Sodium cyanide (NaCN) was identified in space by Turner et al. in 1994 toward CW Leo, also known as IRC +10216 (an object that has recently been found to have changed substantially in less than 10 years). The initial detection was based on four rotational lines, with observations made using the 12m telescope on Kitt Peak then under control of NRAO. He et al. observed nine additional lines of NaCN in IRC +10216. In 2001, Highberger et al. reported the detection of NaCN, MgNC, and AlF toward the protoplanetary nebula CRL 2688. The current best set of molecular constants for NaCN were derived by Müller et al. and published in 2012.

As shown above, NaCN is a non-linear compound that is very ionic, with Na+0.89 and CN–0.89 according to calculated natural charges. Although not truly cyclic, it could be labeled c-NaCN to distinguish it from the two less stable minima on the Na,C,N surface, linear NaCN and NaNC, that are shown on the potential energy curve to the right.