Designing ternary cocrystals with hydrogen bonds and halogen bonds

Tothadi, Srinu; Desiraju, Gautam R.

doi:10.1039/c3cc43822h

Cited by 111 publications

(102 citation statements)

References 27 publications

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“…This is because of the difficulties in introducing three or more components stoichiometrically into a molecular solid. Hypothesis‐driven synthetic methods for higher cocrystals are based on supramolecular synthons, in other words, on the intermolecular interactions and the geometry (shape and size) of the precursor molecules. Beginning with binary cocrystals, we have recently reported the successful design of a six‐component molecular solid using both interaction‐based and solid solution‐based strategies .…”

Section: Figurementioning

confidence: 99%

From a Binary to a Quaternary Cocrystal: An Unusual Supramolecular Synthon

Paul

Desiraju

2019

Angew Chem Int Ed

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Formation of a stoichiometric quaternary cocrystal consisting of resorcinol (RES), tetramethylpyrazine (TMP), phenazine (PHE) and pyrene (PYR) is described. A closed tetrameric resorcinol‐heterocycle synthon, unusual in that it has two different linker bases rather than just one, is observed in this four‐component solid. The tetrameric synthon is formed by two RES molecules and the two pyridine bases TMP and PHE. The stoichiometric quaternary cocrystal grows in an epitaxial fashion on the surfaces of a RES.PHE binary cocrystal which is initially obtained from the mother liquor. By indexing the common crystal faces of the binary and quaternary cocrystals, and noting that no ternary solid is obtained, a plausible mechanism has been proposed for the formation of this rare supramolecular architecture.

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Section: Figurementioning

confidence: 99%

From a Binary to a Quaternary Cocrystal: An Unusual Supramolecular Synthon

Paul

Desiraju

2019

Angew Chem Int Ed

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“…14 The strategy was later shown to be a general one, using different components selected based on the same principles. [15][16][17] A great body of work on the preparation of ternary [18][19][20][21][22] and even quaternary 23,24 co-crystals has been recently reported by Desiraju and co-workers. First, a shapebased approach was devised, where one component in a binary co-crystal can be partially replaced by a third component, 25 in such a way that the molecules participating in (stronger) hydrogen bonding are left in place, while the weakly interacting molecules of the same kind are substituted by similarly shapes ones.…”

Section: Introductionmentioning

confidence: 99%

Systematic Construction of Ternary Cocrystals by Orthogonal and Robust Hydrogen and Halogen Bonds

2016

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ABSTRACT:A carefully designed strategy is presented for construction of ternary co-crystals, based on the orthogonality of two supramolecular interaction modes: hydrogen bonding between crown ethers and thioureas and the halogen bonding between thioureas and perfluorohalocarbons. Tested on a set comprising two crown ethers, two thioureas and five halogen bond donors, the strategy resulted in a high, 75% success rate, with 15/20 component combinations yielding at least one co-crystal. Crystal structure analysis revealed the interplay between the hydrogen and halogen bonding motifs, also shedding light on the variables affecting their formation.

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“…10 There are myriad examples of binary co-crystals in the literature, 4 and increasingly ternary systems are also being studied. 4,11 In order to drive effective cocrystal formation, it is important that there are strong intermolecular interactions between the crystal components. These may take the form of H-bonds, π -π stacking interactions, or van der Waals forces.…”

Section: Introductionmentioning

confidence: 99%

Thermal Behavior of Benzoic Acid/Isonicotinamide Binary Cocrystals

Buanz

Prior

Burley

et al. 2015

Crystal Growth & Design

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YesA comprehensive study of the thermal behavior of the 1:1 and 2:1 benzoic acid/isonicotinamide cocrystals is reported. The 1:1 material shows a simple unit cell expansion followed by melting upon heating. The 2:1 crystal exhibits more complex behavior. Its unit cell first expands upon heating, as a result of C–H···π interactions being lengthened. It then is converted into the 1:1 crystal, as demonstrated by significant changes in its X-ray diffraction pattern. The loss of 1 equiv of benzoic acid is confirmed by thermogravimetric analysis–mass spectrometry. Hot stage microscopy confirms that, as intuitively expected, the transformation begins at the crystal surface. The temperature at which conversion occurs is highly dependent on the sample mass and geometry, being reduced when the sample is under a gas flow or has a greater exposed surface area but increased when the heating rate is elevated

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Designing ternary cocrystals with hydrogen bonds and halogen bonds

Abstract: A graded selection of hydrogen bonds and halogen bonds allows for the isolation of 2 : 1 : 1 ternary cocrystals of the general form 4-nitrobenzamide : diacid : 1,4-dihalogenated benzene, which are mediated by the amide-acid and I···O2N supramolecular synthons.

Cited by 111 publications

References 27 publications

From a Binary to a Quaternary Cocrystal: An Unusual Supramolecular Synthon

From a Binary to a Quaternary Cocrystal: An Unusual Supramolecular Synthon

Systematic Construction of Ternary Cocrystals by Orthogonal and Robust Hydrogen and Halogen Bonds

Thermal Behavior of Benzoic Acid/Isonicotinamide Binary Cocrystals

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