CeAlO3 crystallizes in the orthorhombic Pnma space group. Ce(1) is bonded to four equivalent O(1) and eight equivalent O(2) atoms to form distorted CeO12 cuboctahedra that share corners with twelve equivalent Ce(1)O12 cuboctahedra, faces with six equivalent Ce(1)O12 cuboctahedra, and faces with eight equivalent Al(1)O6 octahedra. Al(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form AlO6 octahedra that share corners with six equivalent Al(1)O6 octahedra and faces with eight equivalent Ce(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 10-13°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to four equivalent Ce(1) and two equivalent Al(1) atoms. In the second O site, O(2) is bonded in a 2-coordinate geometry to four equivalent Ce(1) and two equivalent Al(1) atoms.
CeAlO3 crystallizes in the orthorhombic Pnma space group. Ce(1) is bonded to four equivalent O(1) and eight equivalent O(2) atoms to form distorted CeO12 cuboctahedra that share corners with twelve equivalent Ce(1)O12 cuboctahedra, faces with six equivalent Ce(1)O12 cuboctahedra, and faces with eight equivalent Al(1)O6 octahedra. There are a spread of Ce(1)-O(1) bond distances ranging from 2.46-2.89 Å. There are a spread of Ce(1)-O(2) bond distances ranging from 2.53-2.82 Å. Al(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form AlO6 octahedra that share corners with six equivalent Al(1)O6 octahedra and faces with eight equivalent Ce(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 10-13°. Both Al(1)-O(1) bond lengths are 1.90 Å. All Al(1)-O(2) bond lengths are 1.89 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to four equivalent Ce(1) and two equivalent Al(1) atoms. In the second O site, O(2) is bonded in a 2-coordinate geometry to four equivalent Ce(1) and two equivalent Al(1) atoms.