LiMn4O8 is beta indium sulfide-derived structured and crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form LiO4 tetrahedra that share corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, corners with three equivalent Mn(3)O6 octahedra, and corners with three equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-64°. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), one O(4), one O(6), one O(7), and one O(8) atom to form MnO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. In the second Mn site, Mn(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(7), and one O(8) atom to form distorted MnO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(8) atom to form MnO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(7) atom to form MnO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Mn(1), one Mn(3), and one Mn(4) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Mn(2), one Mn(3), and one Mn(4) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(2), and one Mn(3) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one Mn(4) atom. In the fifth O site, O(5) is bonded to one Li(1), one Mn(2), one Mn(3), and one Mn(4) atom to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(2), and one Mn(4) atom. In the eighth O site, O(8) is bonded to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra.
LiMn4O8 is beta indium sulfide-derived structured and crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form LiO4 tetrahedra that share corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, corners with three equivalent Mn(3)O6 octahedra, and corners with three equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-64°. The Li(1)-O(5) bond length is 2.00 Å. The Li(1)-O(6) bond length is 2.13 Å. The Li(1)-O(7) bond length is 1.93 Å. The Li(1)-O(8) bond length is 1.99 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), one O(4), one O(6), one O(7), and one O(8) atom to form MnO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The Mn(1)-O(1) bond length is 1.95 Å. The Mn(1)-O(3) bond length is 1.94 Å. The Mn(1)-O(4) bond length is 1.90 Å. The Mn(1)-O(6) bond length is 1.98 Å. The Mn(1)-O(7) bond length is 1.94 Å. The Mn(1)-O(8) bond length is 1.98 Å. In the second Mn site, Mn(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(7), and one O(8) atom to form distorted MnO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The Mn(2)-O(2) bond length is 1.97 Å. The Mn(2)-O(3) bond length is 1.97 Å. The Mn(2)-O(4) bond length is 2.22 Å. The Mn(2)-O(5) bond length is 1.98 Å. The Mn(2)-O(7) bond length is 2.20 Å. The Mn(2)-O(8) bond length is 1.98 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(8) atom to form MnO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The Mn(3)-O(1) bond length is 1.94 Å. The Mn(3)-O(2) bond length is 1.93 Å. The Mn(3)-O(3) bond length is 1.93 Å. The Mn(3)-O(5) bond length is 1.96 Å. The Mn(3)-O(6) bond length is 1.97 Å. The Mn(3)-O(8) bond length is 1.96 Å. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(7) atom to form MnO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The Mn(4)-O(1) bond length is 1.95 Å. The Mn(4)-O(2) bond length is 1.94 Å. The Mn(4)-O(4) bond length is 1.90 Å. The Mn(4)-O(5) bond length is 1.98 Å. The Mn(4)-O(6) bond length is 1.98 Å. The Mn(4)-O(7) bond length is 1.93 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Mn(1), one Mn(3), and one Mn(4) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Mn(2), one Mn(3), and one Mn(4) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(2), and one Mn(3) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one Mn(4) atom. In the fifth O site, O(5) is bonded to one Li(1), one Mn(2), one Mn(3), and one Mn(4) atom to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(2), and one Mn(4) atom. In the eighth O site, O(8) is bonded to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra.