Li9Mn2Co5O16 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), two equivalent O(3), and three equivalent O(2) atoms to form LiO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Li(5)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent Li(5)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. In the second Li site, Li(2) is bonded to one O(3), one O(8), two equivalent O(1), and two equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. In the third Li site, Li(3) is bonded to one O(4), one O(7), two equivalent O(5), and two equivalent O(8) atoms to form LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent Co(1)O6 octahedra, and edges with three equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-8°. In the fourth Li site, Li(4) is bonded to one O(5), two equivalent O(7), and three equivalent O(6) atoms to form LiO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Co(3)O6 octahedra, corners with three equivalent Co(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Co(2)O6 octahedra, edges with three equivalent Co(3)O6 octahedra, and edges with four equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. In the fifth Li site, Li(5) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with four equivalent Mn(1)O6 octahedra, and edges with six equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. Mn(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form MnO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with three equivalent Li(1)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(5), two equivalent O(4), and two equivalent O(8) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. In the second Co site, Co(2) is bonded to one O(6), one O(8), two equivalent O(5), and two equivalent O(7) atoms to form CoO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with three equivalent Li(4)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. In the third Co site, Co(3) is bonded to two equivalent O(7) and four equivalent O(6) atoms to form CoO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(4)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, edges with four equivalent Co(2)O6 octahedra, and edges with six equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), two equivalent Mn(1), and one Co(1) atom to form OLi3Mn2Co octahedra that share  a cornercorner with one O(5)Li3Co3 octahedra,  a cornercorner with one O(2)Li5Mn octahedra, corners with two equivalent O(4)Li3MnCo2 octahedra, corners with two equivalent O(3)Li4Mn2 octahedra, edges with two equivalent O(8)Li3Co3 octahedra, edges with two equivalent O(1)Li3Mn2Co octahedra, edges with two equivalent O(2)Li5Mn octahedra, edges with three equivalent O(4)Li3MnCo2 octahedra, and edges with three equivalent O(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the second O site, O(2) is bonded to two equivalent Li(5), three equivalent Li(1), and one Mn(1) atom to form OLi5Mn octahedra that share  a cornercorner with one O(1)Li3Mn2Co octahedra,  a cornercorner with one O(4)Li3MnCo2 octahedra, corners with two equivalent O(3)Li4Mn2 octahedra, corners with two equivalent O(2)Li5Mn octahedra, edges with two equivalent O(1)Li3Mn2Co octahedra, edges with five equivalent O(3)Li4Mn2 octahedra, and edges with five equivalent O(2)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the third O site, O(3) is bonded to one Li(2), one Li(5), two equivalent Li(1), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share  a cornercorner with one O(8)Li3Co3 octahedra,  a cornercorner with one O(3)Li4Mn2 octahedra, corners with two equivalent O(1)Li3Mn2Co octahedra, corners with two equivalent O(2)Li5Mn octahedra, edges with two equivalent O(4)Li3MnCo2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with three equivalent O(1)Li3Mn2Co octahedra, and edges with five equivalent O(2)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Li(2), one Mn(1), and two equivalent Co(1) atoms to form OLi3MnCo2 octahedra that share  a cornercorner with one O(7)Li3Co3 octahedra,  a cornercorner with one O(2)Li5Mn octahedra, corners with two equivalent O(8)Li3Co3 octahedra, corners with two equivalent O(1)Li3Mn2Co octahedra, edges with two equivalent O(5)Li3Co3 octahedra, edges with two equivalent O(4)Li3MnCo2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with three equivalent O(8)Li3Co3 octahedra, and edges with three equivalent O(1)Li3Mn2Co octahedra. The corner-sharing octahedral tilt angles range from 1-5°. In the fifth O site, O(5) is bonded to one Li(4), two equivalent Li(3), one Co(1), and two equivalent Co(2) atoms to form OLi3Co3 octahedra that share  a cornercorner with one O(6)Li3Co3 octahedra,  a cornercorner with one O(1)Li3Mn2Co octahedra, corners with two equivalent O(7)Li3Co3 octahedra, corners with two equivalent O(8)Li3Co3 octahedra, edges