Crystallographic and theoretical interpretation of supramolecular architecture in a new salt hydrate of DL-Tartaric acid and Dimethylamine (DLTA-DA)

Likhitha, U.; Narayana, B.; Sarojini, B. K.; Kumar, Sunil; Karthick, T.

doi:10.1016/j.molstruc.2020.129284

Cited by 8 publications

(1 citation statement)

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“…Above that temperature, the T:TA cocrystal becomes more favorable than its individual components. This high temperature is close to the melting points of both DL-tartaric acid (479 K) 41 and thiourea (454 K) 42 and suggests that T:TA will be unlikely to form experimentally, though possibly through crystallization of the melted mixture. Ultimately, the Gibbs free energies show that the changes in the hydrogen bonding network induced by sulfur make T:TA formation energetically less favorable than that of the readily grown U:TA cocrystalline solid.…”

Section: ■ Theoretical Methodsmentioning

confidence: 59%

Evaluating Hydrogen Bonding in Organic Cocrystals Using Low-Frequency Raman Vibrational Spectroscopy and Quantum Mechanical Simulations

Davis

Korter

2022

Crystal Growth & Design

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Cocrystallization can provide a potential route to usability for active pharmaceutical ingredients that are eliminated in the drug discovery process due to their low bioavailability. In this work, cocrystals of urea and thiourea with glutaric acid and tartaric acid were used as model systems to experimentally and computationally investigate the intermolecular energy factors within heterogeneous molecular crystals. The tools employed in this study were low-frequency Raman vibrational spectroscopy and solid-state density functional theory (ss-DFT). The sub-200 cm–1 Raman spectra give insights into vibrations that are characteristic of the crystal packing and the intermolecular forces within the samples. ss-DFT allows for the analysis of these vibrations and of the specific energies involved in the collective cocrystal. Moreover, ss-DFT permits the computational investigation of hypothetical cocrystals, utilized here to predict the properties of the unrealized thiourea:dl-tartaric acid cocrystal. These analyses demonstrated that it is both experimentally and computationally favorable for the urea and thiourea glutaric acid cocrystals to form, as well as the urea:dl-tartaric acid cocrystal, when compared to the crystallization of the pure component materials. However, changes in the hydrogen bonding network yield a thiourea:dl-tartaric acid cocrystal that corresponds to an energetic minimum on the potential energy surface but has a Gibbs free energy that prevents it from experimental formation under ambient conditions.

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Section: ■ Theoretical Methodsmentioning

confidence: 59%