Recurrent π–π stacking motifs in three new 4,5-dihydropyrazolyl–thiazole–coumarin hybrids: X-ray characterization, Hirshfeld surface analysis and DFT calculations

Madni, Murtaza; Ahmed, Muhammad Naeem; Hafeez, Muhammad; Ashfaq, Muhammad; Tahir, Muhammad Nawaz; Gil, Diego M.; Galmés, Bartomeu; Hameed, Shahid; Frontera, Antonio

doi:10.1039/d0nj02931a

Cited by 58 publications

(23 citation statements)

References 71 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We can quantitate the contribution of each interatomic contact that is the main aspect of the crystal packing of single crystals. For this, 2D fingerprint plots are formed by both compounds . For the interatomic contact calculation, reciprocal contact of each contact is added.…”

Section: Results and Discussionmentioning

confidence: 99%

Single-Crystal Investigation, Hirshfeld Surface Analysis, and DFT Study of Third-Order NLO Properties of Unsymmetrical Acyl Thiourea Derivatives

et al. 2021

Self Cite

View full text Add to dashboard Cite

In the current research work, unsymmetrical acyl thiourea derivatives, 4-((3-benzoylthioureido)methyl)cyclohexane-1-carboxylic acid (BTCC) and methyl 2-(3-benzoylthioureido)benzoate (MBTB), have been synthesized efficiently. The structures of these crystalline thioureas were unambiguously confirmed by single-crystal diffractional analysis. The crystallographic investigation showed that the molecular configuration of both compounds is stabilized by intramolecular N–H···O bonding. The crystal packing of BTCC is stabilized by strong N–H···O bonding and comparatively weak O–H···S, C–H···O, C–H···π, and C–O···π interactions, whereas strong N–H···O bonding and comparatively weak C–H···O, C–H···S, and C–H···π interactions are responsible for the crystal packing of MBTB. The noncovalent interactions that are responsible for the crystal packing are explored by the Hirshfeld surface analysis for both compounds. The void analysis is performed to find the quantitative strength of crystal packing in both compounds. Additionally, state-of-the-art applied quantum chemical techniques are used to further explore the structure–property relationship in the above-entitled molecules. The optimization of molecular geometries showed a reasonably good correlation with their respective experimental structures. Third-order nonlinear optical (NLO) polarizability calculations were performed to see the advanced functional application of entitled compounds as efficient NLO materials. The average static γ amplitudes are found to be 27.30 × 10–36 and 102.91 × 10–36 esu for the compounds BTCC and MBTB, respectively. The γ amplitude of MBTB is calculated to be 3.77 times larger, which is probably due to better charge-transfer characteristics in MBTB. The quantum chemical analysis in the form of 3-D plots was also performed for their frontier molecular orbitals and molecular electrostatic potentials for understanding charge-transfer characteristics. We believe that the current investigation will not only report the new BTCC and MBTB compounds but also evoke the interest of the materials science community in their potential use in NLO applications.

show abstract

Section: Results and Discussionmentioning

confidence: 99%

Single-Crystal Investigation, Hirshfeld Surface Analysis, and DFT Study of Third-Order NLO Properties of Unsymmetrical Acyl Thiourea Derivatives

et al. 2021

Self Cite

View full text Add to dashboard Cite

show abstract

“…Other such interactions are ALL–C, ALL–O, and ALL–N with percentage contributions of 15.2, 6.2, and 1.7%, respectively. These interactions are important to discuss as they help better understand the crystal packing. − Similarly, the interaction of an atom present inside the HS with all the atoms located in the vicinity of the HS is computed to further explore crystal packing, as shown in Figure b. This investigation inferred that the H atom present inside the HS has the strongest interaction with the atoms of neighboring molecules present as compared to other atoms.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Crystal Structure, Hirshfeld Surface Analysis, and Computational Study of a Novel Organic Salt Obtained from Benzylamine and an Acidic Component

et al. 2021

Self Cite

View full text Add to dashboard Cite

A novel Schiff base compound named as phenylmethanaminium ( E )-4-((benzylimino)methyl)benzoate C 7 H 10 N + . C 15 H 12 NO 2 – ( A ) is synthesized by the chemical reaction of benzylamine and 4-carboxybenzaldehyde in ethanol, and the structure of the titled compound is verified using the single-crystal X-ray diffraction technique. Structural investigation inferred that the crystal packing is mainly stabilized by N–H···O and comparatively weak C–H···O bonding between the cation and anion and further stabilized by weak C–H···π and C–O···π interactions. Hirshfeld surface analysis is employed to explore the noncovalent interactions that are responsible for crystal packing quantitatively. Furthermore, we have used state-of-the-art quantum chemical calculations to get comprehensive insights into the structure–optoelectronic property relationship for the entitled compound. The molecular geometry of compound A is optimized at the M06/6-311G* level of theory. The linear polarizability, third-order nonlinear optical (NLO) polarizability, total and partial density of states, and UV–visible spectrum are calculated through quantum chemical calculations. We believe that compound A is not only a new addition to crystallographic data but also possesses good optical and NLO properties for its potential use in lasers and frequency-converting applications.

show abstract

“…14,15 Motivated by the aforementioned findings and pursuing our studies on different five membered heterocycles [16][17][18][19] as well as structural studies 20 we have designed new derivatives with pyrazolyl-thiazole moieties (Scheme 2). Similarly in continuation of our recent studies on antiparallel π-π interactions in isatin based hydrazides, 21 π-hole tetrel bonding in 2-triazolyl-2-oxoacetate derivatives 22 and recurrent π-stacking motifs in pyrazolyl-thiazole-coumarin hybrids, 23 we report herein synthetic protocols to access arylsubstiuted pyrazolyl-thiazole derivatives. The structures reported herein exhibit interesting solid state architectures with an intricate combination of interactions, including…”

Section: Introductionmentioning

confidence: 65%

Crystal engineering with pyrazolyl-thiazole derivatives: structure-directing role of π-stacking and σ-hole interactions

et al. 2021

Self Cite

View full text Add to dashboard Cite

The synthesis and X-ray characterization of 1-(2-(3-(4-bromophenyl)-5-(4-methoxyphenyl)-4,5-dihydro-1H-pyrazol-1-yl)-4-methylthiazol-5-yl)ethanone (7), ethyl 2-(5-(4-bromophenyl)-3-(4-chlorophenyl)-4,5-dihydropyrazol-1-yl)thiazole-4-carboxylate (8) and 2-(5-(4-chlorophenyl)-3-phenyl-4,5-dihydro-1H-pyrazol-1-yl)-N'-(2-hydroxy-3-methoxybenzylidene)thiazole-4-carbohydrazide (10) is described in this manuscript. The structure-directing role of a variety of noncovalent interactions have been...

show abstract

Recurrent π–π stacking motifs in three new 4,5-dihydropyrazolyl–thiazole–coumarin hybrids: X-ray characterization, Hirshfeld surface analysis and DFT calculations

Cited by 58 publications

References 71 publications

Single-Crystal Investigation, Hirshfeld Surface Analysis, and DFT Study of Third-Order NLO Properties of Unsymmetrical Acyl Thiourea Derivatives

Single-Crystal Investigation, Hirshfeld Surface Analysis, and DFT Study of Third-Order NLO Properties of Unsymmetrical Acyl Thiourea Derivatives

Synthesis, Crystal Structure, Hirshfeld Surface Analysis, and Computational Study of a Novel Organic Salt Obtained from Benzylamine and an Acidic Component

Crystal engineering with pyrazolyl-thiazole derivatives: structure-directing role of π-stacking and σ-hole interactions

Contact Info

Product

Resources

About