Li3Mn2O5 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with six equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. In the second Li site, Li(2) is bonded to two equivalent O(4) and four equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 11°. In the third Li site, Li(3) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-16°. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one O(1), one O(4), and three equivalent O(5) atoms. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with three equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-16°. In the second Mn site, Mn(2) is bonded to one O(1), two equivalent O(3), and three equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(4), two equivalent Li(3), one Mn(2), and two equivalent Mn(1) atoms to form distorted OLi3Mn3 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra,  a cornercorner with one O(5)Li5Mn octahedra, corners with two equivalent O(3)Li3Mn3 octahedra, corners with three equivalent O(4)Li3Mn2 square pyramids, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(5)Li5Mn octahedra, edges with three equivalent O(3)Li3Mn3 octahedra, and edges with two equivalent O(4)Li3Mn2 square pyramids. The corner-sharing octahedral tilt angles range from 1-13°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(1), and three equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(1)Li3Mn3 octahedra, corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(3)Li3Mn3 octahedra,  a cornercorner with one O(4)Li3Mn2 square pyramid, edges with two equivalent O(1)Li3Mn3 octahedra, edges with five equivalent O(2)Li3Mn3 octahedra, and edges with five equivalent O(3)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(3), one Mn(1), and two equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(5)Li5Mn octahedra, corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with three equivalent O(1)Li3Mn3 octahedra, edges with five equivalent O(2)Li3Mn3 octahedra, and edges with two equivalent O(4)Li3Mn2 square pyramids. The corner-sharing octahedral tilt angles range from 0-13°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Li(4), and two equivalent Mn(1) atoms to form distorted OLi3Mn2 square pyramids that share  a cornercorner with one O(2)Li3Mn3 octahedra, corners with three equivalent O(1)Li3Mn3 octahedra, corners with three equivalent O(5)Li5Mn octahedra, corners with three equivalent O(4)Li3Mn2 square pyramids, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, and edges with three equivalent O(5)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 1-84°. In the fifth O site, O(5) is bonded to two equivalent Li(2), three equivalent Li(4), and one Mn(1) atom to form OLi5Mn octahedra that share  a cornercorner with one O(1)Li3Mn3 octahedra,  a cornercorner with one O(3)Li3Mn3 octahedra, corners with two equivalent O(5)Li5Mn octahedra, corners with three equivalent O(4)Li3Mn2 square pyramids, edges with two equivalent O(1)Li3Mn3 octahedra, edges with five equivalent O(5)Li5Mn octahedra, and edges with three equivalent O(4)Li3Mn2 square pyramids. The corner-sharing octahedral tilt angles range from 0-5°.
Li3Mn2O5 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with six equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. Both Li(1)-O(3) bond lengths are 2.16 Å. There are two shorter (2.10 Å) and two longer (2.19 Å) Li(1)-O(2) bond lengths. In the second Li site, Li(2) is bonded to two equivalent O(4) and four equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 11°. Both Li(2)-O(4) bond lengths are 2.05 Å. There are two shorter (2.10 Å) and two longer (2.25 Å) Li(2)-O(5) bond lengths. In the third Li site, Li(3) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-16°. The Li(3)-O(2) bond length is 2.17 Å. The Li(3)-O(4) bond length is 2.04 Å. There is one shorter (2.11 Å) and one longer (2.53 Å) Li(3)-O(1) bond length. There is one shorter (2.06 Å) and one longer (2.11 Å) Li(3)-O(3) bond length. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one O(1), one O(4), and three equivalent O(5) atoms. The Li(4)-O(1) bond length is 2.27 Å. The Li(4)-O(4) bond length is 2.17 Å. There are a spread of Li(4)-O(5) bond distances ranging from 2.00-2.06 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with three equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-16°. The Mn(1)-O(3) bond length is 2.05 Å. The Mn(1)-O(5) bond length is 1.82 Å. There is one shorter (2.00 Å) and one longer (2.04 Å) Mn(1)-O(1) bond length. Both Mn(1)-O(4) bond lengths are 1.94 Å. In the second Mn site, Mn(2) is bonded to one O(1), two equivalent O(3), and three equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. The Mn(2)-O(1) bond length is 1.99 Å. There is one shorter (1.94 Å) and one longer (2.22 Å) Mn(2)-O(3) bond length. There are a spread of Mn(2)-O(2) bond distances ranging from 1.95-2.27 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(4), two equivalent Li(3), one Mn(2), and two equivalent Mn(1) atoms to form distorted OLi3Mn3 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra,  a cornercorner with one O(5)Li5Mn octahedra, corners with two equivalent O(3)Li3Mn3 octahedra, corners with three equivalent O(4)Li3Mn2 square pyramids, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(5)Li5Mn octahedra, edges with three equivalent O(3)Li3Mn3 octahedra, and edges with two equivalent O(4)Li3Mn2 square pyramids. The corner-sharing octahedral tilt angles range from 1-13°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(1), and three equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(1)Li3Mn3 octahedra, corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(3)Li3Mn3 octahedra,  a cornercorner with one O(4)Li3Mn2 square pyramid, edges with two equivalent O(1)Li3Mn3 octahedra, edges with five equivalent O(2)Li3Mn3 octahedra, and edges with five equivalent O(3)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(3), one Mn(1), and two equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(5)Li5Mn octahedra, corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with three equivalent O(1)Li3Mn3 octahedra, edges with five equivalent O(2)Li3Mn3 octahedra, and edges with two equivalent O(4)Li3Mn2 square pyramids. The corner-sharing octahedral tilt angles range from 0-13°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Li(4), and two equivalent Mn(1) atoms to form distorted OLi3Mn2 square pyramids that share  a cornercorner with one O(2)Li3Mn3 octahedra, corners with three equivalent O(1)Li3Mn3 octahedra, corners with three equivalent O(5)Li5Mn octahedra, corners with three equivalent O(4)Li3Mn2 square pyramids, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, and edges with three equivalent O(5)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 1-84°. In the fifth O site, O(5) is bonded to two equivalent Li(2), three equivalent Li(4), and one Mn(1) atom to form OLi5Mn octahedra that share  a cornercorner with one O(1)Li3Mn3 octahedra,  a cornercorner with one O(3)Li3Mn3 octahedra, corners with two equivalent O(5)Li5Mn octahedra, corners with three equivalent O(4)Li3Mn2 square pyramids, edges with two equivalent O(1)Li3Mn3 octahedra, edges with five equivalent O(5)Li5Mn octahedra, and edges with three equivalent O(4)Li3Mn2 square pyramids. The corner-sharing octahedral tilt angles range from 0-5°.