Density Functional Theory and Experimental Studies of the Molecular, Vibrational, and Crystal Structure of Bis-Oxadiazole-Bis-Methylene Dinitrate (BODN)

Abstract

Density function theory (DFT) and experimental characterization of energetic materials play important roles in understanding molecular structure−property relations and validating models for their predictive capabilities. Here, we report our modeling and experimental results on the molecular, vibrational, and crystal structure of energetic bisoxadiazole-bis-methylene dinitrate (BODN) obtained by molecular DFT (M-DFT) at the B3LYP-6-31G** level, crystal DFT (C-DFT) using the Perdew−Burke−Ernzerhof functional optimized with norm-conserving pseudopotentials, X-ray diffractometry, infrared and Raman spectroscopy, and thermogravimetric analysis. Both models predict well the experimental bond lengths, bond angles, and torsion angles of BODN. The C-DFT lattice constant values are in excellent agreement with those determined experimentally, with unit cell length and angle values differing by less than 1.2 and 0.7%, respectively. BODN presents van der Waals O•••H and O•••C bifurcated intramolecular contacts and short N•••H and O•••O intermolecular contacts. Overall, the predicted vibrational energies of both models are in line with experiment. M-DFT thermodynamic calculations predict well the experimentally derived lattice energy (−131 kJ/mol) and the M-DFT electrostatic potential calculations reveal a low sensitivity to impact. In addition, C-DFT band gap calculations predict a value of 3.80 eV for BODN, resulting predominantly from the ring O and N atoms, suggesting it is insensitive to impact. These results are compared and contrasted with those obtained in this study or reported previously for 3,3-bis-isoxazole-5,5′-bis-methylene dinitrate (BIDN).

Synthesis, characterization, molecular modeling studies, and biological evaluation of metal piroxicam complexes (M = Ni(II), Pt(IV), Pd(II), Ag(I)) as antibacterial and anticancer agents

“…The more differences in red and blue colors, the more polar the molecule (extreme negative and positive sites). If the white or lighter color shades are the dominant over the molecule, the molecule is mostly non‐polar (Sausa et al, 2018; Suhasini et al, 2015). Figure 11 depicts that the largest positive charges of the complexes are putted down to the metals, nitrogen atoms, and hydrogen atoms bonded to nitrogen, making these groups as electron‐poor areas and susceptible to nucleophilic attack such as binding to DNA bases and amino acid residues.…”

Thermal Decomposition of Gas-Phase Bis(1,2,4-oxadiazole)bis(methylene) Dinitrate (BODN): A CCSD(T)-F12/DFT-Based Study of Reaction Pathways

“…Based on results produced with the CCSD­(T)-F12/aVDZ//M06-2X/6-311+G­(3df,2p) model, BODN’s gas-phase heat of formation at 298 K, Δ f H g (298 K), was predicted to be 8.7 kcal/mol. Coupled with the measured value for BODN’s enthalpy of sublimation (Δ sub H ) (30.2 kcal/mol) (Sausa et al …”

“…Based on results produced with the CCSD(T)-F12/ aVDZ//M06-2X/6-311+G(3df,2p) model, BODN's gas-phase heat of formation at 298 K, Δ f H g (298 K), was predicted to be 8.7 kcal/mol. Coupled with the measured value for BODN's enthalpy of sublimation (Δ sub H) (30.2 kcal/mol) (Sausa et al 12 ), its condensed phase heat of formation at 298 K, Δ f H c (298 K) was predicted to be −21. INT241, and INT170 that generate products that are identical to those produced by their unimolecular decompositions via R1b, R8b, and R5b, respectively, R18a, R19a, and R20a offer lower-energy routes to them.…”

“…9,10 Various physical properties of solid-state BODN have been characterized. 12,13 It was observed that the temperature at which its decomposition onset (457 K) was unusually high for a nitrate ester-functionalized neutral. 11 The thermal kinetic performance and safety of BODN were studied using differential scanning calorimetry (DSC) and thermal gravimetric (TG/TDG) methods, 14 and the apparent activation energy of the first exothermic decomposition reaction was estimated to be 35.2 kcal/mol using the Kissinger and Ozawa methods.…”

In-silico Investigations of quinine and quinidine as potential Inhibitors of AKR1B1 and AKR1B10: Functional and structural characterization

“…The following information will be determined by the current study i . e ., optimized geometric parameters, the frontier molecular orbital (FMO), global and local reactivity descriptors and molecular electrostatic potential (MEP) [ 18 ]. Check files were viewed using Guass View 6 [ 19 ].…”