LiMn2O4 is Spinel-like structured and crystallizes in the trigonal R3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with nine equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-62°. In the second Li site, Li(2) is bonded to three equivalent O(2) and three equivalent O(3) atoms to form LiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Mn(2)O4 tetrahedra, and edges with six equivalent Mn(1)O6 octahedra. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Mn(2)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. In the second Mn site, Mn(2) is bonded to one O(4) and three equivalent O(3) atoms to form MnO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with nine equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-63°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1) and three equivalent Mn(1) atoms to form distorted OLiMn3 trigonal pyramids that share corners with six equivalent O(3)LiMn3 tetrahedra, corners with three equivalent O(2)Li2Mn2 trigonal pyramids, corners with three equivalent O(4)Mn4 trigonal pyramids, and edges with three equivalent O(2)Li2Mn2 trigonal pyramids. 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 trigonal pyramids that share corners with seven equivalent O(3)LiMn3 tetrahedra,  a cornercorner with one O(1)LiMn3 trigonal pyramid, corners with two equivalent O(2)Li2Mn2 trigonal pyramids, corners with two equivalent O(4)Mn4 trigonal pyramids,  an edgeedge with one O(1)LiMn3 trigonal pyramid, and edges with two equivalent O(2)Li2Mn2 trigonal pyramids. In the third O site, O(3) is bonded to one Li(2), one Mn(2), and two equivalent Mn(1) atoms to form distorted OLiMn3 tetrahedra that share corners with two equivalent O(3)LiMn3 tetrahedra,  a cornercorner with one O(4)Mn4 trigonal pyramid, corners with two equivalent O(1)LiMn3 trigonal pyramids, corners with seven equivalent O(2)Li2Mn2 trigonal pyramids, edges with two equivalent O(3)LiMn3 tetrahedra, and  an edgeedge with one O(4)Mn4 trigonal pyramid. In the fourth O site, O(4) is bonded to one Mn(2) and three equivalent Mn(1) atoms to form distorted OMn4 trigonal pyramids that share corners with three equivalent O(3)LiMn3 tetrahedra, corners with three equivalent O(1)LiMn3 trigonal pyramids, corners with six equivalent O(2)Li2Mn2 trigonal pyramids, and edges with three equivalent O(3)LiMn3 tetrahedra.
LiMn2O4 is Spinel-like structured and crystallizes in the trigonal R3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with nine equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-62°. The Li(1)-O(1) bond length is 2.13 Å. All Li(1)-O(2) bond lengths are 1.97 Å. In the second Li site, Li(2) is bonded to three equivalent O(2) and three equivalent O(3) atoms to form LiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Mn(2)O4 tetrahedra, and edges with six equivalent Mn(1)O6 octahedra. All Li(2)-O(2) bond lengths are 2.09 Å. All Li(2)-O(3) bond lengths are 2.08 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Mn(2)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The Mn(1)-O(1) bond length is 1.98 Å. The Mn(1)-O(4) bond length is 2.01 Å. Both Mn(1)-O(2) bond lengths are 1.91 Å. Both Mn(1)-O(3) bond lengths are 1.95 Å. In the second Mn site, Mn(2) is bonded to one O(4) and three equivalent O(3) atoms to form MnO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with nine equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-63°. The Mn(2)-O(4) bond length is 2.08 Å. All Mn(2)-O(3) bond lengths are 2.00 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1) and three equivalent Mn(1) atoms to form distorted OLiMn3 trigonal pyramids that share corners with six equivalent O(3)LiMn3 tetrahedra, corners with three equivalent O(2)Li2Mn2 trigonal pyramids, corners with three equivalent O(4)Mn4 trigonal pyramids, and edges with three equivalent O(2)Li2Mn2 trigonal pyramids. 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 trigonal pyramids that share corners with seven equivalent O(3)LiMn3 tetrahedra,  a cornercorner with one O(1)LiMn3 trigonal pyramid, corners with two equivalent O(2)Li2Mn2 trigonal pyramids, corners with two equivalent O(4)Mn4 trigonal pyramids,  an edgeedge with one O(1)LiMn3 trigonal pyramid, and edges with two equivalent O(2)Li2Mn2 trigonal pyramids. In the third O site, O(3) is bonded to one Li(2), one Mn(2), and two equivalent Mn(1) atoms to form distorted OLiMn3 tetrahedra that share corners with two equivalent O(3)LiMn3 tetrahedra,  a cornercorner with one O(4)Mn4 trigonal pyramid, corners with two equivalent O(1)LiMn3 trigonal pyramids, corners with seven equivalent O(2)Li2Mn2 trigonal pyramids, edges with two equivalent O(3)LiMn3 tetrahedra, and  an edgeedge with one O(4)Mn4 trigonal pyramid. In the fourth O site, O(4) is bonded to one Mn(2) and three equivalent Mn(1) atoms to form distorted OMn4 trigonal pyramids that share corners with three equivalent O(3)LiMn3 tetrahedra, corners with three equivalent O(1)LiMn3 trigonal pyramids, corners with six equivalent O(2)Li2Mn2 trigonal pyramids, and edges with three equivalent O(3)LiMn3 tetrahedra.