Li5MnO5 crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), and three equivalent O(1) atoms to form a mixture of distorted corner and edge-sharing LiO5 square pyramids. In the second Li site, Li(2) is bonded to one O(1), one O(2), and three equivalent O(3) atoms to form a mixture of corner and edge-sharing LiO5 square pyramids. In the third Li site, Li(3) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. Mn(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), three equivalent Li(1), and one Mn(1) atom to form distorted OLi5Mn octahedra that share corners with four equivalent O(1)Li5Mn octahedra, edges with two equivalent O(1)Li5Mn octahedra, edges with three equivalent O(2)Li4Mn2 octahedra, and edges with five equivalent O(3)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 1-23°. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Mn(1) atoms to form distorted OLi4Mn2 octahedra that share corners with two equivalent O(2)Li4Mn2 octahedra, corners with four equivalent O(3)Li5Mn octahedra, edges with four equivalent O(3)Li5Mn octahedra, and edges with six equivalent O(1)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-15°. In the third O site, O(3) is bonded to one Li(1), one Li(3), three equivalent Li(2), and one Mn(1) atom to form OLi5Mn octahedra that share corners with two equivalent O(2)Li4Mn2 octahedra, corners with four equivalent O(3)Li5Mn octahedra, edges with two equivalent O(2)Li4Mn2 octahedra, edges with two equivalent O(3)Li5Mn octahedra, and edges with five equivalent O(1)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 5-22°.
Li5MnO5 crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), and three equivalent O(1) atoms to form a mixture of distorted corner and edge-sharing LiO5 square pyramids. The Li(1)-O(2) bond length is 2.11 Å. The Li(1)-O(3) bond length is 1.99 Å. There are a spread of Li(1)-O(1) bond distances ranging from 1.95-2.19 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), and three equivalent O(3) atoms to form a mixture of corner and edge-sharing LiO5 square pyramids. The Li(2)-O(1) bond length is 2.02 Å. The Li(2)-O(2) bond length is 2.22 Å. There are a spread of Li(2)-O(3) bond distances ranging from 2.01-2.12 Å. In the third Li site, Li(3) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. Both Li(3)-O(1) bond lengths are 1.96 Å. Both Li(3)-O(3) bond lengths are 2.04 Å. Mn(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Mn(1)-O(1) bond lengths are 1.82 Å. There is one shorter (1.72 Å) and one longer (2.40 Å) Mn(1)-O(2) bond length. Both Mn(1)-O(3) bond lengths are 1.93 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), three equivalent Li(1), and one Mn(1) atom to form distorted OLi5Mn octahedra that share corners with four equivalent O(1)Li5Mn octahedra, edges with two equivalent O(1)Li5Mn octahedra, edges with three equivalent O(2)Li4Mn2 octahedra, and edges with five equivalent O(3)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 1-23°. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Mn(1) atoms to form distorted OLi4Mn2 octahedra that share corners with two equivalent O(2)Li4Mn2 octahedra, corners with four equivalent O(3)Li5Mn octahedra, edges with four equivalent O(3)Li5Mn octahedra, and edges with six equivalent O(1)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-15°. In the third O site, O(3) is bonded to one Li(1), one Li(3), three equivalent Li(2), and one Mn(1) atom to form OLi5Mn octahedra that share corners with two equivalent O(2)Li4Mn2 octahedra, corners with four equivalent O(3)Li5Mn octahedra, edges with two equivalent O(2)Li4Mn2 octahedra, edges with two equivalent O(3)Li5Mn octahedra, and edges with five equivalent O(1)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 5-22°.