Substituent effects on the crystallization mechanisms of 7-chloro-4-substituted-quinolines

Copetti, João P. P.; Salbego, Paulo R. S.; Orlando, Tainára; Rosa, Jéssica Maria Luis; Fiss, Gabriela F.; Oliveira, João Paulo Gomes de; Vasconcellos, Mário L. A. A.; Zanatta, Nilo; Bonacorso, Hélio G.; Martins, Marcos A. P.

doi:10.1039/d0ce00214c

Cited by 11 publications

(25 citation statements)

References 29 publications

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“…However, in 6 the O−H⋅⋅⋅O interaction leads to the growth of infinite chains along one direction (Figure 11), and in 8 these interactions lead to the formation of several tetramers in each plane (Figure S30), once, at this stage, the approximation of blocks formed in the previous stage occurs. The supramolecular structure of 6 has the third stage led by the approximation of the blocks formed in the previous step from all sides in the same plane similar to that described in literature [40] . For this compound, the third stage is motivated by the interactions C−H⋅⋅⋅π, O⋅⋅⋅I and C−H⋅⋅⋅I (Figure 11).…”

Section: Introductionmentioning

confidence: 85%

“…The supramolecular structure of 6 has the third stage led by the approximation of the blocks formed in the previous step from all sides in the same plane similar to that described in literature. [40] For this compound, the third stage is motivated by the interactions CÀ H•••π, O•••I and CÀ H•••I (Figure 11). For structure 8 the third stage occurs from CÀ H•••Cl interactions leading to growth in a second direction (Figure S30).…”

Section: Compoundmentioning

confidence: 99%

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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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Section: Introductionmentioning

confidence: 85%

Section: Compoundmentioning

confidence: 99%

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

2022

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“…The QTAIM analysis indicates the presence of intermolecular interactions from a bond critical point (BCP) of attachment along the path that connects two interacting atoms . The stabilization energy in each atom···atom interaction, for the proposed first nuclei of each compound, was obtained utilizing the G AI analysis ,, determined by G AI(X···Y) = (ρ BCP /Σρ BCP ) × G M1···M N , correlating QTAIM data (ρ BCP ) and the stabilization energy of the considered dimer.…”

Section: Methodsmentioning

confidence: 99%

“…To consider the necessary information in regard to all intermolecular interactions present in the crystal, the supramolecular cluster (SC) was used as an initial demarcation. Based on the stabilization energy and contact area data and allied with solution NMR data, crystallization mechanisms have been proposed. , This kind of approach was designed to gain information on the main crystallization stages involved in the formation of the obtained crystal phase and to discuss dominant parameters (stabilization energy and contact area) in each proposed stage . Recently, this concept was used to propose the crystallization mechanism of solvates of [2]rotaxane molecules, and it was possible to infer when water molecules were trapped during the crystallization process …”

Section: Introductionmentioning

confidence: 99%

Persistence of N—H···O═C Interactions in the Crystallization Mechanisms of Trisubstituted Bis-Ureas with Bulky Substituents

Lopes

Orlando

Simões

et al. 2021

Crystal Growth & Design

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Bis-ureas are generally associated with strongly bifurcated hydrogen bonds (NH···OC interactions). For this reason, a series of trisubstituted bis-ureas (TBU) with bulk substituents were designed and used as a study model to gain a better understanding of the persistence of NH···OC interactions as driving interactions of the crystallization process. The TBU molecules possess different substituents (isopropyl, benzyl, and 4-nitro-benzyl) and variations in the methylene spacer. The TBU self-assembly, through crystallization mechanism proposals, is discussed related to the role of intermolecular interactions that drive and participate in the crystallization process. The intermolecular interactions present in the proposed first nuclei of crystallization were studied by concentration-dependent 1H NMR experiments and QTAIM analysis. Our findings showed that even with bulky substituents, the NH···OC interactions in most compounds played an important role in stabilizing the first nuclei formed during the crystallization process. However, in one case the molecular topology prevented the formation of NH···OC as the driving interaction in the first crystallization nuclei. In this case, the crystallization was mainly governed by a set of “weaker” interactions, showing that a subtle molecular change in the methylene spacer favored H···H interactions over directional N–H···O interactions. For some of the compounds studied, we propose both when the symmetry-independent molecules observed in the crystal lattice could be formed and when the water molecules are probably trapped during the crystallization to form the hydrate crystalline phases. This study contributes to the better understanding of issues related to modulating NH···OC hydrogen bonds using bulky substituents in the self-assembly of flexible TBU molecules.

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“…In this work we explored the ring size, in NH-pyrazole cyclamers we successfully studied the effect of the C-substituents [25,26] and, finally, in the case of Ag(I) pyrazolate dimers we studied the effect of ancillary ligands, which can have a marked effect on the Ag•••Ag distance with a concomitant decrease in stability that was compensated for by the ligands [16]. Consequently, the problem is of great complexity and it is useful to remember that the mechanism of crystal growth is also complex and is not fully understood [72,73].…”

Section: Energiesmentioning

confidence: 99%

A Computational Study of Metallacycles Formed by Pyrazolate Ligands and the Coinage Metals M = Cu(I), Ag(I) and Au(I): (pzM)n for n = 2, 3, 4, 5 and 6. Comparison with Structures Reported in the Cambridge Crystallographic Data Center (CCDC)

Elguero

Alkorta

2020

Molecules

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The structures reported in the Cambridge Structural Database (CSD) for neutral metallacycles formed by coinage metals in their valence (I) (cations) and pyrazolate anions were examined. Depending on the metal, dimers and trimers are the most common but some larger rings have also been reported, although some of the larger structures are not devoid of ambiguity. M06-2x calculations were carried out on simplified structures (without C-substituents on the pyrazolate rings) in order to facilitate a comparison with the reported X-ray structures (geometries and energies). The problems of stability of the different ring sizes were also analyzed.

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Substituent effects on the crystallization mechanisms of 7-chloro-4-substituted-quinolines

Abstract: The crystallization mechanisms of a series of fourteen 7-chloro-4-substituted-quinolines were proposed based on a retrocrystallization approach using the supramolecular cluster as demarcation.

Cited by 11 publications

References 29 publications

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

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

Persistence of N—H···O═C Interactions in the Crystallization Mechanisms of Trisubstituted Bis-Ureas with Bulky Substituents

A Computational Study of Metallacycles Formed by Pyrazolate Ligands and the Coinage Metals M = Cu(I), Ag(I) and Au(I): (pzM)n for n = 2, 3, 4, 5 and 6. Comparison with Structures Reported in the Cambridge Crystallographic Data Center (CCDC)

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