Li3Mn3O8 is Spinel-like structured and crystallizes in the hexagonal P6_3mc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra, and edges with three equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. In the second Li site, Li(2) is bonded to one O(3) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra and corners with nine equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-71°. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(4) and three equivalent O(1) atoms. Mn(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), and two equivalent Mn(1) atoms. In the second O site, O(2) is bonded to one Li(1), one Li(2), and two equivalent Mn(1) atoms to form distorted OLi2Mn2 tetrahedra that share corners with two equivalent O(2)Li2Mn2 tetrahedra,  a cornercorner with one O(3)LiMn3 trigonal pyramid, corners with two equivalent O(4)LiMn3 trigonal pyramids, edges with two equivalent O(2)Li2Mn2 tetrahedra, and  an edgeedge with one O(3)LiMn3 trigonal pyramid. In the third O site, O(3) is bonded to one Li(2) and three equivalent Mn(1) atoms to form distorted OLiMn3 trigonal pyramids that share corners with three equivalent O(2)Li2Mn2 tetrahedra, corners with three equivalent O(4)LiMn3 trigonal pyramids, and edges with three equivalent O(2)Li2Mn2 tetrahedra. In the fourth O site, O(4) is bonded to one Li(3) and three equivalent Mn(1) atoms to form distorted OLiMn3 trigonal pyramids that share corners with six equivalent O(2)Li2Mn2 tetrahedra and corners with three equivalent O(3)LiMn3 trigonal pyramids.
Li3Mn3O8 is Spinel-like structured and crystallizes in the hexagonal P6_3mc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra, and edges with three equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. All Li(1)-O(1) bond lengths are 2.08 Å. All Li(1)-O(2) bond lengths are 2.38 Å. In the second Li site, Li(2) is bonded to one O(3) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra and corners with nine equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-71°. The Li(2)-O(3) bond length is 2.18 Å. All Li(2)-O(2) bond lengths are 1.95 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(4) and three equivalent O(1) atoms. The Li(3)-O(4) bond length is 1.82 Å. All Li(3)-O(1) bond lengths are 1.93 Å. Mn(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. The Mn(1)-O(3) bond length is 1.96 Å. The Mn(1)-O(4) bond length is 1.95 Å. Both Mn(1)-O(1) bond lengths are 1.91 Å. Both Mn(1)-O(2) bond lengths are 1.91 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), and two equivalent Mn(1) atoms. In the second O site, O(2) is bonded to one Li(1), one Li(2), and two equivalent Mn(1) atoms to form distorted OLi2Mn2 tetrahedra that share corners with two equivalent O(2)Li2Mn2 tetrahedra,  a cornercorner with one O(3)LiMn3 trigonal pyramid, corners with two equivalent O(4)LiMn3 trigonal pyramids, edges with two equivalent O(2)Li2Mn2 tetrahedra, and  an edgeedge with one O(3)LiMn3 trigonal pyramid. In the third O site, O(3) is bonded to one Li(2) and three equivalent Mn(1) atoms to form distorted OLiMn3 trigonal pyramids that share corners with three equivalent O(2)Li2Mn2 tetrahedra, corners with three equivalent O(4)LiMn3 trigonal pyramids, and edges with three equivalent O(2)Li2Mn2 tetrahedra. In the fourth O site, O(4) is bonded to one Li(3) and three equivalent Mn(1) atoms to form distorted OLiMn3 trigonal pyramids that share corners with six equivalent O(2)Li2Mn2 tetrahedra and corners with three equivalent O(3)LiMn3 trigonal pyramids.