An independent investigation of the crystal structure of 1,8-dinitronaphthalene (orthorhombic form) at 22 and 97°C

Ciechanowicz-Rutkowska, M.

doi:10.1016/0022-4596(77)90036-6

Cited by 11 publications

(9 citation statements)

References 2 publications

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“…The DFT(M06‐2X)/TZVP optimized structures are in good agreement with available X‐ray crystallographic data and previous DFT calculations for 35 of the 63 nitroaromatic energetic molecules. The optimized structures of the 63 nitroaromatic energetic molecules are included in the Supporting Information (Figs.…”

Section: Resultssupporting

confidence: 85%

Trigger bond analysis of nitroaromatic energetic materials using wiberg bond indices

Shoaf

Bayse

2018

J Comput Chem

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The identification of trigger bonds, bonds that break to initiate explosive decomposition, using computational methods could help direct the development of novel, "green" and efficient high energy density materials (HEDMs). Comparing bond densities in energetic materials to reference molecules using Wiberg bond indices (WBIs) provides a relative scale for bond activation (%ΔWBIs) to assign trigger bonds in a set of 63 nitroaromatic conventional energetic molecules. Intramolecular hydrogen bonding interactions enhance contributions of resonance structures that strengthen, or deactivate, the CNO trigger bonds and reduce the sensitivity of nitroaniline-based HEDMs. In contrast, unidirectional hydrogen bonding in nitrophenols strengthens the bond to the hydrogen bond acceptor, but the phenol lone pairs repel and activate an adjacent nitro group. Steric effects, electron withdrawing groups and greater nitro dihedral angles also activate the CNO trigger bonds. %ΔWBIs indicate that nitro groups within an energetic molecule are not all necessarily equally activated to contribute to initiation. %ΔWBIs generally correlate well with impact sensitivity, especially for HEDMs with intramolecular hydrogen bonding, and are a better measure of trigger bond strength than bond dissociation energies (BDEs). However, the method is less effective for HEDMs with significant secondary effects in the solid state. Assignment of trigger bonds using %ΔWBIs could contribute to understanding the effect of intramolecular interactions on energetic properties. © 2018 Wiley Periodicals, Inc.

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Section: Resultssupporting

confidence: 85%

Trigger bond analysis of nitroaromatic energetic materials using wiberg bond indices

Shoaf

Bayse

2018

J Comput Chem

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“…The angle between the NO 2 group plane and the aromatic ring suggests a possibility of a mesomeric interaction of the substituent with the π-electron system. The comparison of the data for optimized molecule and the crystal structure 25 shows an influence of the intermolecular interaction on differentiation of both aromatic rings. The HOMA values for 1,8-dinitronaphthalene optimized and crystal structure are similar and indicate a small decrease of the aromaticity.…”

Section: ■ Results and Discussionmentioning

confidence: 95%

Substituents and Environment Influences on Aromaticity of peri- and para-Substituted Naphthalenes

