Salicylamide Cocrystals: Screening, Crystal Structure, Sublimation Thermodynamics, Dissolution, and Solid-State DFT Calculations

Manin, Alex N.; Voronin, Alexander P.; Manin, N. G.; Vener, Mikhail V.; Shishkina, Anastasia V.; Lermontov, A. S.; Perlovich, German L.

doi:10.1021/jp5032898

Cited by 60 publications

(63 citation statements)

References 48 publications

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“…The cocrystal stability can be measured by crystal lattice energy that is usually obtained from sublimation enthalpy in the sublimation experiment. The experimental measurement of cocrystal sublimation thermodynamics was conducted by the transpiration method as described in our previous work [24]. Solid-state DFT calculations followed by Bader analysis of the periodic electron density were performed to evaluate the energy contributions of acid-amide synthon and secondary interactions to the crystal lattice energy.…”

Section: Scheme 1 Molecular Structure Of Salicylates and 4-hydroxybementioning

confidence: 99%

“…(1). The latter approach provides reasonable values for singlecomponent [37,40] and two-component [24,46] It is assumed that the E latt energy corresponds to the sublimation enthalpy ∆H 0 subl , extrapolated to 0 K. According to [47], the value of the sublimation enthalpy at given temperature T can be written as:…”

Section: Calculation Proceduresmentioning

confidence: 99%

“…[24] [SA+4-OHBZA] (1:1). Figure 3 represents temperature dependences of vapor pressure for cocrystal and its components.…”

Section: Thermodynamic Characteristics Of Cocrystal Sublimationmentioning

confidence: 99%

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Influence of Secondary Interactions on the Structure, Sublimation Thermodynamics, and Solubility of Salicylate:4-Hydroxybenzamide Cocrystals. Combined Experimental and Theoretical Study

et al. 2015

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Cocrystal screening of 4-hydroxybenzamide with a number of salicylates (salicylic acid, SA; 4-aminosalicylic acid, PASA; acetylsalicylic acid, ASA; and salicylsalicylic acid, SSA) was conducted to confirm the formation of two cocrystals, [SA+4-OHBZA] (1:1) and [PASA+4-OHBZA] (1:1). Their structures were determined using single-crystal X-ray diffraction, and the hydrogen-bond network topology was studied. Thermodynamic characteristics of salicylic acid cocrystal sublimation were obtained experimentally. It was proved that PASA cocrystallization with 4-OHBZA makes the drug more stable and prevents the irreversible process of decarboxylation of PASA resulting in formation of toxic 3-aminophenol. The pattern of non-covalent interactions in the cocrystals is described quantitatively using solid-state density functional theory followed by Bader analysis of the periodic electron density. It has been found that the total energy of secondary interactions between synthon atoms and the side hydroxyl group of the acid molecule in [SA+4-OHBZA] (1:1) and [PASA+4-OHBZA] (1:1) cocrystals is comparable to the energy of the primary acid-amide heterosynthon. The theoretical value of the sublimation enthalpy of [SA+4-OHBZA], 231 kJ/mol, agrees fairly well with the experimental one, 272 kJ/mol. The dissolution experiments with [SA+4-OHBZA] have proved that the relatively large cocrystal stability in relation to the stability of its components has a negative effect on the dissolution rate and equilibrium solubility. The [PASA+4-OHBZA] (1:1) cocrystal showed an enhancement of apparent solubility compared to that of the corresponding pure active pharmaceutical ingredient, while their intrinsic dissolution rates are comparable.

