Experimental and Theoretical Characterization of the Hexaazidophosphate(V) Ion

(PPN)[P(N₃)₆] (2) was synthesized by the metathesis of Na[P(N₃)₆] (1) and (PPN)N₃ (PPN⁺ = {(Ph₃P)₂N}⁺), allowing for the isolation and full characterization of a stable hexaazidophosphate(V) salt by ³¹P and ¹⁴N NMR, UV absorption, IR and Raman spectroscopy, elemental and thermal analyses, X-ray diffraction, and Hartree−Fock and density functional theory calculations. The colorless single crystals of 2 are triclinic, space group P1̅, a = 9.6296(9), b = 9.8158(9), c = 10.1414(10) Å, α = 92.635(5)°, β = 93.437(5)°, γ = 92.105(4)°, and Z = 1. The [P(N₃)₆]⁻ ion of 2 is isolated in the solid state and adopts S₆ symmetry both in the crystal and in solution. Thermogravimetric analysis and differential scanning calorimetry measurements reveal a surprising thermal stability of 2 (T_dec ca. 200 °C). No friction sensitivity was encountered.