Butler et al. first demonstrated the presence of the cyclic N−5 in solution through the decomposition of substituted aryl pentazoles at low temperature.

The presence of N5H and N−5 (held in solution through the interaction with zinc ions) was proven primarily using 15N NMR techniques of the decomposition products.

[5][6][7] The pentazolide anion is not expected to last longer than a few seconds in aqueous solution without the aid of complexing agents.

The discovery of pentazoles spurred attempts to create all-nitrogen salts such as N+5N−5, which should be highly potent propellants for space travel.

[11] In 2018, another team reported the high pressure synthesis of LiN5 above 45 GPa from a pure lithium surrounded by molecular nitrogen.