Structure and Bonding in β-HMX-Characterization of a Trans-Annular N···N Interaction

• Published in: Journal of the American Chemical Society Vol. 129; no. 45; pp. 13887 - 13893
• Main Authors: Zhurova, Elizabeth A, Zhurov, Vladimir V, Pinkerton, A. Alan
• Format: Journal Article
• Language: English
• Published: American Chemical Society 14.11.2007
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja073801b

Chemical bonding in the β-phase of the 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) crystal based on the experimental electron density obtained from X-ray diffraction data at 20 K, and solid state theoretical calculations, has been analyzed in terms of the quantum theory of atoms in molecules. Features of the intra- and intermolecular bond critical points and the oxygen atom lone-pair locations are discussed. An unusual N···N bonding interaction across the 8-membered ring has been discovered and characterized. Hydrogen bonding, O···O and O···C intermolecular interactions are reported. Atomic charges and features of the electrostatic potential are discussed.