NaAs crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to two equivalent As(2) and three equivalent As(1) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to three equivalent As(1) and three equivalent As(2) atoms. There are two inequivalent As sites. In the first As site, As(1) is bonded in a 8-coordinate geometry to three equivalent Na(1), three equivalent Na(2), and two equivalent As(2) atoms. In the second As site, As(2) is bonded in a 7-coordinate geometry to two equivalent Na(1), three equivalent Na(2), and two equivalent As(1) atoms.
NaAs crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to two equivalent As(2) and three equivalent As(1) atoms. Both Na(1)-As(2) bond lengths are 3.06 Å. There are a spread of Na(1)-As(1) bond distances ranging from 2.94-3.01 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to three equivalent As(1) and three equivalent As(2) atoms. There are a spread of Na(2)-As(1) bond distances ranging from 2.98-3.11 Å. There are a spread of Na(2)-As(2) bond distances ranging from 3.05-3.16 Å. There are two inequivalent As sites. In the first As site, As(1) is bonded in a 8-coordinate geometry to three equivalent Na(1), three equivalent Na(2), and two equivalent As(2) atoms. There is one shorter (2.46 Å) and one longer (2.49 Å) As(1)-As(2) bond length. In the second As site, As(2) is bonded in a 7-coordinate geometry to two equivalent Na(1), three equivalent Na(2), and two equivalent As(1) atoms.