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Silver pentazolate, a high energy density compound containing the cyclo-N 5 - anion, has recently been synthesized under ambient conditions. However, due to high sensitivity to irradiation, its crystal structure has not been determined. In this work, silver-nitrogen crystalline compounds under ambient conditions and at high pressures, up to 100 GPa, are predicted and characterized by performing first-principles evolutionary crystal structure searching with variable stoichiometry. It is found that newly discovered AgN 5 and AgN 6 are the only thermodynamically stable silver-nitrogen compounds at pressures between 42 and 80 GPa. In contrast to AgN 5 , the pentazolate AgN 6 compound contains N 2 diatomic molecules in addition to cyclo-N 5 - . These AgN 5 and AgN 6 crystals are metastable under ambient conditions with positive formation enthalpies of 54.95 kJ mol -1 and 46.24 kJ mol -1 , respectively. The underlying cause of the stability of cyclo-N 5 - silver pentazolates is the enhanced aromaticity enabled by the charge transfer from silver atoms to nitrogen rings. To aid in the experimental identification of these materials, calculated Raman spectra are reported at ambient pressure: the frequencies of N 5 - vibrational modes of AgN 5 are in good agreement with those measured in the experiment.