Li4MnCo2O7 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one Co(2)O6 octahedra, corners with five equivalent Mn(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 two equivalent Li(5)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-12°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with four equivalent Li(5)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. In the third Li site, Li(3) is bonded to one O(3), one O(5), two equivalent O(4), and two equivalent O(7) 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 four equivalent Co(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. In the fourth Li site, Li(4) is bonded to one O(7), two equivalent O(5), and three equivalent O(6) atoms to form LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra, corners with four equivalent Co(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(4)O6 octahedra, and edges with four equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. 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(3)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. Mn(1) is bonded to one O(2), one O(7), two equivalent O(1), and two equivalent O(3) atoms to form MnO6 octahedra that share  a cornercorner with one Li(4)O6 octahedra, corners with five equivalent Li(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 two equivalent Li(5)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-12°. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(6), two equivalent O(4), and two equivalent O(7) atoms to form CoO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. In the second Co site, Co(2) is bonded to one O(4), two equivalent O(6), and three equivalent O(5) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(3)O6 octahedra, corners with four equivalent Li(4)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(4)O6 octahedra, and edges with four equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), two equivalent Mn(1), and one Co(1) atom to form OLi3Mn2Co octahedra that share  a cornercorner with one O(6)Li3Co3 octahedra,  a cornercorner with one O(1)Li3Mn2Co octahedra, corners with four equivalent O(3)Li4Mn2 octahedra, edges with two equivalent O(4)Li3Co3 octahedra, edges with two equivalent O(1)Li3Mn2Co octahedra, edges with two equivalent O(7)Li3MnCo2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, and edges with four equivalent O(2)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), two equivalent Li(5), and one Mn(1) atom to form OLi5Mn octahedra that share  a cornercorner with one O(4)Li3Co3 octahedra,  a cornercorner with one O(7)Li3MnCo2 octahedra, corners with four equivalent O(2)Li5Mn octahedra, edges with four equivalent O(1)Li3Mn2Co octahedra, edges with four equivalent O(3)Li4Mn2 octahedra, and edges with four equivalent O(2)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third O site, O(3) is bonded to one Li(3), one Li(5), two equivalent Li(1), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share  a cornercorner with one O(5)Li3Co3 octahedra,  a cornercorner with one O(3)Li4Mn2 octahedra, corners with four equivalent O(1)Li3Mn2Co octahedra, edges with two equivalent O(4)Li3Co3 octahedra, edges with two equivalent O(1)Li3Mn2Co octahedra, edges with two equivalent O(7)Li3MnCo2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, and edges with four equivalent O(2)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Li(3), one Co(2), and two equivalent Co(1) atoms to form OLi3Co3 octahedra that share  a cornercorner with one O(5)Li3Co3 octahedra,  a cornercorner with one O(2)Li5Mn octahedra, corners with four equivalent O(7)Li3MnCo2 octahedra, edges with two equivalent O(4)Li3Co3 octahedra, edges with two equivalent O(5)Li3Co3 octahedra, edges with two equivalent O(6)Li3Co3 octahedra, edges with two equivalent O(1)Li3Mn2Co octahedra, edges with two equivalent O(7)Li3MnCo2 octahedra, and edges with two equivalent O(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. In the fifth O site, O(5) is bonded to one Li(3), two equivalent Li(4), and three equivalent Co(2) atoms to form OLi3Co3 octahedra that share  a cornercorner with one O(4)Li3Co3 octahedra,  a cornercorner with one O(3)Li4Mn2 octahedra, corners with four equivalent O(6)Li3Co3 octahedra, edges with two equivalent O(4)Li3Co3 octahedra, edges with two