Experimental and Theoretical Characterization of the Hexaazidophosphate(V) Ion

(PPN)[P(N<sub>3</sub>)<sub>6</sub>] (<b>2</b>) was synthesized by the metathesis of Na[P(N<sub>3</sub>)<sub>6</sub>] (<b>1</b>) and (PPN)N<sub>3</sub> (PPN<sup>+</sup> = {(Ph<sub>3</sub>P)<sub>2</sub>N}<sup>+</sup>), allowing for the isolation and full characterization of a stable hexaazidophosphate(V) salt by <sup>31</sup>P and <sup>14</sup>N 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 <b>2</b> are triclinic, space group <i>P</i>1̅, <i>a</i> = 9.6296(9), <i>b</i> = 9.8158(9), <i>c</i> = 10.1414(10) Å, <i>α</i> = 92.635(5)°, β = 93.437(5)°, γ = 92.105(4)°, and <i>Z</i> = 1. The [P(N<sub>3</sub>)<sub>6</sub>]<sup>−</sup> ion of <b>2</b> is isolated in the solid state and adopts <i>S</i><sub>6</sub> symmetry both in the crystal and in solution. Thermogravimetric analysis and differential scanning calorimetry measurements reveal a surprising thermal stability of <b>2</b> (<i>T</i><sub>dec</sub> ca. 200 °C). No friction sensitivity was encountered.