with two equivalent O(5)Li3Co3 octahedra, edges with two equivalent O(6)Li3Co3 octahedra, edges with two equivalent O(4)Li3MnCo2 octahedra, edges with three equivalent O(7)Li3Co3 octahedra, and edges with three equivalent O(8)Li3Co3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the sixth O site, O(6) is bonded to three equivalent Li(4), one Co(2), and two equivalent Co(3) atoms to form a mixture of corner and edge-sharing OLi3Co3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the seventh O site, O(7) is bonded to one Li(3), two equivalent Li(4), one Co(3), and two equivalent Co(2) atoms to form OLi3Co3 octahedra that share  a cornercorner with one O(7)Li3Co3 octahedra,  a cornercorner with one O(4)Li3MnCo2 octahedra, corners with two equivalent O(5)Li3Co3 octahedra, corners with two equivalent O(6)Li3Co3 octahedra, edges with two equivalent O(7)Li3Co3 octahedra, edges with two equivalent O(8)Li3Co3 octahedra, edges with three equivalent O(5)Li3Co3 octahedra, and edges with five equivalent O(6)Li3Co3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the eighth O site, O(8) is bonded to one Li(2), two equivalent Li(3), one Co(2), and two equivalent Co(1) atoms to form OLi3Co3 octahedra that share  a cornercorner with one O(6)Li3Co3 octahedra,  a cornercorner with one O(3)Li4Mn2 octahedra, corners with two equivalent O(5)Li3Co3 octahedra, corners with two equivalent O(4)Li3MnCo2 octahedra, edges with two equivalent O(7)Li3Co3 octahedra, edges with two equivalent O(8)Li3Co3 octahedra, edges with two equivalent O(1)Li3Mn2Co octahedra, edges with three equivalent O(5)Li3Co3 octahedra, and edges with three equivalent O(4)Li3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-3°.
Li9Mn2Co5O16 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), two equivalent O(3), and three equivalent O(2) atoms to form LiO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Li(5)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent Li(5)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. The Li(1)-O(1) bond length is 2.24 Å. Both Li(1)-O(3) bond lengths are 2.22 Å. There are two shorter (2.01 Å) and one longer (2.22 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) is bonded to one O(3), one O(8), two equivalent O(1), and two equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. The Li(2)-O(3) bond length is 2.08 Å. The Li(2)-O(8) bond length is 2.13 Å. Both Li(2)-O(1) bond lengths are 2.18 Å. Both Li(2)-O(4) bond lengths are 2.12 Å. In the third Li site, Li(3) is bonded to one O(4), one O(7), two equivalent O(5), and two equivalent O(8) atoms to form LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent Co(1)O6 octahedra, and edges with three equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-8°. The Li(3)-O(4) bond length is 2.23 Å. The Li(3)-O(7) bond length is 2.17 Å. Both Li(3)-O(5) bond lengths are 2.20 Å. Both Li(3)-O(8) bond lengths are 2.09 Å. In the fourth Li site, Li(4) is bonded to one O(5), two equivalent O(7), and three equivalent O(6) atoms to form LiO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Co(3)O6 octahedra, corners with three equivalent Co(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Co(2)O6 octahedra, edges with three equivalent Co(3)O6 octahedra, and edges with four equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. The Li(4)-O(5) bond length is 2.21 Å. Both Li(4)-O(7) bond lengths are 2.22 Å. There are two shorter (2.08 Å) and one longer (2.09 Å) Li(4)-O(6) bond length. In the fifth Li site, Li(5) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with four equivalent Mn(1)O6 octahedra, and edges with six equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. Both Li(5)-O(3) bond lengths are 2.14 Å. All Li(5)-O(2) bond lengths are 2.10 Å. Mn(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form MnO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with three equivalent Li(1)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. The Mn(1)-O(2) bond length is 1.83 Å. The Mn(1)-O(4) bond length is 2.12 Å. Both Mn(1)-O(1) bond lengths are 1.97 Å. Both Mn(1)-O(3) bond lengths are 1.93 Å. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(5), two equivalent O(4), and two equivalent O(8) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. The Co(1)-O(1) bond length is 2.07 Å. The Co(1)-O(5) bond length is 2.10 Å. Both Co(1)-O(4) bond lengths are 1.99 Å. Both Co(1)-O(8) bond lengths are 1.98 Å. In the second Co site, Co(2) is bonded to one O(6), one O(8), two equivalent O(5), and two equivalent O(7) atoms to form CoO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with three equivalent Li(4)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. The Co(2)-O(6) bond length is 2.12 Å. The Co(2)-O(8) bond length is 2.16 Å. Both Co(2)-O(5) bond lengths are 1.95 Å. Both Co(2)-O(7) bond lengths are 1.94 Å. In the third Co site, Co(3) is bonded to two equivalent O(7) and four equivalent O(6) atoms to form CoO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(4)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, edges with four equivalent Co(2)O6 octahedra, and edges with six equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. Both Co(3)-O(7) bond lengths are 2.10 Å. All Co(3)-O(6) bond lengths are 2.00 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), two equivalent Mn(1), and one Co(1) atom to form OLi3Mn2Co octahedra that share  a cornercorner with one O(5)Li3Co3 octahedra,  a cornercorner with one O(2)Li5Mn octahedra, corners with two equivalent O(4)Li3MnCo2 octahedra, corners with two equivalent O(3)Li4Mn2 octahedra, edges with two equivalent O(8)Li3Co3 octahedra, edges with two equivalent O(1)Li3Mn2Co octahedra, edges with two equivalent O(2)Li5Mn octahedra, edges with three equivalent O(4)Li3MnCo2 octahedra, and edges with three equivalent O(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the second O site, O(2) is bonded to two equivalent Li(5), three equivalent Li(1), and one Mn(1) atom to form OLi5Mn octahedra that share  a cornercorner with one O(1)Li3Mn2Co octahedra,  a cornercorner with one O(4)Li3MnCo2 octahedra, corners with two equivalent O(3)Li4Mn2 octahedra, corners with two equivalent O(2)Li5Mn octahedra, edges with two equivalent O(1)Li3Mn2Co octahedra, edges with five equivalent O(3)Li4Mn2 octahedra, and edges with five equivalent O(2)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the third O site, O(3) is bonded to one Li(2), one Li(5), two equivalent Li(1), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share  a cornercorner with one O(8)Li3Co3 octahedra,  a cornercorner with one O(3)Li4Mn2 octahedra, corners with two equivalent O(1)Li3Mn2Co octahedra, corners with two equivalent O(2)Li5Mn octahedra, edges with two equivalent O(4)Li3MnCo2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with three equivalent O(1)Li3Mn2Co octahedra, and edges with five equivalent O(2)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Li(2), one Mn(1), and two equivalent Co(1) atoms to form OLi3MnCo2 octahedra that share  a cornercorner with one O(7)Li3Co3 octahedra,  a cornercorner with one O(2)Li5Mn octahedra, corners with two equivalent O(8)Li3Co3 octahedra, corners with two equivalent O(1)Li3Mn2Co octahedra, edges with two equivalent O(5)Li3Co3 octahedra, edges with two equivalent O(4)Li3MnCo2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with three equivalent O(8)Li3Co3 octahedra, and edges with three equivalent O(1)Li3Mn2Co octahedra. The corner-sharing octahedral tilt angles range from 1-5°. In the fifth O site, O(5) is bonded to one Li(4), two equivalent Li(3), one Co(1), and two equivalent Co(2) atoms to form OLi3Co3 octahedra that share  a cornercorner with one O(6)Li3Co3 octahedra,  a cornercorner with one O(1)Li3Mn2Co octahedra, corners with two equivalent O(7)Li3Co3 octahedra, corners with two equivalent O(8)Li3Co3 octahedra, edges with two equivalent O(5)Li3Co3 octahedra, edges with two equivalent O(6)Li3Co3 octahedra, edges with two equivalent O(4)Li3MnCo2 octahedra, edges with three equivalent O(7)Li3Co3 octahedra, and edges with three equivalent O(8)Li3Co3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the sixth O site, O(6) is bonded to three equivalent Li(4), one Co(2), and two equivalent Co(3) atoms to form a mixture of corner and edge-sharing OLi3Co3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the seventh O site, O(7) is bonded to one Li(3), two equivalent Li(4), one Co(3), and two equivalent Co(2) atoms to form OLi3Co3 octahedra that share  a cornercorner with one O(7)Li3Co3 octahedra,  a cornercorner with one O(4)Li3MnCo2 octahedra, corners with two equivalent O(5)Li3Co3 octahedra, corners with two equivalent O(6)Li3Co3 octahedra, edges with two equivalent O(7)Li3Co3 octahedra, edges with two equivalent O(8)Li3Co3 octahedra, edges with three equivalent O(5)Li3Co3 octahedra, and edges with five equivalent O(6)Li3Co3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the eighth O site, O(8) is bonded to one Li(2), two equivalent Li(3), one Co(2), and two equivalent Co(1) atoms to form OLi3Co3 octahedra that share  a cornercorner with one O(6)Li3Co3 octahedra,  a cornercorner with one O(3)Li4Mn2 octahedra, corners with two equivalent O(5)Li3Co3 octahedra, corners with two equivalent O(4)Li3MnCo2 octahedra, edges with two equivalent O(7)Li3Co3 octahedra, edges with two equivalent O(8)Li3Co3 octahedra, edges with two equivalent O(1)Li3Mn2Co octahedra, edges with three equivalent O(5)Li3Co3 octahedra, and edges with three equivalent O(4)Li3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-3°.