Li4Mn3O7 is Caswellsilverite-like 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(6), two equivalent O(1), and three equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with three equivalent Mn(3)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. In the second Li site, Li(2) is bonded to one O(3), one O(5), two equivalent O(2), and two equivalent O(7) atoms to form LiO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(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 two equivalent Li(5)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. In the third Li site, Li(3) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Li(5)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra,  an edgeedge with one Li(5)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 three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. In the fourth Li site, Li(4) is bonded to two equivalent O(7) and four equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(5)O6 octahedra, corners with four equivalent Mn(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-12°. In the fifth Li site, Li(5) is bonded to two equivalent O(7) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. 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(1), and two equivalent O(7) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. In the second Mn site, Mn(2) is bonded to one O(4), two equivalent O(2), and three equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two 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 Mn(3)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 4-9°. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), two equivalent O(4), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)O6 octahedra,  an edgeedge with one Li(4)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, edges with two equivalent Mn(3)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(1), one Mn(3), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(4)Li3Mn3 octahedra, corners with two equivalent O(7)Li4Mn2 octahedra,  an edgeedge with one O(7)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(6)Li3Mn3 octahedra, edges with two equivalent O(3)Li5Mn octahedra, and edges with three equivalent O(4)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(2), one Mn(3), and two equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(6)Li3Mn3 octahedra, corners with two equivalent O(7)Li4Mn2 octahedra,  an edgeedge with one O(7)Li4Mn2 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(3)Li5Mn octahedra, and edges with three equivalent O(6)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-11°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(3), two equivalent Li(5), and one Mn(1) atom to form OLi5Mn octahedra that share corners with two equivalent O(5)Li3Mn3 octahedra, corners with two equivalent O(6)Li3Mn3 octahedra, corners with two equivalent O(3)Li5Mn octahedra,  an edgeedge with one O(6)Li3Mn3 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with three equivalent O(3)Li5Mn octahedra, and edges with four equivalent O(7)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the fourth O site, O(4) is bonded to three equivalent Li(1), one Mn(2), and two equivalent Mn(3) atoms to form a mixture of edge and corner-sharing OLi3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Li(4), one Mn(1), and two equivalent Mn(3) atoms to form OLi3Mn3 octahedra that share corners with two equivalent O(4)Li3Mn3 octahedra, corners with two equivalent O(5)Li3Mn3 octahedra, corners with two equivalent O(3)Li5Mn octahedra,  an edgeedge with one 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(5)Li3Mn3 octahedra, and edges with four equivalent O(7)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the sixth O site, O(6) is bonded to one Li(1), two equivalent Li(3), and three equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(4)Li3Mn3 octahedra, corners with two equivalent O(3)Li5Mn octahedra,  an edgeedge with one O(3)Li5Mn octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with three equivalent O(2)Li3Mn3 octahedra, and edges with four equivalent O(6)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the seventh O site, O(7) is bonded to one Li(4), one Li(5), two equivalent Li(2), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(7)Li4Mn2 octahedra,  an edgeedge with one O(1)Li3Mn3 octahedra,  an edgeedge with one O(2)Li3Mn3 octahedra, edges with two equivalent O(7)Li4Mn2 octahedra, edges with four equivalent O(5)Li3Mn3 octahedra, and edges with four equivalent O(3)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-11°.
