Importance of O⋯N interaction between nitro groups in crystals

Daszkiewicz, Marek

doi:10.1039/c3ce41788c

Cited by 52 publications

(41 citation statements)

References 23 publications

(21 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This mode is relevant for molecules C supporting the most extensive C-HÁ Á ÁO hydrogen bonding. The energy of the (lone pair)Á Á Á hole interaction of the nitro groups (Type 1, E tot = À19.7 kJ mol À1 ) agrees with the range from À8.5 to À33.6 kJ mol À1 reported by Daszkiewicz (2013) for different nitro derivatives and is nearly identical to the value of À19.3 kJ mol À1 for aliphatic 1,3,3-trinitroazetidine (Archibald et al, 1990). The energy of such bonding is superior, by ca 5-8 kJ mol À1 , to the single C-HÁ Á ÁO hydrogen bonds of aliphatic donors and nitro acceptors (Type 2).…”

Section: Type Asupporting

confidence: 85%

Bulk polarity of 3,5,7-trinitro-1-azaadamantane mediated by asymmetric NO₂(lone pair)...NO₂(π-hole) supramolecular bonding

Domasevitch¹,

Senchyk²,

Krautscheid³

2020

Acta Crystallogr C

View full text Add to dashboard Cite

Molecular crystals exhibiting polar symmetry are important paradigms for developing new electrooptical materials. Though accessing bulk polarity still presents a significant challenge, in some cases it may be rationalized as being associated with the specific molecular shapes and symmetries and subtle features of supramolecular interactions. In the crystal structure of 3,5,7‐trinitro‐1‐azaadamantane, C9H12N4O6, the polar symmetry of the molecular arrangement is a result of complementary prerequisites, namely the C3v symmetry of the molecules is suited to the generation of polar stacks and the inherent asymmetry of the principal supramolecular bonding, as is provided by NO2(lone pair)…NO2(π‐hole) interactions. These bonds arrange the molecules into a trigonal network. In spite of the apparent simplicity, the structure comprises three unique molecules (Z′ = + + ), two of which are donors and acceptors of three N…O interactions and the third being primarily important for weak C—H…O hydrogen bonding. These distinct structural roles agree with the results of Hirshfeld surface analysis. A set of weak C—H…O and C—H…N hydrogen bonds yields three kinds of stacks. The orientation of the stacks is identical and therefore the polarity of each molecule contributes additively to the net dipole moment of the crystal. This suggests a special potential of asymmetric NO2(lone pair)…NO2(π‐hole) interactions for the supramolecular synthesis of acentric materials.

show abstract

Section: Type Asupporting

confidence: 85%

Bulk polarity of 3,5,7-trinitro-1-azaadamantane mediated by asymmetric NO₂(lone pair)...NO₂(π-hole) supramolecular bonding

Domasevitch¹,

Senchyk²,

Krautscheid³

2020

Acta Crystallogr C

View full text Add to dashboard Cite

show abstract

“…They play a key role in supramolecular chemistry which is defined as ''chemistry beyond the molecule'' and are without doubt the dominant type of interaction in maintaining the three-dimensional structure of large systems such as proteins, nucleic acids and other large molecules [1][2][3][4][5][6][7][8]. In these systems, NCI involving aromatic rings can be distinguished and those are for instance: p-stacking, cation/p, anion-p, C-H/p and N-H/p interactions [9][10][11][12][13][14].…”

Section: Introductionmentioning

confidence: 99%

The intricacies of the stacking interaction in a pyrrole–pyrrole system

Sierański

2016

Struct Chem

View full text Add to dashboard Cite

Extensive calculations of potential energy surfaces for parallel-displaced configurations of pyrrole-pyrrole systems have been carried out by the use of a dispersion-corrected density functional. System geometries associated with the energy minima have been found. The minimum interaction energy has been calculated as -5.38 kcal/mol. However, bonding boundaries appeared to be relatively broad, and stacking interactions can be binding even for ring centroid distances larger than 6 Å . Though the contribution of the correlation energy to intermolecular interaction in pyrrole dimers appeared to be relatively small (around 1.6 smaller than it is in a benzenebenzene system), this system's minimum interaction energy is lower than those calculated for benzene-benzene, benzene-pyridine and even pyridine-pyridine configurations. The calculation of the charges and energy decomposition analysis revealed that the specific charge distribution in a pyrrole molecule and its relatively high polarization are the significant source of the intermolecular interaction in pyrrole dimer systems.

