Theoretical and Experimental Evaluation of Homo- and Heterodimeric Hydrogen-Bonded Motifs Containing Boronic Acids, Carboxylic Acids, and Carboxylate Anions:  Application for the Generation of Highly Stable Hydrogen-Bonded Supramolecular Systems

Rodríguez-Cuamatzi, Patricia; Arillo-Flores, O. I.; Bernal-Uruchurtu, Margarita I.; Höpfl, Herbert

doi:10.1021/cg0498453

Cited by 80 publications

(42 citation statements)

References 66 publications

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“…The basis set used is adequate, given the small BSSE obtained. While the interaction energy obtained for the carboxylic acid dimer is comparable to earlier reports, a significantly lower value was obtained for the boronic acid dimer [38]. The data obtained supports the formation of co-crystals of phenylboronic acids with ALP and PHEN because the cyclic OH···N hydrogen bonds (Scheme 3; Synthon I and II) are energetically more favorable than the boronic acid dimers.…”

Section: Csd Analysissupporting

confidence: 84%

Phenylboronic acids in crystal engineering: Utility of the energetically unfavorable syn,syn-conformation in co-crystal design

2011

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Phenylboronic acids can exist, in principle, in three different conformers (syn,syn; syn,anti and anti,anti) with distinct energy profiles. In their native state, these compounds prefer the energetically favored syn,anti-conformation. In molecular complexes, however, the functionality exhibits conformational diversity. In this paper we report a series of co-crystals, with N-donor compounds, prepared by a design strategy involving the synthons based on the syn,syn-conformation of the boronic acid functionality. For this purpose, we employed compounds with the 1,2-diazo fragment (alprazolam, 1H-tetrazole, acetazolamide and benzotriazole), 1,10-phenanthroline and 2,2'-bipyridine for the co-crystallization experiments. However, our study shows that the mere presence of the 1,2-diazo fragment in the coformer does not guarantee the successful formation of co-crystals with a syn,syn-conformation of the boronic acid.Typical cyclic OH···N hydrogen bonds formed by boronic acids with alprazolam (a) and 1,10-phenanthroline (b).The -B(OH) 2 fragment makes unsymmetrical O-H···N heterosynthons with alprazolam (ALP) and 1,10-phenanthroline (PHEN). In the co-crystals of phenylboronic acids with 1H-tetrazole (TETR) and 2,2'-bipyridine (BPY), the symmetrical boronic acid dimer is the major synthon. In the BPY complex, boronic acid forms linear chains and the pyridine compound interacts with the lateral OH of boronic acid dimers that acts as a connector, thus forming a ladder structure. In the TETR complex, each heterocycle interacts with three boronic acids. While two boronic acids interact using the phenolic group, the third molecule generates O-H···N hydrogen bonds using the extra OH group, of -B(OH) 2 fragment, left after the dimer formation. Thus, although molecules were selected retrosynthetically with the 1,2-diazo fragment or with nearby hetero-atoms to induce co-crystal formation using the syn,syn-orientation of the -B(OH) 2 functionality, co-crystal formation is in fact selective and is probably driven by energy factors. Acetazolamide (ACET) contains self-complementary functional groups and hence creates stable homosynthons. Phenylboronic acids being weak competitors fail to perturb the homosynthons and hence the components crystallize separately. Therefore, besides the availability of possible hydrogen bond acceptors in the required position and orientation, the ability of the phenyl-boronic acid to perturb the existing interactions is also a prerequisite to form co-crystals. This is illustrated in the 1910 Varughese S, et al. Sci China Chem December (2011) Vol.54 No.12 table below. In the case of ALP, PHEN and BPY, the native structures are stabilized by weak interactions and may be influenced by the boronic acid fragment. Thus phenylboronic acids can attain co-crystals with those compounds, wherein the cyclic O-H···N hydrogen bonds are stronger than the individual homo-interactions. This can lower the lattice energy of the molecular complex as compared with the individual crystals.Heterosynthons formed by boronic a...

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Section: Csd Analysissupporting

confidence: 84%

Phenylboronic acids in crystal engineering: Utility of the energetically unfavorable syn,syn-conformation in co-crystal design

2011

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“…Since charged [RCOOH· · ·OOCR] 2 systems form significantly stronger hydrogen bonds than the [RCOOH· · ·HOOCR] dimers (< 2 31 kcal/mol $ < 2 19 kcal/mol) [49], recently carboxylate based systems have been the subject of several studies in crystal engineering [50 -64]. Such systems, and in particular those having [RCOOH· · ·OOCR] 2 and [ROH· · ·OOCR] 2 interactions, play also an important role for the structural organization and chemistry of biomolecules [65 -68].…”

mentioning

confidence: 99%

Experimental and Theoretical Analysis of the Hydrogen-bonding Motifs Formed Between the Carboxyl and the Carboxylate Group: Towards a Systematic Classification of their Supramolecular Motifs

Rodríguez-Cuamatzi

Arillo-Flores

Bernal-Uruchurtu

et al. 2007

Supramolecular Chemistry

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Nine tetraalkylammonium salts, with R 5 Me, Et, n Pr and n Bu, of four different carboxylic acids, namely isophthalic acid, 5-nitroisophthalic acid, trimesic acid and pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid), have been prepared and their supramolecular structures analyzed by X-ray crystallography. The [RCOOH· · ·HOOCR] homodimeric motif characteristic for carboxylic acids has not been detected, but instead, in all compounds a [RCOOH· · ·OOCR] 2 unit was present. The hydrogen-bonding geometries and interaction energies of the different discrete and water-expanded hydrogen-bonding patterns formed between the carboxyl and the carboxylate group have been analyzed systematically by theoretical calculations at the MP2/6-31G(d,p) level of theory.Carboxylates are promising candidates for crystal engineering and [OZH· · ·O] 2 interactions play an important role for the structural organization and chemistry of biomolecules.

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“…Recently arylboronic acids have also been employed as promising building blocks in crystal engineering and various types of novel supramoolecular assemblies have been generated [3,4]. Analogous to carboxylic acids, they are capable of forming dimeric units, this is the most basic and frequent structural motif found in the solid state [5]. The title crystal structure has two crystallographically independent molecules in the asymmetric unit.…”

Section: Discussionmentioning

confidence: 99%

Refinement of crystal structure of 2-biphenylboronic acid, C12H11BO2

Bai¹,

Liu²,

Li³

et al. 2010

Zeitschrift Für Kristallographie - New Crystal Structures

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Theoretical and Experimental Evaluation of Homo- and Heterodimeric Hydrogen-Bonded Motifs Containing Boronic Acids, Carboxylic Acids, and Carboxylate Anions: Application for the Generation of Highly Stable Hydrogen-Bonded Supramolecular Systems

Cited by 80 publications

References 66 publications

Phenylboronic acids in crystal engineering: Utility of the energetically unfavorable syn,syn-conformation in co-crystal design

Phenylboronic acids in crystal engineering: Utility of the energetically unfavorable syn,syn-conformation in co-crystal design

Experimental and Theoretical Analysis of the Hydrogen-bonding Motifs Formed Between the Carboxyl and the Carboxylate Group: Towards a Systematic Classification of their Supramolecular Motifs

Refinement of crystal structure of 2-biphenylboronic acid, C12H11BO2

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