14N NQR frequencies and spin–lattice relaxation times were measured in technologically important 5-aminotetrazole and 5-aminotetrazole monohydrate at different temperatures between 77 K and 300 K. Five NQR triplets ν +, ν − and ν 0 were found for the five inequivalent nitrogen atoms in each compound between 0.7 MHz and 4 MHz. Carr-Purcell based multipulse sequences were used to accumulate quadrupole echo signals before the FFT analysis. Assignment of the frequencies to atomic positions was made and the results are analysed in relation to the molecular chemical bonds and possible H-bonds in the crystal structures. The new NQR frequencies are reasonably related to the previously published NQR spectrum of the third family member, 1H-tetrazole.