Combined gas-phase electron diffraction and coupled cluster determination of the molecular structure of 3,4-dinitrofurazan - A propellant ingredient

Combined gas-phase electron diffraction and coupled cluster determination of the molecular structure of 3,4-dinitrofurazan - A propellant ingredient Full article

Journal

Journal of Molecular Structure
ISSN: 0022-2860 , E-ISSN: 1872-8014

Output data

Year: 2022, Volume: 1250, Article number : 131669, Pages count : DOI: 10.1016/j.molstruc.2021.131669

Authors

Belyakov Alexander V. ¹ , Losev Vitalii A. ¹ , Rykov Anatolii N. ² , Shishkov Igor F. ² , Kuznetsov Vladimir V. ³ , Khakhalev Artem V. ³ , Sheremetev Aleksei B. ³

Affiliations

1	Saint-Petersburg State Technological Institute, Saint Petersburg 190013, Russia
2	Department of Chemistry, Moscow State University, Moscow 119992, Russia
3	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 119991, Russia

The equilibrium molecular structure of the first pernitroheterocycle, 3,4-dinitrofurazan, in terms of the dynamic model with relaxation of all structural parameters, has been calculated for the first time using gas-phase electron diffraction (GED) with coupled cluster calculations up to CCSD(T)-AE/aug-cc-pwCVQZ level of theory. A model with C2 symmetry was found to be the best match for the observed scattering intensities. The structural parameters of 3,4-dinitrofurazan were compared to those of the parent furazan molecule calculated at the CCSD(T)-AE/aug-cc-pwCVQZ level of theory. The mean amplitudes and vibrational corrections necessary for the GED analysis were computed at the B3LYP/SNST//MP2/aug-cc-PVTZ level of theory using quadratic and cubic force fields. With the help of several topological, magnetic, and orbital descriptors, peculiar characteristics of the electronic and geometric structure of 3,4-dinitrofurazan were studied. Comparison of the structures obtained at the CCSD(T)-AE/aug-cc-pwCVQZ and CCSD(T)-AE/cc-pwCVQZ levels shows that, when going from furazan to 3,4-dinitrofurazan, the presence of the electron-withdrawing NO2 group decreases the bond lengths and increases the C–C=N bond angles of the furazan ring. According to ICSSZZ aromaticity descriptors, the aromaticity of furoxan and 3,4-dinitrofurazan is lower than that of furazan. This is in agreement with the calculated ring current densities induced by an external magnetic field.

Belyakov A.V. , Losev V.A. , Rykov A.N. , Shishkov I.F. , Kuznetsov V.V. , Khakhalev A.V. , Sheremetev A.B.
Combined gas-phase electron diffraction and coupled cluster determination of the molecular structure of 3,4-dinitrofurazan - A propellant ingredient
Journal of Molecular Structure. 2022. V.1250. 131669 . DOI: 10.1016/j.molstruc.2021.131669 WOS Scopus OpenAlex

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