A stable superatomic nitrogen ring crystal under ambient conditions

The nitrogen ring structure represented by the pentazolate anion (N 5 − ) has received widespread attention due to its potential to form high–energy-density materials. However, the inherent high-energy properties of nitrogen rings make obtaining their stable crystals under ambient conditions a recognized key challenge. Here, we report a stable polynitrogen crystal Li 4 (N 5 ) 2 under ambient conditions by first-principles structural and dynamic studies. In its primitive cell, electron transfer from lithium (Li) atoms to N 5 rings occupies their delocalized orbitals, forming anionic N 5 − in a superatomic state, where Li-N 5 ionic interactions and N 5 -N 5 van der Waals interactions jointly maintain the structural stability. These interactions result in structure anisotropy, where the ab -plane direction is governed by both ionic and covalent interactions, while the c -axis direction is dominated by ionic interactions. Our findings provide an important foundation for the development of high–energy-density materials based on nitrogen rings and for related artificial unit crystallization pathways.