Li7Mn5O12 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(6), two equivalent O(2), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one Mn(3)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 Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-10°. In the second Li site, Li(2) is bonded to one O(2), two equivalent O(6), and three equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, edges with three equivalent Mn(2)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. In the third Li site, Li(3) is bonded to one O(5), two equivalent O(3), and three equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Li(4)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. In the fourth Li site, Li(4) 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, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 10°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(5), two equivalent O(4), and two equivalent O(6) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with three equivalent Li(3)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges 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(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. In the second Mn site, Mn(2) is bonded to one O(2), one O(6), two equivalent O(1), and two equivalent O(3) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with three equivalent Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(1)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, and edges with three equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-8°. In the third Mn site, Mn(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. There are six inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2), one Mn(3), and two equivalent Mn(2) atoms to form a mixture of corner and edge-sharing OLi3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), one Mn(2), and two equivalent Mn(3) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(1)Li3Mn3 octahedra,  a cornercorner with one O(6)Li3Mn3 octahedra, corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(5)Li5Mn octahedra,  an edgeedge with one O(5)Li5Mn octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(6)Li3Mn3 octahedra, edges with three equivalent O(2)Li3Mn3 octahedra, and edges with four equivalent O(1)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. 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(6)Li3Mn3 octahedra,  a cornercorner with one O(5)Li5Mn octahedra, corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(4)Li4Mn2 octahedra,  an edgeedge with one O(1)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(6)Li3Mn3 octahedra, edges with two equivalent O(5)Li5Mn octahedra, and edges with three equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 2-9°. In the fourth O site, O(4) is bonded to one Li(4), three equivalent Li(3), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share  a cornercorner with one O(4)Li4Mn2 octahedra,  a cornercorner with one O(5)Li5Mn octahedra, corners with two equivalent O(3)Li3Mn3 octahedra, corners with two equivalent O(6)Li3Mn3 octahedra,  an edgeedge with one O(6)Li3Mn3 octahedra, edges with three equivalent O(3)Li3Mn3 octahedra, edges with four equivalent O(4)Li4Mn2 octahedra, and edges with four equivalent O(5)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fifth O site, O(5) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(4), and one Mn(1) atom to form OLi5Mn octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(4)Li4Mn2 octahedra, corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(5)Li5Mn octahedra,  an edgeedge with one O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(6)Li3Mn3 octahedra, edges with three equivalent O(5)Li5Mn octahedra, and edges with four equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the sixth O site, O(6) is bonded to one Li(1), two equivalent Li(2), one Mn(2), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra,  a cornercorner with one O(3)Li3Mn3 octahedra, corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(4)Li4Mn2 octahedra,  an edgeedge with one O(4)Li4Mn2 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(6)Li3Mn3 octahedra, edges with two equivalent O(5)Li5Mn octahedra, and edges with three equivalent O(1)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-7°.
Li7Mn5O12 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(6), two equivalent O(2), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one Mn(3)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 Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-10°. The Li(1)-O(3) bond length is 2.10 Å. The Li(1)-O(6) bond length is 2.15 Å. Both Li(1)-O(2) bond lengths are 2.26 Å. Both Li(1)-O(5) bond lengths are 2.03 Å. In the second Li site, Li(2) is bonded to one O(2), two equivalent O(6), and three equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, edges with three equivalent Mn(2)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. The Li(2)-O(2) bond length is 2.11 Å. Both Li(2)-O(6) bond lengths are 2.31 Å. There are two shorter (2.12 Å) and one longer (2.13 Å) Li(2)-O(1) bond length. In the third Li site, Li(3) is bonded to one O(5), two equivalent O(3), and three equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Li(4)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. The Li(3)-O(5) bond length is 2.07 Å. Both Li(3)-O(3) bond lengths are 2.15 Å. There is one shorter (2.14 Å) and two longer (2.28 Å) Li(3)-O(4) bond lengths. In the fourth Li site, Li(4) 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, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 10°. Both Li(4)-O(4) bond lengths are 2.06 Å. All Li(4)-O(5) bond lengths are 2.15 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(5), two equivalent O(4), and two equivalent O(6) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with three equivalent Li(3)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges 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(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. The Mn(1)-O(3) bond length is 2.01 Å. The Mn(1)-O(5) bond length is 1.82 Å. Both Mn(1)-O(4) bond lengths are 1.95 Å. Both Mn(1)-O(6) bond lengths are 2.05 Å. In the second Mn site, Mn(2) is bonded to one O(2), one O(6), two equivalent O(1), and two equivalent O(3) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with three equivalent Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(1)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, and edges with three equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-8°. The Mn(2)-O(2) bond length is 1.92 Å. The Mn(2)-O(6) bond length is 1.95 Å. Both Mn(2)-O(1) bond lengths are 2.15 Å. Both Mn(2)-O(3) bond lengths are 2.07 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. Both Mn(3)-O(1) bond lengths are 1.94 Å. All Mn(3)-O(2) bond lengths are 2.11 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2), one Mn(3), and two equivalent Mn(2) atoms to form a mixture of corner and edge-sharing OLi3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), one Mn(2), and two equivalent Mn(3) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(1)Li3Mn3 octahedra,  a cornercorner with one O(6)Li3Mn3 octahedra, corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(5)Li5Mn octahedra,  an edgeedge with one O(5)Li5Mn octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(6)Li3Mn3 octahedra, edges with three equivalent O(2)Li3Mn3 octahedra, and edges with four equivalent O(1)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. 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(6)Li3Mn3 octahedra,  a cornercorner with one O(5)Li5Mn octahedra, corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(4)Li4Mn2 octahedra,  an edgeedge with one O(1)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(6)Li3Mn3 octahedra, edges with two equivalent O(5)Li5Mn octahedra, and edges with three equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 2-9°. In the fourth O site, O(4) is bonded to one Li(4), three equivalent Li(3), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share  a cornercorner with one O(4)Li4Mn2 octahedra,  a cornercorner with one O(5)Li5Mn octahedra, corners with two equivalent O(3)Li3Mn3 octahedra, corners with two equivalent O(6)Li3Mn3 octahedra,  an edgeedge with one O(6)Li3Mn3 octahedra, edges with three equivalent O(3)Li3Mn3 octahedra, edges with four equivalent O(4)Li4Mn2 octahedra, and edges with four equivalent O(5)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fifth O site, O(5) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(4), and one Mn(1) atom to form OLi5Mn octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(4)Li4Mn2 octahedra, corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(5)Li5Mn octahedra,  an edgeedge with one O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(6)Li3Mn3 octahedra, edges with three equivalent O(5)Li5Mn octahedra, and edges with four equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the sixth O site, O(6) is bonded to one Li(1), two equivalent Li(2), one Mn(2), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra,  a cornercorner with one O(3)Li3Mn3 octahedra, corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(4)Li4Mn2 octahedra,  an edgeedge with one O(4)Li4Mn2 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(6)Li3Mn3 octahedra, edges with two equivalent O(5)Li5Mn octahedra, and edges with three equivalent O(1)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-7°.