corners with six equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 trigonal pyramids, edges with two equivalent Li(3)O4 tetrahedra, and edges with three equivalent Li(2)O4 trigonal pyramids. In the second Li site, Li(2) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form distorted LiO4 trigonal pyramids that share corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra, corners with six equivalent Li(2)O4 trigonal pyramids,  an edgeedge with one Mn(1)O4 tetrahedra, and edges with three equivalent Li(1)O4 tetrahedra. In the third Li site, Li(3) is bonded to one O(2) and three equivalent O(1) atoms to form LiO4 tetrahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Mn(1)O4 tetrahedra, corners with six equivalent Li(2)O4 trigonal pyramids, and edges with three equivalent Li(1)O4 tetrahedra. Mn(1) is bonded to one O(3) and three equivalent O(1) atoms to form MnO4 tetrahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent Li(3)O4 tetrahedra, and edges with three equivalent Li(2)O4 trigonal pyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), and one Mn(1) atom to form corner-sharing OLi4Mn trigonal bipyramids. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Li(3), three equivalent Li(1), and three equivalent Li(2) atoms. In the third O site, O(3) is bonded in a 7-coordinate geometry to three equivalent Li(1), three equivalent Li(2), and one Mn(1) atom.
Li8MnO6 crystallizes in the hexagonal P6_3cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Mn(1)O4 tetrahedra, corners with six equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 trigonal pyramids, edges with two equivalent Li(3)O4 tetrahedra, and edges with three equivalent Li(2)O4 trigonal pyramids. The Li(1)-O(1) bond length is 2.01 Å. The Li(1)-O(3) bond length is 2.01 Å. Both Li(1)-O(2) bond lengths are 1.99 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form distorted LiO4 trigonal pyramids that share corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra, corners with six equivalent Li(2)O4 trigonal pyramids,  an edgeedge with one Mn(1)O4 tetrahedra, and edges with three equivalent Li(1)O4 tetrahedra. The Li(2)-O(1) bond length is 2.05 Å. The Li(2)-O(3) bond length is 2.17 Å. Both Li(2)-O(2) bond lengths are 1.98 Å. In the third Li site, Li(3) is bonded to one O(2) and three equivalent O(1) atoms to form LiO4 tetrahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Mn(1)O4 tetrahedra, corners with six equivalent Li(2)O4 trigonal pyramids, and edges with three equivalent Li(1)O4 tetrahedra. The Li(3)-O(2) bond length is 2.04 Å. All Li(3)-O(1) bond lengths are 1.98 Å. Mn(1) is bonded to one O(3) and three equivalent O(1) atoms to form MnO4 tetrahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent Li(3)O4 tetrahedra, and edges with three equivalent Li(2)O4 trigonal pyramids. The Mn(1)-O(3) bond length is 1.96 Å. All Mn(1)-O(1) bond lengths are 1.77 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), and one Mn(1) atom to form corner-sharing OLi4Mn trigonal bipyramids. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Li(3), three equivalent Li(1), and three equivalent Li(2) atoms. In the third O site, O(3) is bonded in a 7-coordinate geometry to three equivalent Li(1), three equivalent Li(2), and one Mn(1) atom.