Ti3AlO6 is beta indium sulfide-derived structured and crystallizes in the trigonal P-3m1 space group. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(2), two equivalent O(4), and two equivalent O(5) atoms to form TiO6 octahedra that share  a cornercorner with one Al(2)O4 tetrahedra, corners with three equivalent Al(1)O4 tetrahedra,  an edgeedge with one Ti(3)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. In the second Ti site, Ti(2) is bonded to two equivalent O(3) and four equivalent O(6) atoms to form TiO6 octahedra that share corners with four equivalent Al(2)O4 tetrahedra, edges with two equivalent Ti(4)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. In the third Ti site, Ti(3) is bonded to six equivalent O(4) atoms to form TiO6 octahedra that share corners with six equivalent Al(1)O4 tetrahedra and edges with six equivalent Ti(1)O6 octahedra. In the fourth Ti site, Ti(4) is bonded to three equivalent O(5) and three equivalent O(6) atoms to form TiO6 octahedra that share corners with three equivalent Al(2)O4 tetrahedra, edges with three equivalent Ti(1)O6 octahedra, and edges with three equivalent Ti(2)O6 octahedra. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1) and three equivalent O(4) atoms to form AlO4 tetrahedra that share corners with three equivalent Ti(3)O6 octahedra and corners with nine equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-57°. In the second Al site, Al(2) is bonded to one O(2) and three equivalent O(6) atoms to form AlO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra, corners with three equivalent Ti(4)O6 octahedra, and corners with six equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-58°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Ti(1) and one Al(1) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to three equivalent Ti(1) and one Al(2) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Ti(2) atoms. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Ti(3), two equivalent Ti(1), and one Al(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Ti(4) and two equivalent Ti(1) atoms. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Ti(4), two equivalent Ti(2), and one Al(2) atom.
Ti3AlO6 is beta indium sulfide-derived structured and crystallizes in the trigonal P-3m1 space group. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(2), two equivalent O(4), and two equivalent O(5) atoms to form TiO6 octahedra that share  a cornercorner with one Al(2)O4 tetrahedra, corners with three equivalent Al(1)O4 tetrahedra,  an edgeedge with one Ti(3)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The Ti(1)-O(1) bond length is 2.15 Å. The Ti(1)-O(2) bond length is 2.10 Å. Both Ti(1)-O(4) bond lengths are 2.08 Å. Both Ti(1)-O(5) bond lengths are 2.01 Å. In the second Ti site, Ti(2) is bonded to two equivalent O(3) and four equivalent O(6) atoms to form TiO6 octahedra that share corners with four equivalent Al(2)O4 tetrahedra, edges with two equivalent Ti(4)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. Both Ti(2)-O(3) bond lengths are 1.96 Å. All Ti(2)-O(6) bond lengths are 2.11 Å. In the third Ti site, Ti(3) is bonded to six equivalent O(4) atoms to form TiO6 octahedra that share corners with six equivalent Al(1)O4 tetrahedra and edges with six equivalent Ti(1)O6 octahedra. All Ti(3)-O(4) bond lengths are 2.10 Å. In the fourth Ti site, Ti(4) is bonded to three equivalent O(5) and three equivalent O(6) atoms to form TiO6 octahedra that share corners with three equivalent Al(2)O4 tetrahedra, edges with three equivalent Ti(1)O6 octahedra, and edges with three equivalent Ti(2)O6 octahedra. All Ti(4)-O(5) bond lengths are 1.91 Å. All Ti(4)-O(6) bond lengths are 2.20 Å. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1) and three equivalent O(4) atoms to form AlO4 tetrahedra that share corners with three equivalent Ti(3)O6 octahedra and corners with nine equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-57°. The Al(1)-O(1) bond length is 1.78 Å. All Al(1)-O(4) bond lengths are 1.78 Å. In the second Al site, Al(2) is bonded to one O(2) and three equivalent O(6) atoms to form AlO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra, corners with three equivalent Ti(4)O6 octahedra, and corners with six equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-58°. The Al(2)-O(2) bond length is 1.78 Å. All Al(2)-O(6) bond lengths are 1.82 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Ti(1) and one Al(1) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to three equivalent Ti(1) and one Al(2) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Ti(2) atoms. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Ti(3), two equivalent Ti(1), and one Al(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Ti(4) and two equivalent Ti(1) atoms. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Ti(4), two equivalent Ti(2), and one Al(2) atom.