LiMn3O6 is Ilmenite-like structured and crystallizes in the monoclinic Cc space group. Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, corners with four equivalent Mn(3)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra, and  a faceface with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-58°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with three equivalent Mn(2)O6 octahedra, edges with three equivalent Mn(3)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 16°. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form MnO6 octahedra that share corners with four equivalent Li(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-50°. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form MnO6 octahedra that share corners with four equivalent Li(1)O6 octahedra,  an edgeedge with one 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 range from 11-58°. There are six 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), one Mn(2), and one Mn(3) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom. In the third O site, O(3) is bonded to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom to form a mixture of corner and edge-sharing OLiMn3 trigonal pyramids. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom. In the sixth O site, O(6) 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 trigonal pyramids.
LiMn3O6 is Ilmenite-like structured and crystallizes in the monoclinic Cc space group. Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, corners with four equivalent Mn(3)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra, and  a faceface with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-58°. The Li(1)-O(1) bond length is 2.08 Å. The Li(1)-O(2) bond length is 2.26 Å. The Li(1)-O(3) bond length is 2.15 Å. The Li(1)-O(4) bond length is 2.18 Å. The Li(1)-O(5) bond length is 2.36 Å. The Li(1)-O(6) bond length is 2.34 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with three equivalent Mn(2)O6 octahedra, edges with three equivalent Mn(3)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 16°. The Mn(1)-O(1) bond length is 1.91 Å. The Mn(1)-O(2) bond length is 2.00 Å. The Mn(1)-O(3) bond length is 1.96 Å. The Mn(1)-O(4) bond length is 1.93 Å. The Mn(1)-O(5) bond length is 1.92 Å. The Mn(1)-O(6) bond length is 1.95 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form MnO6 octahedra that share corners with four equivalent Li(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-50°. The Mn(2)-O(1) bond length is 1.93 Å. The Mn(2)-O(2) bond length is 1.95 Å. The Mn(2)-O(3) bond length is 1.99 Å. The Mn(2)-O(4) bond length is 1.98 Å. The Mn(2)-O(5) bond length is 1.92 Å. The Mn(2)-O(6) bond length is 1.95 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form MnO6 octahedra that share corners with four equivalent Li(1)O6 octahedra,  an edgeedge with one 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 range from 11-58°. The Mn(3)-O(1) bond length is 2.23 Å. The Mn(3)-O(2) bond length is 1.95 Å. The Mn(3)-O(3) bond length is 1.96 Å. The Mn(3)-O(4) bond length is 1.99 Å. The Mn(3)-O(5) bond length is 2.18 Å. The Mn(3)-O(6) bond length is 1.97 Å. There are six 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), one Mn(2), and one Mn(3) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom. In the third O site, O(3) is bonded to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom to form a mixture of corner and edge-sharing OLiMn3 trigonal pyramids. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom. In the sixth O site, O(6) 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 trigonal pyramids.