The recent high-pressure synthesis of pentazolates and the subsequent stabilization of the aromatic [N-5](-) 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-6 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-6](4-). Here we present the synthesis of this species, realized in the high-pressure potassium nitrogen compound K9N56 formed at high pressures (46 and 61 GPa) and high temperature (estimated to be above 2,000 K) by direct reaction between nitrogen and KN3 in a laser-heated diamond anvil cell. The complex structure of K9N56-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-6](4-) is planar and proposed to be aromatic.
Funding: Alexander von Humboldt Foundation; Deutsche Forschungsgemeinschaft (DFG) [LA-4916/1-1, DU 954-11/1, DU 393-9/2, DU 393-13/1]; UKRI Future Leaders Fellowship [MR/V025724/1]; Federal Ministry of Education and Research, Germany (BMBF) [05K19WC1]; Swedish Research Council (VR) [2019-05600]; Swedish Government Strategic Research Areas in Materials Science on Functional Materials at Linkoeping University [2009 00971]; SeRC; Knut and Alice Wallenberg Foundation (Wallenberg Scholar grant) [KAW-2018.0194]