Multicomponent Supramolecular Assemblies of Melamine and α-Hydroxycarboxylic Acids: Understanding the Hydrogen Bonding Patterns and Their Physicochemical Consequences

Castiñeiras, Alfonso; García‐Santos, Isabel; González‐Pérez, Josefa María; Bauzá, Antonio; Zarȩba, Jan K.; Niclós‐Gutiérrez, Juan; Torres, Rocío; Vilchez, Esther

doi:10.1021/acs.cgd.8b01035

Cited by 24 publications

(12 citation statements)

References 66 publications

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“…In this way, supramolecular environments of molecules can be systematically compared to each other in quantitative terms. This approach proved to be particularly helpful in the identification of substituent, counterion, and (de)protonation effects on the HSs of related compounds. − …”

Section: Resultsmentioning

confidence: 99%

Recurrent Supramolecular Motifs in a Series of Acid–Base Adducts Based on Pyridine-2,5-Dicarboxylic Acid N-Oxide and Organic Bases: Inter- and Intramolecular Hydrogen Bonding

Mirzaei

Sadeghi

Molčanov

et al. 2020

Crystal Growth & Design

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Salts and ionic cocrystals simultaneously comprising N-oxide and carboxylic acid functional groups constitute a very fertile ground for the investigation of various proton transfer phenomena. This is because such compounds combine two types of proton transfer: that is, inter-and intramolecular hydrogen bonding in acid−base systems. To this end, a series of novel salts based on pyridine-2,5-dicarboxylic acid N-oxide (H 2 pydco) as an organic acid and 2,4,6-triamino-1,3,5-triazine (tata), 2-aminopyrimidine (2a-pym), 2-amino-6-methylpyridine (2a-6mpy), 1,10phenanthroline (phen), and 9-aminoacridine (9a-acr) as organic bases have been synthesized and characterized by elemental analyses, infrared spectroscopy, and single-crystal X-ray diffraction: (Htata) + (Hpydco) − (1), (H2a-pym) + (Hpydco) − (2), (H2a-6mpy) + (Hpydco) − (3A,B), [(Hphen) + (Hpydco) − ](H 2 pydco) (4), and [(H9a-acr) + (Hpydco) − ]•EtOH (5). The unit cells of 3A and 3B differ slightly; however, 3A crystallizes in a chiral orthorhombic space group P2 1 2 1 2 1 , while 3B crystallizes in the achiral space group P2 1 /n. In both cases, the asymmetric unit comprises one cation and one anion. The influence of different organic cations on the packing of Hpydco − in the crystal lattice is studied. The most important feature of these crystals is the presence of extensive O− Hbond networks, which form base-dependent supramolecular synthons: 1, 2, and 3A,B comprise an α-aminopyridinium moiety, and all involve the hydrogen-bonded motif R 2 2 (8) with the Hpydco − anion. Compounds 4 and 5, which lack the α-aminopyridinium moiety, reveal different hydrogen-bonding patterns. The interaction energies of each individual hydrogen bond have been estimated using the quantum theory of "atoms-in-molecules", which led us to the identification of the energetically favorable antielectrostatic N−H•••N hydrogen bonds (stabilization energy of 4.0 kcal/mol) between positively charged melaminium species in 1. It has been also established that charge-assisted hydrogen bonding does not always offer an energetic advantage over "noncharged" hydrogen bonds. With the use of Hirshfeld surface (HS) analysis we have also explored the influence of the protonation state of pydco species on the composition of contact contributions, as well as established specific properties of their 2D fingerprint plots. Finally, a comment is provided on the applicability of HS analysis for the exploration of polymorphs featuring intramolecular proton transfer.