show abstract

“…The molecular electrostatic potential and electric moments derived from the charge density help to determine the recognition properties, such as reactivity in a desired molecule in a chemical reaction. Due to the importance of the intermolecular C-H...O, ..., and nitro-nitro (NO 2 ...NO 2 ) interactions in crystal engineering [5], we decided to obtain an insight of the nature of the chemical bonds and the important molecular interactions of the title compound by X-ray charge density and compare it to the results obtained from the Quantum Theory of Atoms In Molecules (QTAIM) by AIM2000 program package [6].…”

Section: Introductionmentioning

confidence: 99%

Experimental and Theoretical X-ray Charge-Density Study of 1-Cycloheptylidene-2-(2,4-dinitrophenyl)hydrazine: A Hydrazone Derivative

Sharafi

2016

Scientia Iranica

View full text Add to dashboard Cite

The experimental charge density of a hydrazone derivative has been determined from low temperature (100 K) single crystal X-ray di raction data by multipolar Hansen-Coppens formalism re nement and gas phase ab initio theoretical calculations. The topology of the electron density within the molecule as well as the intramolecular and intermolecular interactions have been analyzed. The topological properties of electron density determined by the experiment were compared with the theoretical results obtained from Gaussian03 at the B3LYP/6-311++G** level of theory. The covalent nature of the bonds in the molecule has been established by (3,-1) bond critical points associated with relatively large electron densities (1.59-3.34 e. A 3) and highly negative Laplacian values (4.73-21.30 e. A 5). Numerical and analytical procedures were used to derive the charges integrated with each atomic basin. The highest charge magnitude (-0.66 e) was found in N2 and N4 atoms. The crystal packing is stabilized by the weak intermolecular ..., C-H...O and NO 2 (N)...(O)NO 2 interactions, as con rmed by the presence of critical points in the topological analysis.

show abstract

Importance of O⋯N interaction between nitro groups in crystals

Cited by 52 publications

References 23 publications

Bulk polarity of 3,5,7-trinitro-1-azaadamantane mediated by asymmetric NO₂(lone pair)...NO₂(π-hole) supramolecular bonding

Bulk polarity of 3,5,7-trinitro-1-azaadamantane mediated by asymmetric NO₂(lone pair)...NO₂(π-hole) supramolecular bonding

The intricacies of the stacking interaction in a pyrrole–pyrrole system

Experimental and Theoretical X-ray Charge-Density Study of 1-Cycloheptylidene-2-(2,4-dinitrophenyl)hydrazine: A Hydrazone Derivative

Contact Info

Product

Resources

About

Importance of O⋯N interaction between nitro groups in crystals

Cited by 52 publications

References 23 publications

Bulk polarity of 3,5,7-trinitro-1-azaadamantane mediated by asymmetric NO2(lone pair)...NO2(π-hole) supramolecular bonding

Bulk polarity of 3,5,7-trinitro-1-azaadamantane mediated by asymmetric NO2(lone pair)...NO2(π-hole) supramolecular bonding

The intricacies of the stacking interaction in a pyrrole–pyrrole system

Experimental and Theoretical X-ray Charge-Density Study of 1-Cycloheptylidene-2-(2,4-dinitrophenyl)hydrazine: A Hydrazone Derivative

Contact Info

Product

Resources

About

Bulk polarity of 3,5,7-trinitro-1-azaadamantane mediated by asymmetric NO₂(lone pair)...NO₂(π-hole) supramolecular bonding

Bulk polarity of 3,5,7-trinitro-1-azaadamantane mediated by asymmetric NO₂(lone pair)...NO₂(π-hole) supramolecular bonding