Sodium pentazolates NaN5 and Na2N5, new high energy density materials, are discovered during first principles crystal structure search for the compounds of varying amounts of elemental sodium and nitrogen. The pentazole anion (N-5) is stabilized in the condensed phase by sodium Na+ cations at pressures exceeding 20 GPa, and becomes metastable upon release of pressure. The sodium azide (NaN3) precursor is predicted to undergo a chemical transformation above 50 GPa into sodium pentazolates NaN5 and Na2N5. The calculated Raman spectrum of NaN5 is in agreement with the experimental Raman spectrum of a previously unidentified substance appearing upon compression and heating of NaN3. (C) 2015 Elsevier B.V. All rights reserved.