Na3AlP2 crystallizes in the orthorhombic Ibam space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to four equivalent P(1) atoms. In the second Na site, Na(2) is bonded in a 2-coordinate geometry to four equivalent P(1) atoms. Al(1) is bonded to four equivalent P(1) atoms to form distorted edge-sharing AlP4 tetrahedra. P(1) is bonded in a 8-coordinate geometry to two equivalent Na(1), four equivalent Na(2), and two equivalent Al(1) atoms.
Na3AlP2 crystallizes in the orthorhombic Ibam space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to four equivalent P(1) atoms. All Na(1)-P(1) bond lengths are 2.87 Å. In the second Na site, Na(2) is bonded in a 2-coordinate geometry to four equivalent P(1) atoms. There are a spread of Na(2)-P(1) bond distances ranging from 2.84-3.22 Å. Al(1) is bonded to four equivalent P(1) atoms to form distorted edge-sharing AlP4 tetrahedra. All Al(1)-P(1) bond lengths are 2.41 Å. P(1) is bonded in a 8-coordinate geometry to two equivalent Na(1), four equivalent Na(2), and two equivalent Al(1) atoms.