Aromatic hexazine [N 6 ] 4- anion featured in the complex structure of the high-pressure potassium nitrogen compound K 9 N 56

The recent high-pressure synthesis of pentazolates and the subsequent stabilization of the aromatic [N ] anion at atmospheric pressure have had an immense impact on nitrogen chemistry. Other aromatic nitrogen species have also been actively sought, including the hexaazabenzene N ring. Although a variety of configurations and geometries have been proposed based on ab initio calculations, one that stands out as a likely candidate is the aromatic hexazine anion [N ] . Here we present the synthesis of this species, realized in the high-pressure potassium nitrogen compound K N formed at high pressures (46 and 61 GPa) and high temperature (estimated to be above 2,000 K) by direct reaction between nitrogen and KN in a laser-heated diamond anvil cell. The complex structure of K N -composed of 520 atoms per unit cell-was solved based on synchrotron single-crystal X-ray diffraction and corroborated by density functional theory calculations. The observed hexazine anion [N ] is planar and proposed to be aromatic.