LiMn3O6 is Ilmenite-like structured and crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-15°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with six equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles are 14°. In the second Mn site, Mn(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)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 are 15°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), and two equivalent Mn(2) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), and two equivalent Mn(2) atoms.
LiMn3O6 is Ilmenite-like structured and crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-15°. Both Li(1)-O(1) bond lengths are 2.09 Å. All Li(1)-O(2) bond lengths are 2.24 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with six equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles are 14°. Both Mn(1)-O(1) bond lengths are 2.26 Å. All Mn(1)-O(2) bond lengths are 1.95 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)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 are 15°. Both Mn(2)-O(1) bond lengths are 1.91 Å. There are two shorter (1.95 Å) and two longer (1.98 Å) Mn(2)-O(2) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), and two equivalent Mn(2) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), and two equivalent Mn(2) atoms.