Majerz

Dziembowska

2014

J. Phys. Chem. A

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The influence of substituents and environment on the aromaticity of the naphthalene ring is shown for a series of peri-and para-substituted naphthalenes. Crystal structure geometries are compared with the single molecule structures in vacuum (optimized at the B3LYP/6-311++G** level) and with structures determined in media of different polarity. The harmonic oscillator model of aromaticity (HOMA) index of the naphthalene rings has been used to characterize the aromaticity of the investigated molecules. It has been shown that the ellipticity of the C2−C3 (C6−C7) bonds can be applied as a measure of participation of the quinoid resonance structure and through-resonance effect between the para-substituents. ■ INTRODUCTIONPeri-interaction in 1,8-disubstituted naphthalenes has attracted attention for a long time, due to their influence on physical and chemical properties of the compounds. 1−6 Two substituents in peri-positions of naphthalene are forced to be in close contact, generally closer than the sum of their van der Waals radii, leading to strong through-space interactionsattractive or repulsive depending on their properties. To release the steric strain, the substituents generally adopt nonplanar conformations. This through-space interaction leads to a change of exocyclic bonds and torsion angles and a disturbance of the naphthalene skeleton. When into the 4 and/or 5 position of the naphthalene ring having a pair of the peri-substituents in the 1,8 positions we introduce substituents with opposite electronic properties, the through-resonance effect may appear. 7,8 The through-resonance effectassociated with a charge transfer from electron-donor to electron-acceptor group in the para positionresults in an increase of the weight of the canonical quinoid structure. The electronic structure and geometry of the naphthalene derivatives with two pairs of peri substituents of opposite electronic properties in the para positions is the effect of compromise between the effects of through-space (peri) and through-bonds (through-resonance) interactions. 4,7,8 One of the best known groups of naphthalene derivatives, with substituents in peri and para positions, are 1,8-bis(dialkylamino)naphthalenes, called the "proton sponges". 4−6 Exceptional basicity of 1,8-bis(dimethylamino)-napthalene (pK a = 12.1 9 ) results from the repulsive steric and electrostatic interactions between the dimethylamino groups. The 1,8-bis(dialkylamino)naphthalenes additionally substituted with electron-accepting groups in 4,5 positions, called "the pushpull proton sponges", exhibit some interesting properties caused by a through-resonance (push−pull) interaction. 7,8 It was shown that these compounds are very sensitive to the solvent effect. 7,8,10 The through-space and through-bond interaction between the pairs of substituents in peri and para positions in the naphthalene ring affects both the π-electron delocalization and geometry of the aromatic ring. A consequence of these interactions is a change of aromaticity of the naphthalene ring. A π-e...

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“…Remarkably, the intermolecular N py Á Á ÁNO 2 (n-*) interaction plays a crucial role in the molecular self-assembly and crystal packing of compound (II). The nitro N atoms have been observed to interact with electron-rich centres, such as an O atom of another nitro group (Daszkiewicz, 2013), the N atom of a dimethylamino group in perinaphthalenes (Egli et al, 1986;Ciechanowicz-Rutkowska, 1977) and the pyridinelike N atom of azole compounds (Yap et al, 2005). The geometric parameters of the intermolecular NÁ Á ÁNO 2 interactions in (II) are similar to the values found in the crystal structure of 2-methyl-4,6-dinitro-1-(2,4,6-trinitrophenyl)benzimidazole (Freyer et al, 1992), with NÁ Á ÁN = 3.089 Å and CÁ Á ÁNÁ Á ÁN = 95.4 .…”

Section: Tablementioning

confidence: 99%

Involvement of conformational isomerism in the complexity of the crystal network of 1-(4-nitrophenyl)-1H-1,3-benzimidazole derivatives driven by C—H...A (A = NO₂, N_py and π) and orthogonal N_py...NO₂ and ONO...Csp ² interactions

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An independent investigation of the crystal structure of 1,8-dinitronaphthalene (orthorhombic form) at 22 and 97°C

Cited by 11 publications

References 2 publications

Trigger bond analysis of nitroaromatic energetic materials using wiberg bond indices

Trigger bond analysis of nitroaromatic energetic materials using wiberg bond indices

Substituents and Environment Influences on Aromaticity of peri- and para-Substituted Naphthalenes

Involvement of conformational isomerism in the complexity of the crystal network of 1-(4-nitrophenyl)-1H-1,3-benzimidazole derivatives driven by C—H...A (A = NO₂, N_py and π) and orthogonal N_py...NO₂ and ONO...Csp ² interactions

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An independent investigation of the crystal structure of 1,8-dinitronaphthalene (orthorhombic form) at 22 and 97°C

Cited by 11 publications

References 2 publications

Trigger bond analysis of nitroaromatic energetic materials using wiberg bond indices

Trigger bond analysis of nitroaromatic energetic materials using wiberg bond indices

Substituents and Environment Influences on Aromaticity of peri- and para-Substituted Naphthalenes

Involvement of conformational isomerism in the complexity of the crystal network of 1-(4-nitrophenyl)-1H-1,3-benzimidazole derivatives driven by C—H...A (A = NO2, Npy and π) and orthogonal Npy...NO2 and ONO...Csp 2 interactions

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Involvement of conformational isomerism in the complexity of the crystal network of 1-(4-nitrophenyl)-1H-1,3-benzimidazole derivatives driven by C—H...A (A = NO₂, N_py and π) and orthogonal N_py...NO₂ and ONO...Csp ² interactions