NaN(CN)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded to one N(3), two equivalent N(2), and three equivalent N(1) atoms to form edge-sharing NaN6 octahedra. There are two inequivalent C sites. In the first C site, C(1) is bonded in a linear geometry to one N(1) and one N(3) atom. In the second C site, C(2) is bonded in a linear geometry to one N(2) and one N(3) atom. There are three inequivalent N sites. In the first N site, N(1) is bonded in a rectangular see-saw-like geometry to three equivalent Na(1) and one C(1) atom. In the second N site, N(2) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one C(2) atom. In the third N site, N(3) is bonded in a trigonal planar geometry to one Na(1), one C(1), and one C(2) atom.
NaN(CN)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded to one N(3), two equivalent N(2), and three equivalent N(1) atoms to form edge-sharing NaN6 octahedra. The Na(1)-N(3) bond length is 2.54 Å. There is one shorter (2.49 Å) and one longer (2.50 Å) Na(1)-N(2) bond length. There are a spread of Na(1)-N(1) bond distances ranging from 2.54-2.57 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a linear geometry to one N(1) and one N(3) atom. The C(1)-N(1) bond length is 1.19 Å. The C(1)-N(3) bond length is 1.30 Å. In the second C site, C(2) is bonded in a linear geometry to one N(2) and one N(3) atom. The C(2)-N(2) bond length is 1.18 Å. The C(2)-N(3) bond length is 1.30 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a rectangular see-saw-like geometry to three equivalent Na(1) and one C(1) atom. In the second N site, N(2) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one C(2) atom. In the third N site, N(3) is bonded in a trigonal planar geometry to one Na(1), one C(1), and one C(2) atom.