NaCN2H crystallizes in the orthorhombic Pbcm space group. Na(1) is bonded to two equivalent N(2) and four equivalent N(1) atoms to form a mixture of distorted corner, face, and edge-sharing NaN6 octahedra. The corner-sharing octahedral tilt angles are 44°. C(1) is bonded in a linear geometry to one N(1) and one N(2) atom. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 5-coordinate geometry to four equivalent Na(1) and one C(1) atom. In the second N site, N(2) is bonded in a 4-coordinate geometry to two equivalent Na(1), one C(1), and one H(1) atom. H(1) is bonded in a single-bond geometry to one N(2) atom.
NaCN2H crystallizes in the orthorhombic Pbcm space group. Na(1) is bonded to two equivalent N(2) and four equivalent N(1) atoms to form a mixture of distorted corner, face, and edge-sharing NaN6 octahedra. The corner-sharing octahedral tilt angles are 44°. Both Na(1)-N(2) bond lengths are 2.51 Å. There are two shorter (2.51 Å) and two longer (2.71 Å) Na(1)-N(1) bond lengths. C(1) is bonded in a linear geometry to one N(1) and one N(2) atom. The C(1)-N(1) bond length is 1.20 Å. The C(1)-N(2) bond length is 1.28 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 5-coordinate geometry to four equivalent Na(1) and one C(1) atom. In the second N site, N(2) is bonded in a 4-coordinate geometry to two equivalent Na(1), one C(1), and one H(1) atom. The N(2)-H(1) bond length is 1.03 Å. H(1) is bonded in a single-bond geometry to one N(2) atom.