Insights on conformation in the solid state: a case study – s-cis and/or s-trans crystallization of 5(3)-aryl-3(5)-carboxyethyl-1-tert-butylpyrazoles

Zimmer, Geórgia C.; Pagliari, Anderson B.; Bender, Caroline R.; Salbego, Paulo R. S.; Orlando, Tainára; Hörner, Manfredo; Zanatta, Nilo; Bonacorso, Hélio G.; Martins, Marcos A. P.

doi:10.1039/c8ce00984h

Cited by 12 publications

(22 citation statements)

References 41 publications

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“…It was also observed that, regardless of the investigated rotaxane, a preferential formation of a one‐dimensional block for the first nuclei and in fewer cases the formation of dimers is observed in the first stage. This is different from the behavior of smaller molecules previously described by our research group , , , . The formation of one‐dimensional blocks corroborates with crystallization mechanisms proposed for polymorphs of [2]rotaxanes recently reported …”

Section: Resultssupporting

confidence: 77%

“…It was proposed crystallization mechanisms using a retrocrystallization process, which uses formed crystal data to presume how the stages of crystallization process occurred. Some investigations reported by our research group proposed crystallization mechanisms for a series of isoxazoles, triazenes N ‐oxides, substituted pyrazoles, N ‐phenilamides, and polymorph of [2]rotaxane …”

Section: Resultsmentioning

confidence: 99%

“…Concerned with this topic, our research group has been continuously investigating different classes of molecules in the crystalline state by using the supramolecular cluster as demarcation , . The supramolecular cluster furnishes reliable energetic and contact area data that represents the whole crystalline lattice and not just fragments, which allows the proposal of crystallization mechanisms , . Therefore, improved knowledge of how crystallization processes in different molecules occur is an important subject, especially regarding the design of new materials.…”

Section: Introductionmentioning

confidence: 99%

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Crystallization Mechanisms Applied to Understand the Crystal Formation of Rotaxanes

et al. 2019

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The present study discusses the crystalline packing formation of several [2]rotaxanes with Leigh‐type tetralactam macrocycle bearing different threads. The presence of solvent molecules in some structures are also addressed to shed some light on this matter. Additionally, the degree of similarity between supramolecular structures of rotaxanes was discussed using similarity indices. For this, new descriptors and crystallization mechanisms, which were proposed in terms of contact area and stabilization energy, were carried out to evaluate the rotaxane molecules. It was possible to observe similar general stages of crystallization dominated by the formation of 1D‐blocks and, in fewer cases, by dimers in the first stage of nucleation. The preference for the formation of 1D nuclei resides in the large contact area and complementarity involved in the large set of interactions between the rotaxanes at the earliest stages of crystallization. In this context, it was possible to propose when solvent molecules are trapped between the rotaxanes during crystal formation. Therefore, a unique example of a rotaxane whose topology favored the entrapment of water molecules between rotaxanes during the first stage of the crystallization process is presented. Crystallization mechanisms showed to be a valuable asset in the supramolecular investigation of rotaxanes in the crystalline state.

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Section: Resultssupporting

confidence: 77%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Crystallization Mechanisms Applied to Understand the Crystal Formation of Rotaxanes

et al. 2019

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“…The differences in the types of connections provide a simple way to differentiate the target materials, helping in the search for the most strategically favourable synthetic route due to the energy involved in the processes of forming and breaking connections in the construction of superstructures [10] . More recently, an approach to better understanding the crystallization phenomenon has been reported, while considering topological and energetic factors [11] associated with these types of interactions that play a decisive role in the formation of crystals, explored as a supramolecular cluster [12–16] . The concept of supramolecular cluster creates the idea of a fixed number of molecules that provide information to help understand the supramolecular interactions of the crystalline system, that is, a cluster formed by the first coordination sphere [11] .…”

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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“…However, there is steady growing evidence that improved potency of specific conformers under physiological conditions led to an increase in the focus on relatively stable conformers, as evidenced by recent reports [51][52][53][54][55][56][57][58][59][60][61][62][63][64][65][66][67][68]. Since crystallization is the main purification and separation unit operation in the development of new medicines, studies about molecular flexibility and the effect of the presence of conformation stability and conversion in solution on nucleation, crystal growth and polymorphism has also been steadily increasing [50,[69][70][71][72][73][74][75][76][77][78][79][80][81][82].…”

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confidence: 99%

Review and Modeling of Crystal Growth of Atropisomers from Solutions

2019

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In this paper, theories on anisotropic crystal growth and crystallization of atropisomers are reviewed and a model for anisotropic crystal growth from solution containing slow inter-converting conformers is presented. The model applies to systems with growth-dominated crystallization from solutions and assumes that only one conformation participates in the solute integration step and is present in the crystal lattice. Other conformers, defined as the wrong conformers, must convert to the right conformer before they can assemble to the crystal lattice. The model presents a simple implicit method for evaluating the growth inhibition effect by the wrong conformers. The crystal growth model applies to anisotropic growth in two main directions, namely a slow-growing face and a fast-growing face and requires the knowledge of solute crystal face integration coefficients in both directions. A parameter estimation algorithm was derived to extract those coefficients from data about temporal concentration and crystal size during crystallization and was designed to have a short run time, while providing a high-resolution estimation. The model predicts a size-dependent growth rate and simulations indicated that for a given seed size and solvent system and for an isothermal anti-solvent addition crystallization, the seed loading and the supersaturation at seeding are the main factors impacting the final aspect ratio. The model predicts a decrease of the growth inhibition effect by the wrong conformer with increasing temperature, likely due to faster equilibration between conformers and/or a decrease of the population of the wrong conformer, if of low energy, at elevated temperatures. Finally, the model predicts that solute surface integration becomes the rate-limiting mechanism for high solute integration activation energies, resulting in no impact of the WC on the overall crystal growth process.

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Insights on conformation in the solid state: a case study – s-cis and/or s-trans crystallization of 5(3)-aryl-3(5)-carboxyethyl-1-tert-butylpyrazoles

Abstract: The conformation adopted by COOEt group in solid state were influenced by supramolecular environment and intramolecular interaction for 1,3- and 1,5-regioisomers, respectively.

Cited by 12 publications

References 41 publications

Crystallization Mechanisms Applied to Understand the Crystal Formation of Rotaxanes

Crystallization Mechanisms Applied to Understand the Crystal Formation of Rotaxanes

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

Review and Modeling of Crystal Growth of Atropisomers from Solutions

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