equivalent O(7)Li3MnCo2 octahedra, edges with four equivalent O(5)Li3Co3 octahedra, and edges with four equivalent O(6)Li3Co3 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. In the sixth O site, O(6) is bonded to three equivalent Li(4), one Co(1), and two equivalent Co(2) atoms to form OLi3Co3 octahedra that share  a cornercorner with one O(1)Li3Mn2Co octahedra,  a cornercorner with one O(7)Li3MnCo2 octahedra, corners with four equivalent O(5)Li3Co3 octahedra, edges with two equivalent O(4)Li3Co3 octahedra, edges with two equivalent O(7)Li3MnCo2 octahedra, edges with four equivalent O(5)Li3Co3 octahedra, and edges with four equivalent O(6)Li3Co3 octahedra. The corner-sharing octahedral tilt angles range from 1-4°. In the seventh O site, O(7) is bonded to one Li(4), two equivalent Li(3), one Mn(1), and two equivalent Co(1) atoms to form OLi3MnCo2 octahedra that share  a cornercorner with one O(6)Li3Co3 octahedra,  a cornercorner with one O(2)Li5Mn octahedra, corners with four equivalent O(4)Li3Co3 octahedra, edges with two equivalent O(4)Li3Co3 octahedra, edges with two equivalent O(5)Li3Co3 octahedra, edges with two equivalent O(6)Li3Co3 octahedra, edges with two equivalent O(1)Li3Mn2Co octahedra, edges with two equivalent O(7)Li3MnCo2 octahedra, and edges with two equivalent O(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-6°.
Li4MnCo2O7 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one Co(2)O6 octahedra, corners with five equivalent Mn(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 two equivalent Li(5)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-12°. The Li(1)-O(2) bond length is 2.06 Å. The Li(1)-O(4) bond length is 2.20 Å. There is one shorter (2.18 Å) and one longer (2.30 Å) Li(1)-O(1) bond length. There is one shorter (2.15 Å) and one longer (2.27 Å) Li(1)-O(3) bond length. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with four equivalent Li(5)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. Both Li(2)-O(1) bond lengths are 2.13 Å. There are two shorter (2.06 Å) and two longer (2.11 Å) Li(2)-O(2) bond lengths. In the third Li site, Li(3) is bonded to one O(3), one O(5), two equivalent O(4), and two equivalent O(7) 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 four equivalent Co(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. The Li(3)-O(3) bond length is 2.04 Å. The Li(3)-O(5) bond length is 2.09 Å. There is one shorter (2.11 Å) and one longer (2.20 Å) Li(3)-O(4) bond length. There is one shorter (2.12 Å) and one longer (2.19 Å) Li(3)-O(7) bond length. In the fourth Li site, Li(4) is bonded to one O(7), two equivalent O(5), and three equivalent O(6) atoms to form LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra, corners with four equivalent Co(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(4)O6 octahedra, and edges with four equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. The Li(4)-O(7) bond length is 2.10 Å. There is one shorter (2.10 Å) and one longer (2.17 Å) Li(4)-O(5) bond length. There are a spread of Li(4)-O(6) bond distances ranging from 2.07-2.20 Å. 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(3)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. Both Li(5)-O(3) bond lengths are 2.04 Å. There are two shorter (2.07 Å) and two longer (2.16 Å) Li(5)-O(2) bond lengths. Mn(1) is bonded to one O(2), one O(7), two equivalent O(1), and two equivalent O(3) atoms to form MnO6 octahedra that share  a cornercorner with one Li(4)O6 octahedra, corners with five equivalent Li(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 two equivalent Li(5)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-12°. The Mn(1)-O(2) bond length is 1.82 Å. The Mn(1)-O(7) bond length is 2.02 Å. There is one shorter (2.01 Å) and one longer (2.03 Å) Mn(1)-O(1) bond length. There is one shorter (1.95 Å) and one longer (1.96 Å) Mn(1)-O(3) bond length. