Li3MnAl2O6 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with four equivalent Al(1)O4 tetrahedra, and  an edgeedge with one Al(2)O4 tetrahedra. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(6) atom. In the third Li site, Li(3) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent Al(2)O4 tetrahedra, and  an edgeedge with one Al(1)O4 tetrahedra. Mn(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), one O(5), and one O(6) atom. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form AlO4 tetrahedra that share corners with two equivalent Al(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. In the second Al site, Al(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form AlO4 tetrahedra that share corners with two equivalent Al(1)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. There are six inequivalent O sites. In the first O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Mn(1), and one Al(2) atom. In the second O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Mn(1), and one Al(1) atom. In the third O site, O(2) is bonded to one Li(1), one Li(2), one Mn(1), and one Al(1) atom to form corner-sharing OLi2MnAl tetrahedra. In the fourth O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), one Al(1), and one Al(2) atom. In the fifth O site, O(4) is bonded to one Li(2), one Li(3), one Mn(1), and one Al(2) atom to form distorted corner-sharing OLi2MnAl tetrahedra. In the sixth O site, O(5) is bonded in a 5-coordinate geometry to one Li(1), one Li(3), one Mn(1), one Al(1), and one Al(2) atom.
Li3MnAl2O6 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with four equivalent Al(1)O4 tetrahedra, and  an edgeedge with one Al(2)O4 tetrahedra. The Li(1)-O(1) bond length is 1.93 Å. The Li(1)-O(2) bond length is 1.89 Å. The Li(1)-O(3) bond length is 2.01 Å. The Li(1)-O(5) bond length is 2.05 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(6) atom. The Li(2)-O(1) bond length is 2.13 Å. The Li(2)-O(2) bond length is 1.95 Å. The Li(2)-O(3) bond length is 2.58 Å. The Li(2)-O(4) bond length is 1.96 Å. The Li(2)-O(6) bond length is 2.12 Å. In the third Li site, Li(3) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent Al(2)O4 tetrahedra, and  an edgeedge with one Al(1)O4 tetrahedra. The Li(3)-O(3) bond length is 2.03 Å. The Li(3)-O(4) bond length is 1.88 Å. The Li(3)-O(5) bond length is 2.03 Å. The Li(3)-O(6) bond length is 1.91 Å. Mn(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), one O(5), and one O(6) atom. The Mn(1)-O(1) bond length is 1.93 Å. The Mn(1)-O(2) bond length is 1.93 Å. The Mn(1)-O(4) bond length is 1.93 Å. The Mn(1)-O(5) bond length is 2.61 Å. The Mn(1)-O(6) bond length is 1.93 Å. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form AlO4 tetrahedra that share corners with two equivalent Al(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The Al(1)-O(1) bond length is 1.76 Å. The Al(1)-O(2) bond length is 1.77 Å. The Al(1)-O(3) bond length is 1.81 Å. The Al(1)-O(5) bond length is 1.81 Å. In the second Al site, Al(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form AlO4 tetrahedra that share corners with two equivalent Al(1)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The Al(2)-O(3) bond length is 1.81 Å. The Al(2)-O(4) bond length is 1.77 Å. The Al(2)-O(5) bond length is 1.80 Å. The Al(2)-O(6) bond length is 1.77 Å. There are six inequivalent O sites. In the first O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Mn(1), and one Al(2) atom. In the second O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Mn(1), and one Al(1) atom. In the third O site, O(2) is bonded to one Li(1), one Li(2), one Mn(1), and one Al(1) atom to form corner-sharing OLi2MnAl tetrahedra. In the fourth O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), one Al(1), and one Al(2) atom. In the fifth O site, O(4) is bonded to one Li(2), one Li(3), one Mn(1), and one Al(2) atom to form distorted corner-sharing OLi2MnAl tetrahedra. In the sixth O site, O(5) is bonded in a 5-coordinate geometry to one Li(1), one Li(3), one Mn(1), one Al(1), and one Al(2) atom.