NaAlCO5 crystallizes in the orthorhombic Imma space group. Na(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form distorted NaO6 octahedra that share edges with two equivalent Na(1)O6 octahedra and edges with four equivalent Al(1)O6 octahedra. Al(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form AlO6 octahedra that share edges with two equivalent Al(1)O6 octahedra and edges with four equivalent Na(1)O6 octahedra. C(1) is bonded in a trigonal planar geometry to one O(1) and two equivalent O(2) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one C(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Al(1), and one C(1) atom. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one Na(1) and two equivalent Al(1) atoms.
NaAlCO5 crystallizes in the orthorhombic Imma space group. Na(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form distorted NaO6 octahedra that share edges with two equivalent Na(1)O6 octahedra and edges with four equivalent Al(1)O6 octahedra. Both Na(1)-O(3) bond lengths are 2.46 Å. All Na(1)-O(2) bond lengths are 2.58 Å. Al(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form AlO6 octahedra that share edges with two equivalent Al(1)O6 octahedra and edges with four equivalent Na(1)O6 octahedra. Both Al(1)-O(2) bond lengths are 2.03 Å. All Al(1)-O(3) bond lengths are 1.85 Å. C(1) is bonded in a trigonal planar geometry to one O(1) and two equivalent O(2) atoms. The C(1)-O(1) bond length is 1.27 Å. Both C(1)-O(2) bond lengths are 1.30 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one C(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Al(1), and one C(1) atom. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one Na(1) and two equivalent Al(1) atoms.