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Tidey, Jeremiah P.; Zhurov, Vladimir V.; Gianopoulos, Christopher G.; Hermann, Tobias S.; Pinkerton, A. Alan (2018): QTAIM Assessment of the Intra- and Intermolecular Bonding in a Bis(nitramido-oxadiazolate) Energetic Ionic Salt at 20 K. In: Journal of Physical Chemistry A, Vol. 122, No. 50: pp. 9676-9687
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Abstract

Accurate experimental determination of the electron density distribution for the energetic ionic salt bis(ammonium) 2,2'-dinitramido-5,5'-bis(1-oxa-3,4-diazolate) dihydrate (1) is obtained from multipole modeling of single-crystal X-ray diffraction data collected at 20 K. The intra- and intermolecular bonding is assessed in terms of the quantum theory of atoms in molecules (QTAIM) with a view to better understanding the physicochemical properties in relation to chemical bonding. Topological analysis reveals stronger bonding for the N-NO2 bond relative to energetic nitramines RDX and HMX and the indication of a trend between this and impact sensitivity of nitro-containing energetic materials is noted. The intermolecular bonding of 1 is dominated by classical H-bonds but includes multiple R pi-bonding interactions and interactions between H-bond donor and acceptor atoms where bond paths are deflected by H atoms. There also exists a weak O center dot center dot center dot O interaction between end-on nitro groups, as well as an intramolecular ring-forming 1,5-type interaction. An anharmonic description of thermal motion was required to obtain the best fitting model, despite the low temperature of the study. The experimental study was complemented by periodic boundary DFT calculations at the experimental geometry as well as gas phase calculations on the isolated dianion.