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Section: Scheme 1 Molecular Structure Of Salicylates and 4-hydroxybementioning

confidence: 99%

Section: Calculation Proceduresmentioning

confidence: 99%

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Influence of Secondary Interactions on the Structure, Sublimation Thermodynamics, and Solubility of Salicylate:4-Hydroxybenzamide Cocrystals. Combined Experimental and Theoretical Study

et al. 2015

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“…Also many other physicochemical properties can be modulated by cocrystallization including stability [21][22][23][24], hygroscopicity [25] and prolonged shelf life [26]. Among many drugs, aromatic amides acting either as APIs or as excipients attract nowadays substantial attention [27][28][29][30][31][32][33][34][35]. These compounds are known for their important roles in medical applications.…”

Section: Introductionmentioning

confidence: 99%

“…Although many pharmaceutical cocrystals containing amides have been studied [27][28][29][30][31][32][33][34][35], the data deposited in the Cambridge Structural Database (CSD) [41] are rather variable in the sense that many coformers were used for synthesis of diverse cocrystals. For example cocrystals of fumaric acid with benzamide, isonicotinamide or nicotinamide are known under refcodes YOPBUB, LUNNOX and EDAPOQ, respectively, but there is no information about solids of these coformers with temozolomide.…”

Section: Introductionmentioning

confidence: 99%

Transferability of cocrystallization propensities between aromatic and heteroaromatic amides

Cysewski

2016

Struct Chem

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New virtual cocrystal screening was proposed taking advantage of the similarities between cocrystallization landscapes of different compounds. Assuming that cocrystallization propensities can be modeled by miscibility affinities of liquid components under supercooled conditions, the quantitative rules of likeness were formulated and validated for 45 aromatic and heteroaromatic amides interacting with a variety of coformers. The most important finding comes from the observed linear trends between the values of mixing enthalpies of amides with respect to a reference molecule. Particularly isonicotinamide was found as a very convenient comparative system since it constitutes 97 binary cocrystals. Many experimentally observed cocrystals were used for supporting the analogy hypothesis, which states that a properly selected reference molecule, for which cocrystals were experimentally documented, can provide practical information about cocrystallization propensities of another compound provided that two criterions are met, namely sufficiently high similarities and high enough affinities. Hence, it is not necessary to perform experimental cocrystallization of every pair of coformers since miscibility in the solid state of one compound can be transferred to another one at least in the case of aromatic or heteroaromatic amides.

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Pressure-imposed changes of benzoic acid crystals

Cysewski

2015

J Mol Model

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Structural and energetic properties of benzoic acid crystals at pressure elevated from ambient condition up to 2.21 GPa were characterized. The directly observed variations of cell parameters and consequently cell volume are associated with many other changes including energetic, geometric, and electronic characteristics. First of all the non-monotonous change of lattice energy are noticed with the rise of pressure since the increase of stabilization up to 1GPa is followed by systematic decrease of lattice energies after extending the hydrostatic compression. There is also an observed increase of C22(8) synthon stabilization interaction with increase of pressure. The lattice response rather than interaction within synthons are source of observed pressure-related trend of lattice energy changes. The energy decomposition analysis revealed that the total steric interactions determine the overall trend of lattice energy change with the rise of pressure. Besides geometric aromaticity index was used as a measure of geometric changes. Serious discrepancies were noticed between HOMA values computed with the use of experimental and optimized geometries of the ring. Even inclusion of uncertainties of experimental geometries related to limited precision of X-ray diffraction measurements does not cancel mentioned discrepancies. Although HOMA exhibit similar trends at modest pressures the diversity became surprisingly high at more extreme conditions. This might suggest limitations of periodic DFT computations at elevated pressures and the experimentally observed breaking of molecules at very high pressures will probably not be accounted properly in this approach. Also limitation of direct use of experimental geometries were highlighted.Electronic supplementary materialThe online version of this article (doi:10.1007/s00894-015-2635-z) contains supplementary material, which is available to authorized users.

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Salicylamide Cocrystals: Screening, Crystal Structure, Sublimation Thermodynamics, Dissolution, and Solid-State DFT Calculations

Cited by 60 publications

References 48 publications

Influence of Secondary Interactions on the Structure, Sublimation Thermodynamics, and Solubility of Salicylate:4-Hydroxybenzamide Cocrystals. Combined Experimental and Theoretical Study

Influence of Secondary Interactions on the Structure, Sublimation Thermodynamics, and Solubility of Salicylate:4-Hydroxybenzamide Cocrystals. Combined Experimental and Theoretical Study

Transferability of cocrystallization propensities between aromatic and heteroaromatic amides

Pressure-imposed changes of benzoic acid crystals

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