The equilibrium molecular structure of 3-methyl-4-nitro- and 4-methyl-3-nitrofuroxans by gas-phase electron diffraction and coupled cluster calculations

Belyakov, A. V.; Oskorbin, Alexander A.; Losev, Vitalii A.; Rykov, Anatolii N.; Shishkov, Igor F.; Ферштат, Леонид Л.; Larin, Alexander А.; Кузнецов, В. В.; Махова, Нина Н.

doi:10.1016/j.molstruc.2020.128856

Cited by 7 publications

(2 citation statements)

References 61 publications

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“…This feature is attributed to the absence of strong intra- and intermolecular interactions (e.g., hydrogen bonds or π-stacking) in the structural motif of the species studied. The previous structural investigations demonstrated that most of the furoxan derivatives have only short O⋯O contacts that do not provide sufficient stabilization via a supramolecular organization [ 20 , 52 ]. The possible ways to resolve this issue could be: (i) the design of novel materials with high-molar mass substituents capable of formation of strong intermolecular bonds to decrease the volatility (cf.…”

Section: Resultsmentioning

confidence: 99%

Nitro-, Cyano-, and Methylfuroxans, and Their Bis-Derivatives: From Green Primary to Melt-Cast Explosives

et al. 2020

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In the present work, we studied in detail the thermochemistry, thermal stability, mechanical sensitivity, and detonation performance for 20 nitro-, cyano-, and methyl derivatives of 1,2,5-oxadiazole-2-oxide (furoxan), along with their bis-derivatives. For all species studied, we also determined the reliable values of the gas-phase formation enthalpies using highly accurate multilevel procedures W2-F12 and/or W1-F12 in conjunction with the atomization energy approach and isodesmic reactions with the domain-based local pair natural orbital (DLPNO) modifications of the coupled-cluster techniques. Apart from this, we proposed reliable benchmark values of the formation enthalpies of furoxan and a number of its (azo)bis-derivatives. Additionally, we reported the previously unknown crystal structure of 3-cyano-4-nitrofuroxan. Among the monocyclic compounds, 3-nitro-4-cyclopropyl and dicyano derivatives of furoxan outperformed trinitrotoluene, a benchmark melt-cast explosive, exhibited decent thermal stability (decomposition temperature >200 °C) and insensitivity to mechanical stimuli while having notable volatility and low melting points. In turn, 4,4′-azobis-dicarbamoyl furoxan is proposed as a substitute of pentaerythritol tetranitrate, a benchmark brisant high explosive. Finally, the application prospects of 3,3′-azobis-dinitro furoxan, one of the most powerful energetic materials synthesized up to date, are limited due to the tremendously high mechanical sensitivity of this compound. Overall, the investigated derivatives of furoxan comprise multipurpose green energetic materials, including primary, secondary, melt-cast, low-sensitive explosives, and an energetic liquid.

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Section: Resultsmentioning

confidence: 99%

Nitro-, Cyano-, and Methylfuroxans, and Their Bis-Derivatives: From Green Primary to Melt-Cast Explosives

et al. 2020

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“…В то время уже была исследована структура нитросодержащих производных фуроксанов в газовой фазе, таких как 3-метил-4-нитро-и 4-метил-3нитрофуроксан, методом газовой электронографии (ГЭ) и квантово-химических расчетов [9]. Также с использованием этих же методов был Тонкие химические технологии = Fine Chemical Technologies.…”

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Quantum chemical research of the molecular structure of 3,4-dicyanofuroxan

Kolesnikova

Lobanov

et al. 2023

Fine Chem. Technol.

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Objectives. The study set out to determine the equilibrium parameters of the 3,4-dicyanofuroxan molecule by means of molecule geometry optimization by quantum chemistry methods, verify the adequacy of the methods used, and compare the obtained results with X-ray diffraction analysis (XRD) and gas electron diffraction (GED) data.Methods. Quantum chemical calculations were carried out using B3LYP, MP2, and CCSD(T) methods with 6-31G(d,p), cc-pVTZ, and aug-cc-pVTZ basis sets.Results. The equilibrium molecular structure of 3,4-dicyanofuroxan was refined by means of quantum chemical calculations using the Gaussian09 program. The geometrical parameters were compared with the structure of this compound in the solid phase and a number of related compounds in gas and solid phases. It was theoretically established that the planar equilibrium structure of the dicyanofuroxan molecule has CS symmetry. The structure of the free dicyanofuroxan molecule was found to differ depending on the phase. The B3LYP and CCSD(T) methods describe the molecular structure of dicyanofuroxan more accurately than the MP2 method. A regularity was revealed, according to which an increase in the basis, as a rule, leads to a better agreement of the geometry, regardless of the functional.Conclusions. The calculations performed are in good agreement with the literature data and results of joint analysis by GED and XRD. The effect of cyano substituents on the ring geometry is observed in comparison with the literature data for the dicyanofuroxan molecule. For the molecule in question, it is better to use the B3LYP/aug-cc-pVTZ method. The values of geometric parameters obtained by this method are in better agreement with the structure in the gas phase. The discrepancies with the experimental XRD results may be due to interactions in the crystal structure. Differences in the geometric parameters obtained on the basis of different functionals and bases make this molecule interesting for experimental structural studies using GED or microwave spectroscopy, which will permit the identification of optimal methods and bases for obtaining the geometric parameters of furoxan class molecules.

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Database with Equilibrium Structures of Free Molecules

Vogt,

Demaison

2023

Lecture Notes in Chemistry

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The equilibrium molecular structure of 3-methyl-4-nitro- and 4-methyl-3-nitrofuroxans by gas-phase electron diffraction and coupled cluster calculations

Cited by 7 publications

References 61 publications

Nitro-, Cyano-, and Methylfuroxans, and Their Bis-Derivatives: From Green Primary to Melt-Cast Explosives

Nitro-, Cyano-, and Methylfuroxans, and Their Bis-Derivatives: From Green Primary to Melt-Cast Explosives

Quantum chemical research of the molecular structure of 3,4-dicyanofuroxan

Database with Equilibrium Structures of Free Molecules

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