Li4Mn3O7 is Caswellsilverite-like 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(6), two equivalent O(1), and three equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with three equivalent Mn(3)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. The Li(1)-O(6) bond length is 2.11 Å. There is one shorter (2.15 Å) and one longer (2.41 Å) Li(1)-O(1) bond length. There are a spread of Li(1)-O(4) bond distances ranging from 2.12-2.14 Å. In the second Li site, Li(2) is bonded to one O(3), one O(5), two equivalent O(2), and two equivalent O(7) atoms to form LiO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(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 two equivalent Li(5)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. The Li(2)-O(3) bond length is 2.08 Å. The Li(2)-O(5) bond length is 2.27 Å. There is one shorter (2.14 Å) and one longer (2.15 Å) Li(2)-O(2) bond length. There is one shorter (2.13 Å) and one longer (2.41 Å) Li(2)-O(7) bond length. In the third Li site, Li(3) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Li(5)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra,  an edgeedge with one Li(5)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 three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. The Li(3)-O(1) bond length is 2.12 Å. The Li(3)-O(2) bond length is 2.13 Å. There is one shorter (1.99 Å) and one longer (2.08 Å) Li(3)-O(3) bond length. There is one shorter (2.21 Å) and one longer (2.26 Å) Li(3)-O(6) bond length. In the fourth Li site, Li(4) is bonded to two equivalent O(7) and four equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(5)O6 octahedra, corners with four equivalent Mn(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-12°. Both Li(4)-O(7) bond lengths are 2.06 Å. There are two shorter (2.15 Å) and two longer (2.16 Å) Li(4)-O(5) bond lengths. In the fifth Li site, Li(5) is bonded to two equivalent O(7) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. Both Li(5)-O(7) bond lengths are 2.06 Å. There are two shorter (2.06 Å) and two longer (2.25 Å) Li(5)-O(3) bond lengths. 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(1), and two equivalent O(7) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. The Mn(1)-O(3) bond length is 1.82 Å. The Mn(1)-O(5) bond length is 2.03 Å. There is one shorter (2.00 Å) and one longer (2.07 Å) Mn(1)-O(1) bond length. There is one shorter (1.94 Å) and one longer (1.96 Å) Mn(1)-O(7) bond length. In the second Mn site, Mn(2) is bonded to one O(4), two equivalent O(2), and three equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two 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 Mn(3)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 4-9°. The Mn(2)-O(4) bond length is 1.99 Å. There is one shorter (1.96 Å) and one longer (2.25 Å) Mn(2)-O(2) bond length. There are a spread of Mn(2)-O(6) bond distances ranging from 1.94-2.24 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), two equivalent O(4), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)O6 octahedra,  an edgeedge with one Li(4)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, edges with two equivalent Mn(3)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. The Mn(3)-O(1) bond length is 1.98 Å. The Mn(3)-O(2) bond length is 1.97 Å. There is one shorter (1.97 Å) and one longer (2.28 Å) Mn(3)-O(4) bond length. There is one shorter (1.92 Å) and one longer (2.20 Å) Mn(3)-O(5) bond length. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(1), one Mn(3), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(4)Li3Mn3 octahedra, corners with two equivalent O(7)Li4Mn2 octahedra,  an edgeedge with one O(7)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(6)Li3Mn3 octahedra, edges with two equivalent O(3)Li5Mn octahedra, and edges with three equivalent O(4)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(2), one Mn(3), and two equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(6)Li3Mn3 octahedra, corners with two equivalent O(7)Li4Mn2 octahedra,  an edgeedge with one O(7)Li4Mn2 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(3)Li5Mn octahedra, and edges with three equivalent O(6)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-11°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(3), two equivalent Li(5), and one Mn(1) atom to form OLi5Mn octahedra that share corners with two equivalent O(5)Li3Mn3 octahedra, corners with two equivalent O(6)Li3Mn3 octahedra, corners with two equivalent O(3)Li5Mn octahedra,  an edgeedge with one O(6)Li3Mn3 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn3 octahedra, edges with three equivalent O(3)Li5Mn octahedra, and edges with four equivalent O(7)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the fourth O site, O(4) is bonded to three equivalent Li(1), one Mn(2), and two equivalent Mn(3) atoms to form a mixture of edge and corner-sharing OLi3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Li(4), one Mn(1), and two equivalent Mn(3) atoms to form OLi3Mn3 octahedra that share corners with two equivalent O(4)Li3Mn3 octahedra, corners with two equivalent O(5)Li3Mn3 octahedra, corners with two equivalent O(3)Li5Mn octahedra,  an edgeedge with one 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(5)Li3Mn3 octahedra, and edges with four equivalent O(7)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the sixth O site, O(6) is bonded to one Li(1), two equivalent Li(3), and three equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(4)Li3Mn3 octahedra, corners with two equivalent O(3)Li5Mn octahedra,  an edgeedge with one O(3)Li5Mn octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with three equivalent O(2)Li3Mn3 octahedra, and edges with four equivalent O(6)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the seventh O site, O(7) is bonded to one Li(4), one Li(5), two equivalent Li(2), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(7)Li4Mn2 octahedra,  an edgeedge with one O(1)Li3Mn3 octahedra,  an edgeedge with one O(2)Li3Mn3 octahedra, edges with two equivalent O(7)Li4Mn2 octahedra, edges with four equivalent O(5)Li3Mn3 octahedra, and edges with four equivalent O(3)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-11°.