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(6), two equivalent O(4), and two equivalent O(7) atoms to form CoO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. The Co(1)-O(1) bond length is 1.95 Å. The Co(1)-O(6) bond length is 1.92 Å. There is one shorter (1.94 Å) and one longer (2.18 Å) Co(1)-O(4) bond length. There is one shorter (1.91 Å) and one longer (2.13 Å) Co(1)-O(7) bond length. In the second Co site, Co(2) is bonded to one O(4), two equivalent O(6), and three equivalent O(5) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(3)O6 octahedra, corners with four equivalent Li(4)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(4)O6 octahedra, and edges with four equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. The Co(2)-O(4) bond length is 1.97 Å. There is one shorter (2.03 Å) and one longer (2.07 Å) Co(2)-O(6) bond length. There are a spread of Co(2)-O(5) bond distances ranging from 1.95-2.09 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), two equivalent Mn(1), and one Co(1) atom to form OLi3Mn2Co octahedra that share  a cornercorner with one O(6)Li3Co3 octahedra,  a cornercorner with one O(1)Li3Mn2Co octahedra, corners with four equivalent O(3)Li4Mn2 octahedra, edges with two equivalent O(4)Li3Co3 octahedra, edges with two equivalent O(1)Li3Mn2Co octahedra, edges with two equivalent O(7)Li3MnCo2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, and edges with four equivalent O(2)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), two equivalent Li(5), and one Mn(1) atom to form OLi5Mn octahedra that share  a cornercorner with one O(4)Li3Co3 octahedra,  a cornercorner with one O(7)Li3MnCo2 octahedra, corners with four equivalent O(2)Li5Mn octahedra, edges with four equivalent O(1)Li3Mn2Co octahedra, edges with four equivalent O(3)Li4Mn2 octahedra, and edges with four equivalent O(2)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third O site, O(3) is bonded to one Li(3), one Li(5), two equivalent Li(1), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share  a cornercorner with one O(5)Li3Co3 octahedra,  a cornercorner with one O(3)Li4Mn2 octahedra, corners with four equivalent O(1)Li3Mn2Co octahedra, edges with two equivalent O(4)Li3Co3 octahedra, edges with two equivalent O(1)Li3Mn2Co octahedra, edges with two equivalent O(7)Li3MnCo2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, and edges with four equivalent O(2)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Li(3), one Co(2), and two equivalent Co(1) atoms to form OLi3Co3 octahedra that share  a cornercorner with one O(5)Li3Co3 octahedra,  a cornercorner with one O(2)Li5Mn octahedra, corners with four equivalent O(7)Li3MnCo2 octahedra, edges with two equivalent O(4)Li3Co3 octahedra, edges with two equivalent O(5)Li3Co3 octahedra, edges with two equivalent O(6)Li3Co3 octahedra, edges with two equivalent O(1)Li3Mn2Co octahedra, edges with two equivalent O(7)Li3MnCo2 octahedra, and edges with two equivalent O(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. In the fifth O site, O(5) is bonded to one Li(3), two equivalent Li(4), and three equivalent Co(2) atoms to form OLi3Co3 octahedra that share  a cornercorner with one O(4)Li3Co3 octahedra,  a cornercorner with one O(3)Li4Mn2 octahedra, corners with four equivalent O(6)Li3Co3 octahedra, edges with two equivalent O(4)Li3Co3 octahedra, edges with two equivalent O(7)Li3MnCo2 octahedra, edges with four equivalent O(5)Li3Co3 octahedra, and edges with four equivalent O(6)Li3Co3 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. In the sixth O site, O(6) is bonded to three equivalent Li(4), one Co(1), and two equivalent Co(2) atoms to form OLi3Co3 octahedra that share  a cornercorner with one O(1)Li3Mn2Co octahedra,  a cornercorner with one O(7)Li3MnCo2 octahedra, corners with four equivalent O(5)Li3Co3 octahedra, edges with two equivalent O(4)Li3Co3 octahedra, edges with two equivalent O(7)Li3MnCo2 octahedra, edges with four equivalent O(5)Li3Co3 octahedra, and edges with four equivalent O(6)Li3Co3 octahedra. The corner-sharing octahedral tilt angles range from 1-4°. In the seventh O site, O(7) is bonded to one Li(4), two equivalent Li(3), one Mn(1), and two equivalent Co(1) atoms to form OLi3MnCo2 octahedra that share  a cornercorner with one O(6)Li3Co3 octahedra,  a cornercorner with one O(2)Li5Mn octahedra, corners with four equivalent O(4)Li3Co3 octahedra, edges with two equivalent O(4)Li3Co3 octahedra, edges with two equivalent O(5)Li3Co3 octahedra, edges with two equivalent O(6)Li3Co3 octahedra, edges with two equivalent O(1)Li3Mn2Co octahedra, edges with two equivalent O(7)Li3MnCo2 octahedra, and edges with two equivalent O(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-6°.