LaAlO3 crystallizes in the tetragonal I4/mcm space group. La(1) is bonded to four equivalent O(2) and eight equivalent O(1) atoms to form LaO12 cuboctahedra that share corners with twelve equivalent La(1)O12 cuboctahedra, faces with six equivalent La(1)O12 cuboctahedra, and faces with eight equivalent Al(1)O6 octahedra. Al(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form AlO6 octahedra that share corners with six equivalent Al(1)O6 octahedra and faces with eight equivalent La(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-12°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to four equivalent La(1) and two equivalent Al(1) atoms. In the second O site, O(2) is bonded in a distorted linear geometry to four equivalent La(1) and two equivalent Al(1) atoms.
LaAlO3 crystallizes in the tetragonal I4/mcm space group. La(1) is bonded to four equivalent O(2) and eight equivalent O(1) atoms to form LaO12 cuboctahedra that share corners with twelve equivalent La(1)O12 cuboctahedra, faces with six equivalent La(1)O12 cuboctahedra, and faces with eight equivalent Al(1)O6 octahedra. All La(1)-O(2) bond lengths are 2.67 Å. There are four shorter (2.54 Å) and four longer (2.83 Å) La(1)-O(1) bond lengths. Al(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form AlO6 octahedra that share corners with six equivalent Al(1)O6 octahedra and faces with eight equivalent La(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-12°. Both Al(1)-O(2) bond lengths are 1.90 Å. All Al(1)-O(1) bond lengths are 1.90 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to four equivalent La(1) and two equivalent Al(1) atoms. In the second O site, O(2) is bonded in a distorted linear geometry to four equivalent La(1) and two equivalent Al(1) atoms.