Towards ab initio screening of co-crystal formation through lattice energy calculations and crystal structure prediction of nicotinamide, isonicotinamide, picolinamide and paracetamol multi-component crystals

Chan, H.C.; Kendrick, John; Neumann, Marcus A.; Leusen, Frank J. J.

doi:10.1039/c3ce40107c

Cited by 109 publications

(111 citation statements)

References 30 publications

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“…The computational settings used are also in line with those used in other work employing DFT in VASP for accurate energy evaluations of organic crystal structures. 17,30,36,37 …”

Section: Methods and Computational Detailsmentioning

confidence: 99%

Evaluating the Energetic Driving Force for Cocrystal Formation

Taylor

Day

2017

Crystal Growth & Design

170

182

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We present a periodic density functional theory study of the stability of 350 organic cocrystals relative to their pure single-component structures, the largest study of cocrystals yet performed with high-level computational methods. Our calculations demonstrate that cocrystals are on average 8 kJ mol–1 more stable than their constituent single-component structures and are very rarely (<5% of cases) less stable; cocrystallization is almost always a thermodynamically favorable process. We consider the variation in stability between different categories of systems—hydrogen-bonded, halogen-bonded, and weakly bound cocrystals—finding that, contrary to chemical intuition, the presence of hydrogen or halogen bond interactions is not necessarily a good predictor of stability. Finally, we investigate the correlation of the relative stability with simple chemical descriptors: changes in packing efficiency and hydrogen bond strength. We find some broad qualitative agreement with chemical intuition—more densely packed cocrystals with stronger hydrogen bonding tend to be more stable—but the relationship is weak, suggesting that such simple descriptors do not capture the complex balance of interactions driving cocrystallization. Our conclusions suggest that while cocrystallization is often a thermodynamically favorable process, it remains difficult to formulate general rules to guide synthesis, highlighting the continued importance of high-level computation in predicting and rationalizing such systems.

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“…The computational settings used are also in line with those used in other work employing DFT in VASP for accurate energy evaluations of organic crystal structures. 17,30,36,37 …”

Section: Methods and Computational Detailsmentioning

confidence: 99%

Evaluating the Energetic Driving Force for Cocrystal Formation

Taylor

Day

2017

Crystal Growth & Design

170

182

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“…The stabilization energy of organic molecular co-crystals relative to their single components is typically on the order of a few kJ mol -1 , 37,38 so that co-crystal formation and structure are sensitive to small chemical changes. The -26 kJ mol -1 stabilization predicted by these dimer calculations is on the upper end of the distribution of known co-crystal stabilization energies 37,38 suggesting a robust energetic driving force to co-crystallization of TCC2-R and TCC2-S, which might lead to heterochiral window-to-window interactions. When considering the potential heterochiral co-crystallization of TCC2-R with the tetrahedral cage, CC3-S, a more complex picture emerged due to the weaker binding energy of TCC2-R/CC3-S dimers compared to pure CC3-S dimers.…”

