Li5AlO4 is Ilmenite-like structured and crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Al(1)O4 tetrahedra, corners with eight equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Al(1)O4 tetrahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with four equivalent Al(1)O4 tetrahedra, corners with eight equivalent Li(1)O4 trigonal pyramids, and edges with four equivalent Li(1)O4 trigonal pyramids. Al(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form AlO4 tetrahedra that share corners with four equivalent Li(2)O4 tetrahedra, corners with eight equivalent Li(1)O4 trigonal pyramids, and edges with four equivalent Li(1)O4 trigonal pyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), four equivalent Li(1), and one Al(1) atom to form a mixture of distorted corner and edge-sharing OLi5Al octahedra. The corner-sharing octahedral tilt angles range from 61-66°. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(2), four equivalent Li(1), and one Al(1) atom.
Li5AlO4 is Ilmenite-like structured and crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Al(1)O4 tetrahedra, corners with eight equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Al(1)O4 tetrahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. There is one shorter (1.95 Å) and one longer (2.01 Å) Li(1)-O(1) bond length. There is one shorter (1.91 Å) and one longer (2.09 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with four equivalent Al(1)O4 tetrahedra, corners with eight equivalent Li(1)O4 trigonal pyramids, and edges with four equivalent Li(1)O4 trigonal pyramids. Both Li(2)-O(1) bond lengths are 1.97 Å. Both Li(2)-O(2) bond lengths are 1.94 Å. Al(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form AlO4 tetrahedra that share corners with four equivalent Li(2)O4 tetrahedra, corners with eight equivalent Li(1)O4 trigonal pyramids, and edges with four equivalent Li(1)O4 trigonal pyramids. Both Al(1)-O(1) bond lengths are 1.77 Å. Both Al(1)-O(2) bond lengths are 1.76 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), four equivalent Li(1), and one Al(1) atom to form a mixture of distorted corner and edge-sharing OLi5Al octahedra. The corner-sharing octahedral tilt angles range from 61-66°. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(2), four equivalent Li(1), and one Al(1) atom.