Li3Mn2O4 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent Li(2), two equivalent Li(3), two equivalent O(1), and two equivalent O(2) atoms to form LiLi4O4 tetrahedra that share corners with six equivalent Mn(1)O6 octahedra, corners with six equivalent Mn(2)O6 octahedra, and corners with four equivalent Li(1)Li4O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-56°. In the second Li site, Li(2) is bonded in a 8-coordinate geometry to two equivalent Li(1), two equivalent O(1), and four equivalent O(2) atoms. In the third Li site, Li(3) is bonded in a 8-coordinate geometry to two equivalent Li(1), two equivalent O(2), and four equivalent O(1) atoms. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MnO6 octahedra that share corners with six equivalent Li(1)Li4O4 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. In the second Mn site, Mn(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Li(1)Li4O4 tetrahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), two equivalent Li(3), one Mn(2), and two equivalent Mn(1) atoms. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Li(1), one Li(3), two equivalent Li(2), one Mn(1), and two equivalent Mn(2) atoms.
Li3Mn2O4 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent Li(2), two equivalent Li(3), two equivalent O(1), and two equivalent O(2) atoms to form LiLi4O4 tetrahedra that share corners with six equivalent Mn(1)O6 octahedra, corners with six equivalent Mn(2)O6 octahedra, and corners with four equivalent Li(1)Li4O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-56°. Both Li(1)-Li(2) bond lengths are 1.91 Å. Both Li(1)-Li(3) bond lengths are 1.90 Å. Both Li(1)-O(1) bond lengths are 1.89 Å. Both Li(1)-O(2) bond lengths are 1.89 Å. In the second Li site, Li(2) is bonded in a 8-coordinate geometry to two equivalent Li(1), two equivalent O(1), and four equivalent O(2) atoms. Both Li(2)-O(1) bond lengths are 2.13 Å. There are two shorter (2.13 Å) and two longer (2.32 Å) Li(2)-O(2) bond lengths. In the third Li site, Li(3) is bonded in a 8-coordinate geometry to two equivalent Li(1), two equivalent O(2), and four equivalent O(1) atoms. Both Li(3)-O(2) bond lengths are 2.10 Å. There are two shorter (2.10 Å) and two longer (2.36 Å) Li(3)-O(1) bond lengths. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MnO6 octahedra that share corners with six equivalent Li(1)Li4O4 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. Both Mn(1)-O(2) bond lengths are 2.07 Å. There are two shorter (2.06 Å) and two longer (2.49 Å) Mn(1)-O(1) bond lengths. In the second Mn site, Mn(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Li(1)Li4O4 tetrahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. Both Mn(2)-O(1) bond lengths are 2.04 Å. There are two shorter (2.04 Å) and two longer (2.52 Å) Mn(2)-O(2) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), two equivalent Li(3), one Mn(2), and two equivalent Mn(1) atoms. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Li(1), one Li(3), two equivalent Li(2), one Mn(1), and two equivalent Mn(2) atoms.