Li3Mn2O4 crystallizes in the orthorhombic Imma space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with six equivalent Mn(1)O6 octahedra, corners with six equivalent Mn(2)O6 octahedra, faces with two equivalent Li(2)O6 octahedra, and faces with two equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-58°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with six equivalent Mn(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, edges with four equivalent Mn(1)O6 octahedra, and faces with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 2°. In the third Li site, Li(3) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, edges with four equivalent Mn(2)O6 octahedra, and faces with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 1-7°. 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(3)O6 octahedra, corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. 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(2)O6 octahedra, corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 2°. 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 to one Li(1), one Li(3), two equivalent Li(2), one Mn(1), and two equivalent Mn(2) atoms to form a mixture of distorted face, corner, and edge-sharing OLi4Mn3 pentagonal bipyramids.
Li3Mn2O4 crystallizes in the orthorhombic Imma space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with six equivalent Mn(1)O6 octahedra, corners with six equivalent Mn(2)O6 octahedra, faces with two equivalent Li(2)O6 octahedra, and faces with two equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-58°. Both Li(1)-O(1) bond lengths are 1.90 Å. Both Li(1)-O(2) bond lengths are 1.90 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with six equivalent Mn(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, edges with four equivalent Mn(1)O6 octahedra, and faces with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 2°. Both Li(2)-O(1) bond lengths are 2.27 Å. All Li(2)-O(2) bond lengths are 2.21 Å. In the third Li site, Li(3) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, edges with four equivalent Mn(2)O6 octahedra, and faces with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 1-7°. Both Li(3)-O(2) bond lengths are 2.08 Å. All Li(3)-O(1) bond lengths are 2.19 Å. 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(3)O6 octahedra, corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. Both Mn(1)-O(2) bond lengths are 2.16 Å. All Mn(1)-O(1) bond lengths are 2.25 Å. 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(2)O6 octahedra, corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 2°. Both Mn(2)-O(1) bond lengths are 1.98 Å. All Mn(2)-O(2) bond lengths are 2.22 Å. 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 to one Li(1), one Li(3), two equivalent Li(2), one Mn(1), and two equivalent Mn(2) atoms to form a mixture of distorted face, corner, and edge-sharing OLi4Mn3 pentagonal bipyramids.