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Section: Resultsmentioning

confidence: 99%

Recurrent Supramolecular Motifs in a Series of Acid–Base Adducts Based on Pyridine-2,5-Dicarboxylic Acid N-Oxide and Organic Bases: Inter- and Intramolecular Hydrogen Bonding

Mirzaei

Sadeghi

Molčanov

et al. 2020

Crystal Growth & Design

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“…As possible co-formers of salts or cocrystals against inh, we have considered αhydroxycarboxylic acids, glycolic (H 2 ga) and D,L-mandelic (H 2 ma) [16,17] (Scheme 1). The common molecular features of these analogous co-formers are expected to influence the molecular packing in crystals with both directional H-bonds and no directional van der Waals interactions.…”

Section: Cocrystal Screeningmentioning

confidence: 99%

“…Figure16. Distribution of bond and ring critical points (pink and yellow spheres, respectively) and bond paths in a trimeric assembly of 2.…”

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confidence: 99%

Weak Interactions in Cocrystals of Isoniazid with Glycolic and Mandelic Acids

et al. 2021

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This work deals with the preparation of pyridine-3-carbohydrazide (isoniazid, inh) cocrystals with two α-hydroxycarboxylic acids. The interaction of glycolic acid (H2ga) or d,l-mandelic acid (H2ma) resulted in the formation of cocrystals or salts of composition (inh)·(H2ga) (1) and [Hinh]+[Hma]–·(H2ma) (2) when reacted with isoniazid. An N′-(propan-2-ylidene)isonicotinic hydrazide hemihydrate, (pinh)·1/2(H2O) (3), was also prepared by condensation of isoniazid with acetone in the presence of glycolic acid. These prepared compounds were well characterized by elemental analysis, and spectroscopic methods, and their three-dimensional molecular structure was determined by single crystal X-ray crystallography. Hydrogen bonds involving the carboxylic acid occur consistently with the pyridine ring N atom of the isoniazid and its derivatives. The remaining hydrogen-bonding sites on the isoniazid backbone vary based on the steric influences of the derivative group. These are contrasted in each of the molecular systems. Finally, Hirshfeld surface analysis and Density-functional theory (DFT) calculations (including NCIplot and QTAIM analyses) have been performed to further characterize and rationalize the non-covalent interactions.

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“…As possible coformers of salts or co-crystals against inh, we have considered αhydroxycarboxylic acids, glycolic (H2ga) and DL-mandelic (H2ma) (Scheme 1) [9,10]. From the point of view of hydrogen bonding, each of them contains three acceptor oxygen atoms and two donor O-H groups.…”

Section: Scheme 1 Molecular Structures Of the Formers/coformersmentioning

confidence: 99%

Interactions between Isoniazid and α-Hydroxycarboxylic Acids

Álvarez-Vidaurre

Castiñeiras

García‐Santos

et al. 2020

The 24th International Electronic Conference on Synthetic Organic Chemistry

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The present study refers to the preparation of isonicotinic acid hydrazide (isoniazid, inh) co-crystals with two α-hydroxycarboxylic acids. The interaction of glycolic acid (H2ga) or DLmandelic acid (H2ma) resulted in the formation of co-crystals or salts of composition (inh)•(H2ga) (1) and [Hinh] + [Hma] − •(H2ma) (2) when reacted with isoniazid. An N'-(propan-2-ylidene)isonicotinic hydrazide hemihydrate, (pinh)•1/2(H2O) (3), was also prepared by condensation of isoniazid with acetone in the presence of glycolic acid. The prepared compounds were well characterized by elemental analysis, and spectroscopic methods, and their three-dimensional molecular structure was determined by single crystal X-ray crystallography. Hydrogen bonds involving the carboxylic acid occur consistently with the pyridine ring N atom of the isoniazid and its derivatives. The remaining hydrogen-bonding sites on the isoniazid backbone vary based on the steric influences of the derivative group. These are contrasted in each of the molecular systems.

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Multicomponent Supramolecular Assemblies of Melamine and α-Hydroxycarboxylic Acids: Understanding the Hydrogen Bonding Patterns and Their Physicochemical Consequences

Cited by 24 publications

References 66 publications

Recurrent Supramolecular Motifs in a Series of Acid–Base Adducts Based on Pyridine-2,5-Dicarboxylic Acid N-Oxide and Organic Bases: Inter- and Intramolecular Hydrogen Bonding

Recurrent Supramolecular Motifs in a Series of Acid–Base Adducts Based on Pyridine-2,5-Dicarboxylic Acid N-Oxide and Organic Bases: Inter- and Intramolecular Hydrogen Bonding

Weak Interactions in Cocrystals of Isoniazid with Glycolic and Mandelic Acids

Interactions between Isoniazid and α-Hydroxycarboxylic Acids

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