Li7Mn5O12 is Caswellsilverite-like structured and crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)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 6-14°. In the second Li site, Li(2) is bonded to one O(4), two equivalent O(2), and three equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with three equivalent Mn(2)O6 octahedra, edges with three equivalent Mn(3)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(1), two equivalent O(5), and three equivalent O(6) atoms. In the fourth Li site, Li(4) is bonded to two equivalent O(5) and four equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 11°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(4), one O(6), two equivalent O(1), and two equivalent O(5) atoms to form MnO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-14°. In the second Mn site, Mn(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(3)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 5-7°. In the third Mn site, Mn(3) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, edges with four equivalent Mn(2)O6 octahedra, and edges with six equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(1), one Mn(2), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(6)Li5Mn octahedra, corners with two equivalent O(4)Li3Mn3 octahedra, corners with two equivalent O(5)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(6)Li5Mn octahedra, edges with three equivalent O(4)Li3Mn3 octahedra, and edges with three equivalent O(5)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one Mn(3), and two equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra,  a cornercorner with one O(5)Li4Mn2 octahedra, corners with two equivalent O(3)Li3Mn3 octahedra, corners with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with three equivalent O(4)Li3Mn3 octahedra, and edges with five equivalent O(3)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the third O site, O(3) is bonded to three equivalent Li(2), one Mn(2), and two equivalent Mn(3) atoms to form a mixture of corner and edge-sharing OLi3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the fourth O site, O(4) is bonded to one Li(2), two equivalent Li(1), 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(6)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 two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li4Mn2 octahedra, edges with three equivalent O(1)Li3Mn3 octahedra, and edges with three equivalent O(2)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the fifth O site, O(5) is bonded to one Li(1), one Li(4), two equivalent Li(3), and two equivalent Mn(1) atoms to form distorted OLi4Mn2 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra,  a cornercorner with one O(5)Li4Mn2 octahedra, corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(6)Li5Mn octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li4Mn2 octahedra, edges with three equivalent O(1)Li3Mn3 octahedra, and edges with five equivalent O(6)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-18°. In the sixth O site, O(6) is bonded to two equivalent Li(4), three equivalent Li(3), and one Mn(1) atom to form OLi5Mn octahedra that share  a cornercorner with one O(1)Li3Mn3 octahedra,  a cornercorner with one O(4)Li3Mn3 octahedra, corners with two equivalent O(5)Li4Mn2 octahedra, corners with two equivalent O(6)Li5Mn octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with five equivalent O(5)Li4Mn2 octahedra, and edges with five equivalent O(6)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-18°.
Li7Mn5O12 is Caswellsilverite-like structured and crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)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 6-14°. The Li(1)-O(2) bond length is 2.17 Å. The Li(1)-O(5) bond length is 2.05 Å. There is one shorter (2.14 Å) and one longer (2.48 Å) Li(1)-O(1) bond length. There is one shorter (2.08 Å) and one longer (2.12 Å) Li(1)-O(4) bond length. In the second Li site, Li(2) is bonded to one O(4), two equivalent O(2), and three equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with three equivalent Mn(2)O6 octahedra, edges with three equivalent Mn(3)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. The Li(2)-O(4) bond length is 2.17 Å. There is one shorter (2.13 Å) and one longer (2.19 Å) Li(2)-O(2) bond length. There are a spread of Li(2)-O(3) bond distances ranging from 2.13-2.17 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(1), two equivalent O(5), and three equivalent O(6) atoms. The Li(3)-O(1) bond length is 2.26 Å. There is one shorter (2.19 Å) and one longer (2.57 Å) Li(3)-O(5) bond length. There are a spread of Li(3)-O(6) bond distances ranging from 2.01-2.07 Å. In the fourth Li site, Li(4) is bonded to two equivalent O(5) and four equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 11°. Both Li(4)-O(5) bond lengths are 2.05 Å. There are two shorter (2.08 Å) and two longer (2.27 Å) Li(4)-O(6) bond lengths. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(4), one O(6), two equivalent O(1), and two equivalent O(5) atoms to form MnO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-14°. The Mn(1)-O(4) bond length is 2.05 Å. The Mn(1)-O(6) bond length is 1.82 Å. There is one shorter (2.00 Å) and one longer (2.06 Å) Mn(1)-O(1) bond length. There is one shorter (1.94 Å) and one longer (1.95 Å) Mn(1)-O(5) bond length. In the second Mn site, Mn(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(3)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 5-7°. The Mn(2)-O(1) bond length is 1.99 Å. The Mn(2)-O(3) bond length is 1.98 Å. There is one shorter (1.96 Å) and one longer (2.28 Å) Mn(2)-O(2) bond length. There is one shorter (1.94 Å) and one longer (2.22 Å) Mn(2)-O(4) bond length. In the third Mn site, Mn(3) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, edges with four equivalent Mn(2)O6 octahedra, and edges with six equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. Both Mn(3)-O(2) bond lengths are 1.99 Å. There are two shorter (1.95 Å) and two longer (2.26 Å) Mn(3)-O(3) bond lengths. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(1), one Mn(2), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(6)Li5Mn octahedra, corners with two equivalent O(4)Li3Mn3 octahedra, corners with two equivalent O(5)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(6)Li5Mn octahedra, edges with three equivalent O(4)Li3Mn3 octahedra, and edges with three equivalent O(5)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one Mn(3), and two equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra,  a cornercorner with one O(5)Li4Mn2 octahedra, corners with two equivalent O(3)Li3Mn3 octahedra, corners with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with three equivalent O(4)Li3Mn3 octahedra, and edges with five equivalent O(3)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the third O site, O(3) is bonded to three equivalent Li(2), one Mn(2), and two equivalent Mn(3) atoms to form a mixture of corner and edge-sharing OLi3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the fourth O site, O(4) is bonded to one Li(2), two equivalent Li(1), 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(6)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 two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li4Mn2 octahedra, edges with three equivalent O(1)Li3Mn3 octahedra, and edges with three equivalent O(2)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the fifth O site, O(5) is bonded to one Li(1), one Li(4), two equivalent Li(3), and two equivalent Mn(1) atoms to form distorted OLi4Mn2 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra,  a cornercorner with one O(5)Li4Mn2 octahedra, corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(6)Li5Mn octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li4Mn2 octahedra, edges with three equivalent O(1)Li3Mn3 octahedra, and edges with five equivalent O(6)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-18°. In the sixth O site, O(6) is bonded to two equivalent Li(4), three equivalent Li(3), and one Mn(1) atom to form OLi5Mn octahedra that share  a cornercorner with one O(1)Li3Mn3 octahedra,  a cornercorner with one O(4)Li3Mn3 octahedra, corners with two equivalent O(5)Li4Mn2 octahedra, corners with two equivalent O(6)Li5Mn octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with five equivalent O(5)Li4Mn2 octahedra, and edges with five equivalent O(6)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-18°.