Li3Mn4O8 crystallizes in the trigonal R-3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(2) and three equivalent O(1) atoms. In the second Li site, Li(2) is bonded to six equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra and edges with six equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles are 12°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to six equivalent O(1) atoms to form distorted MnO6 octahedra that share corners with six equivalent Li(2)O6 octahedra and edges with six equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles are 12°. In the second Mn site, Mn(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MnO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Mn(1), and two equivalent Mn(2) atoms to form distorted OLi2Mn3 trigonal bipyramids that share corners with six equivalent O(1)Li2Mn3 trigonal bipyramids, corners with three equivalent O(2)LiMn3 trigonal pyramids, edges with six equivalent O(1)Li2Mn3 trigonal bipyramids, and  an edgeedge with one O(2)LiMn3 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1) and three equivalent Mn(2) atoms to form distorted OLiMn3 trigonal pyramids that share corners with nine equivalent O(1)Li2Mn3 trigonal bipyramids, corners with three equivalent O(2)LiMn3 trigonal pyramids, and edges with three equivalent O(1)Li2Mn3 trigonal bipyramids.
Li3Mn4O8 crystallizes in the trigonal R-3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(2) and three equivalent O(1) atoms. The Li(1)-O(2) bond length is 1.91 Å. All Li(1)-O(1) bond lengths are 2.11 Å. In the second Li site, Li(2) is bonded to six equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra and edges with six equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles are 12°. All Li(2)-O(1) bond lengths are 2.09 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to six equivalent O(1) atoms to form distorted MnO6 octahedra that share corners with six equivalent Li(2)O6 octahedra and edges with six equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles are 12°. All Mn(1)-O(1) bond lengths are 2.20 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MnO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. Both Mn(2)-O(2) bond lengths are 2.00 Å. All Mn(2)-O(1) bond lengths are 1.97 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Mn(1), and two equivalent Mn(2) atoms to form distorted OLi2Mn3 trigonal bipyramids that share corners with six equivalent O(1)Li2Mn3 trigonal bipyramids, corners with three equivalent O(2)LiMn3 trigonal pyramids, edges with six equivalent O(1)Li2Mn3 trigonal bipyramids, and  an edgeedge with one O(2)LiMn3 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1) and three equivalent Mn(2) atoms to form distorted OLiMn3 trigonal pyramids that share corners with nine equivalent O(1)Li2Mn3 trigonal bipyramids, corners with three equivalent O(2)LiMn3 trigonal pyramids, and edges with three equivalent O(1)Li2Mn3 trigonal bipyramids.