Thermodynamic, energetic, and topological properties of crystal packing of pyrazolo[1,5-a]pyrimidines governed by weak electrostatic intermolecular interactions

Frizzo, Clarissa P.; Tier, Aniele Z.; Gindri, Izabelle M.; Meyer, Alexandre R.; Black, Gabrielle; Belladona, Andrei L.; Martins, Marcos A. P.

doi:10.1039/c5ce00613a

Cited by 16 publications

(17 citation statements)

References 54 publications

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“…Some of the parameters used were related to the substituent (e.g., the Hammet substituent effect and electronegativity), while others were related to the molecule (e.g., melting enthalpy and sublimation enthalpy). Parameters related to the unit cell (e.g., crystal packing efficiency—CPE 27 ) and to the cluster (e.g., the total cluster surface contact area, energy, energy per area, volume, surface, globularity, and asphericity (Ω)) were also correlated. Correlations were done with all the indexes ( I D , I C , I G , and I DCG ), and the absolute difference was determined between the values of the parameters considered from each compared cluster.…”

Section: Resultsmentioning

confidence: 99%

“…Recently, we proposed an approach for better understanding the crystallization phenomenon, which considers the topological and energetic properties of a crystal, explored as a lattice that grows from a supramolecular cluster. − Therefore, using this concept, we proposed a model that may lead to further understanding the similarity between crystal structures and enable classification in different ranges of similarity. The focus of previous analyses, such as XPac, is finding similar substructures, whereas the focus of this study is to compare complete structures.…”

Section: Introductionmentioning

confidence: 99%

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Insights on the Similarity of Supramolecular Structures in Organic Crystals Using Quantitative Indexes

et al. 2018

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The quest for concepts of isostructurality in organic crystals has been long and mostly based on geometric data, even with the development of modern software. This field of study is of great interest to the pharmaceutical industry and for the prediction of crystal structures. Despite this, there is still no methodology that provides broad quantitative and comparable similarity data between two complete crystalline structures. The present study demonstrated that the similarity between two crystalline structures could be estimated from the similarity between the two “supramolecular clusters”. Quantitative indexes for similarity comparisons of crystal structures were shown using nine 5-aryl-1-(1,1-dimethylethyl)-1 H -pyrazoles as a model. This proposal includes the quantitative data of a geometric parameter ( I D ), a contact area parameter ( I C ), and an energetic parameter ( I G ). The proposed indexes exhibited good perspective regarding the similarity data and distinct regions of similarity. The range of similarity was set at I X ≥ 0.80, 0.80 > I X > 0.60, and I X ≤ 0.60 (X = D, C, or G). Indexes with a value near 1.0 indicate systems with isostructural, isocontact, and isoenergetic behavior. The results indicated that supramolecular structures with high similarity must have high values for all three indexes ( I D , I C , and I G ).

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Insights on the Similarity of Supramolecular Structures in Organic Crystals Using Quantitative Indexes

et al. 2018

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“…The most stable crystal was compound 3, followed by compound 2, and finally compound 1. The crystalline packing efficiency (CPE) 13 of compounds 1-3 was determined. The CPE represents an estimation of molecules that occupy the unit cell, as well as gives an idea of how close the molecules are in the unit cell-the closer they are, the more efficient the packing is.…”

Section: Proposed Crystallization Mechanismmentioning

confidence: 99%

“…11 This approach is a powerful tool because it analyzes all the interactions that form the crystal, which is the final product of the crystallization process. [11][12][13] Our objective herein is to further our study of the analysis of the crystal packing of heterocycles, taking into account the consequences arising from small changes in the molecular structures, in order to suggest a possible route for crystallization and its final result in the crystal. For this purpose, 1 H NMR titration will be used to generate data for the first crystallization steps, and X-ray diffraction will be used to characterize the crystal packing and quantum mechanical calculations, in order to provide energetic data about the supramolecular interactions.…”

Section: Introductionmentioning

confidence: 99%

Proposal for crystallization of 3-amino-4-halo-5-methylisoxazoles: an energetic and topological approach

et al. 2015

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a The supramolecular structure of 3-amino-4-halo-5-methylisoxazoles (with halo = Cl, Br, I) was investigated in order to suggest a route for crystallization of small molecules. The hierarchy of intermolecular interactions during the growth of the crystal was established by x-ray diffraction, 1 H NMR titration, QTAIM analysis and quantum mechanical calculations. The relationship between QTAIM and energetic data was the fundamental innovation in this work. It allowed the partitioning of the dimer interaction energy between interacting atoms. Partitioning shows the cooperation of intermolecular interactions in the stabilization of dimers and led to observation of the energetic consequences that small changes in the molecular structure of each compound may have on the crystal packing. The proposed route for crystallization of the supramolecular cluster was based on the energetic hierarchy, in which the hydrogen bond is the strongest interaction and the first to form, and the π-interactions are weaker than the hydrogen bond and cannot compete with it. However, the πinteractions are responsible for the growth of the crystal connecting the rising layers of the hydrogen bond dimers. The other interaction formed, the halogen bond, is too weak to compete with the other two interactions, but it is fundamental for linking the layer that leads to the final three-dimensional arrangement. Finally, a new way of understanding the crystallization process and the design of new materials is presented. 11-13Our objective herein is to further our study of the analysis of the crystal packing of heterocycles, taking into account consequences arising from small changes in molecular

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“…Thus, halogenated phenols can be considered good molecular models for supramolecular studies, due to the variations of halogen and the position of halogen in the ring, as well as variations in the classes of intermolecular interactions present in crystal packing. Furthermore, in the literature [24,29] there is a shortage of supramolecular studies that address energy and topological data on which our work will be based.…”

Section: Introductionmentioning

confidence: 99%

Energetic and Topological Supramolecular Study and Nucleation Mechanism Proposal of Halogenated Phenols

2022

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In this work, an energetic and topological supramolecular study of 10 different halogenated phenols, X−C6H4−OH (X=F, Cl, Br and I) in the ortho, meta, and para positions was carried out, except for X=Br, in ortho‐ and meta‐X‐phenols. Most compounds have a molecular coordination number (MCN) of fourteen. All intermolecular interactions were classified, and the robustness was evaluated. Strong intermolecular interactions such as O−H⋅⋅⋅O and π⋅⋅⋅π contributed half the energy of the cluster, although interactions considered weak as C−H⋅⋅⋅X and C−H⋅⋅⋅π reached 40 % in energetic contribution, as they revealed a greater number of occurrences. Additionally, these theoretical data of energy were correlated with experimental data of melting point and packing density revealing a notable trend. In almost all cases evaluating the same position, the higher the density, the higher the melting point and the higher the stabilizing energy. Finally, nucleation proposals were suggested for all compounds and revealed that six compounds needed three stages, while four compounds needed only two stages to promote the growth of the supramolecular structure in three directions.

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Thermodynamic, energetic, and topological properties of crystal packing of pyrazolo[1,5-a]pyrimidines governed by weak electrostatic intermolecular interactions

Abstract: The relationship between energetic and topological properties of crystals with weak electrostatic intermolecular interactions and thermodynamic data are presented.

Cited by 16 publications

References 54 publications

Insights on the Similarity of Supramolecular Structures in Organic Crystals Using Quantitative Indexes

Insights on the Similarity of Supramolecular Structures in Organic Crystals Using Quantitative Indexes

Proposal for crystallization of 3-amino-4-halo-5-methylisoxazoles: an energetic and topological approach

Energetic and Topological Supramolecular Study and Nucleation Mechanism Proposal of Halogenated Phenols

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