mentioning

confidence: 99%

Reticular synthesis of porous molecular 1D nanotubes and 3D networks

et al. 2016

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Synthetic control over pore size and pore connectivity is the crowning achievement for porous metal-organic frameworks. The same level of control has not been achieved for molecular crystals, which are not defined by strong, directional intermolecular coordination bonds. Hence, molecular crystallization is inherently less controllable than framework crystallization, and there are fewer examples of 'reticular synthesis'-where multiple building blocks can be assembled according to a common assembly motif.Here, we apply a chiral recognition strategy to a new family of tubular covalent cages, to create both 1-D porous nanotubes and 3-D diamondoid pillared porous networks.The diamondoid networks are analogous to metal-organic frameworks prepared from tetrahedral metal nodes and linear, ditopic organic linkers. The crystal structures can be rationalized by computational lattice energy searches, which provide an in silico screening method to evaluate candidate molecular building blocks. These results are a blueprint for applying the 'node and strut' principles of reticular synthesis to molecular crystals.Despite many advances in supramolecular chemistry, it is still challenging to control molecular crystallization to create a specific, useful property. 1,2 This is important in the emerging area of porous molecular solids, 3 which have practical advantages such as solution processability. The crystal packing in porous molecular crystals defines the pore dimensions, which in turn define properties such as guest selectivity. 4,5 The same challenge-control over solid state structure-applies to all 2 functional molecular crystals because crystal packing defines physical properties such as electronic band gap and thermal or electrical conductivity.A central paradigm in crystal engineering is to synthesize building blocks, or 'tectons', with strong, directional interactions, such as hydrogen bonding 6 or metal-ligand binding, 7 which direct assembly into a targeted three-dimensional superstructure (Fig. 1). 1,2,8,9 For metal-organic frameworks (MOFs) and porous coordination polymers (PCPs), directional metal-ligand bonds are used to do this (Fig. 1a). [10][11][12][13][14] Likewise, hydrogen bonding can be used to create organic molecular crystals with defined network structures (Fig. 1b). 9,15,16 We have used chiral recognition to assemble porous organic cages 3 (POCs) into structures with 3-D pore channels (Fig. 1c). 3 POCs are rigid molecules with a permanent internal void that is accessible to guests via 'windows' in the cage. [17][18][19] Control of structure and function for POCs can be difficult, however, because slight changes in the molecular structure 19 or the crystallization solvent 20 can cause a profound change in the crystal packing. Chiral window-towindow interactions (Fig. 1e,f) can direct these POCs to assemble into 3-D pore networks in several cases, 19,21,22 but this is not ubiquitous. For example, some cages require specific solvents to template the window-to-window packing. 20 The chiral cage CC3-S (...

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“…Cocrystallisation energies of ca. −11 kJ mol −1 have been reported for molecular organic materials at ambient pressure, 45 an order of magnitude that does not seem to pose forbidding thermodynamic obstacles. Thus, a sensible hypothesis involves the kinetic control of pore opening that would allow the escape of solvent molecules either for the preformed crystal or, more likely, at the nucleation stage, but only under ambient conditions.…”

Section: Discussionmentioning

confidence: 99%

X-ray diffraction and computational studies of the pressure-dependent tetrachloroethane solvation of diphenylanthracene

et al. 2016

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The crystal structure of the organic semiconductor 9,10-diphenylanthracene (DPA) has been studied by single-crystal X-ray diffraction at variable pressure up to 3 GPa. Under ambient conditions and in the presence of 1,1,2,2-tetrachloroethane, the material invariably crystallises in an unsolvated form, in the space group C2/c, with Z′ = 1/2, as reported in the literature. As pressure is increased to a modest 0.5 GPa, crystallisation occurs in the form of a newly discovered solvate with a 1 : 2 DPA-tetrachloroethane stoichi- . Monte Carlo simulations show that the mobility of the solvent in its cage would be extremely reduced even under ambient conditions, ruling out a mechanism of solvate formation and subsequent release. According to a structure-oriented perspective, the kinetics of the process could then be such that the nucleating system at ambient pressure separates out the solvent, while a 0.5 GPa pressure provides a solute-solvent grip that forces cocrystallisation, in agreement with both experiments and simulations. Even in the absence of experimental or computational proof of the thermodynamic stability of the solvate at high pressure, this appears to be a plausible and sensible case scenario in its own right.

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Towards ab initio screening of co-crystal formation through lattice energy calculations and crystal structure prediction of nicotinamide, isonicotinamide, picolinamide and paracetamol multi-component crystals

Abstract: Towards ab initio screening of co-crystal formation through lattice energy calculations and crystal structure prediction of nicotinamide, isonicotinamide, picolinamide and paracetamol multi-component crystals3

Cited by 109 publications

References 30 publications

Evaluating the Energetic Driving Force for Cocrystal Formation

Evaluating the Energetic Driving Force for Cocrystal Formation

Reticular synthesis of porous molecular 1D nanotubes and 3D networks

X-ray diffraction and computational studies of the pressure-dependent tetrachloroethane solvation of diphenylanthracene

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