LiMn3O4 is Caswellsilverite-like structured and crystallizes in the monoclinic C2 space group. Li(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with eight equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form MnO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with eight equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with six equivalent Mn(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, edges with four equivalent Mn(1)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-13°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Mn(1), and two equivalent Mn(2) atoms to form OLi2Mn4 octahedra that share corners with six equivalent O(1)Li2Mn4 octahedra, edges with four equivalent O(1)Li2Mn4 octahedra, edges with four equivalent O(2)LiMn5 octahedra, and edges with four equivalent O(3)LiMn5 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to one Li(1), one Mn(1), and four equivalent Mn(2) atoms to form OLiMn5 octahedra that share corners with six equivalent O(3)LiMn5 octahedra, edges with two equivalent O(2)LiMn5 octahedra, edges with two equivalent O(3)LiMn5 octahedra, and edges with eight equivalent O(1)Li2Mn4 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to one Li(1), one Mn(1), and four equivalent Mn(2) atoms to form OLiMn5 octahedra that share corners with six equivalent O(2)LiMn5 octahedra, edges with two equivalent O(2)LiMn5 octahedra, edges with two equivalent O(3)LiMn5 octahedra, and edges with eight equivalent O(1)Li2Mn4 octahedra. The corner-sharing octahedral tilt angles range from 0-2°.
LiMn3O4 is Caswellsilverite-like structured and crystallizes in the monoclinic C2 space group. Li(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with eight equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. The Li(1)-O(2) bond length is 2.37 Å. The Li(1)-O(3) bond length is 2.27 Å. There are two shorter (2.16 Å) and two longer (2.43 Å) Li(1)-O(1) bond lengths. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form MnO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with eight equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. The Mn(1)-O(2) bond length is 2.00 Å. The Mn(1)-O(3) bond length is 2.00 Å. There are two shorter (1.98 Å) and two longer (2.38 Å) Mn(1)-O(1) bond lengths. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with six equivalent Mn(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, edges with four equivalent Mn(1)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-13°. There is one shorter (2.17 Å) and one longer (2.19 Å) Mn(2)-O(1) bond length. There is one shorter (2.21 Å) and one longer (2.26 Å) Mn(2)-O(2) bond length. There is one shorter (2.21 Å) and one longer (2.27 Å) Mn(2)-O(3) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Mn(1), and two equivalent Mn(2) atoms to form OLi2Mn4 octahedra that share corners with six equivalent O(1)Li2Mn4 octahedra, edges with four equivalent O(1)Li2Mn4 octahedra, edges with four equivalent O(2)LiMn5 octahedra, and edges with four equivalent O(3)LiMn5 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to one Li(1), one Mn(1), and four equivalent Mn(2) atoms to form OLiMn5 octahedra that share corners with six equivalent O(3)LiMn5 octahedra, edges with two equivalent O(2)LiMn5 octahedra, edges with two equivalent O(3)LiMn5 octahedra, and edges with eight equivalent O(1)Li2Mn4 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to one Li(1), one Mn(1), and four equivalent Mn(2) atoms to form OLiMn5 octahedra that share corners with six equivalent O(2)LiMn5 octahedra, edges with two equivalent O(2)LiMn5 octahedra, edges with two equivalent O(3)LiMn5 octahedra, and edges with eight equivalent O(1)Li2Mn4 octahedra. The corner-sharing octahedral tilt angles range from 0-2°.