Structural landscape of benzoic acid: using experimental crystal structures of fluorobenzoic acids as a probe

Dubey, Ritesh; Pavan, Mysore S.; Desiraju, Gautam R.

doi:10.1039/c2cc33811d

Cited by 53 publications

(63 citation statements)

References 23 publications

(11 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The chemical probe of fluoro substitution again shows its usefulness in the exploration of the crystal structure landscape. 3,18 CSD Studies. On the basis of our statistical studies, molecular cocrystals of DPE-I and DPE-II show a nearly …”

Section: ■ Discussionmentioning

confidence: 99%

Exploring the Crystal Structure Landscape with a Heterosynthon Module: Fluorobenzoic Acid:1,2-Bis(4-pyridyl)ethylene 2:1 Cocrystals

Dubey

Desiraju

2014

Crystal Growth & Design

Self Cite

View full text Add to dashboard Cite

The crystal structure landscape of the 2:1 benzoic acid:dipyridylethylene cocrystal (BA:DPE-I) is explored experimentally with fluorosubstituted benzoic acids and extended with studies employing the Cambridge Structural Database (CSD). The interpretation of the cocrystal landscape is facilitated by considering the kinetically favored and robust acid−pyridine heterosynthon as a modular unit. Information based on high-throughput crystallography shows that polymorphs and pseudopolymorphs may belong to the same landscape but arise from different crystallization pathways because of complex and different kinetic features, and secondary synthon preferences. Using the CSD as a guide, the coformer was changed from 1,2-bis(4pyridyl)ethylene (DPE-I) to 1,2-bis(4-pyridyl)ethane (DPE-II) and this provides an extended interpretation of the BA:DPE-I cocrystal landscape, also highlighting the complexity of the kinetic−thermodynamic dichotomy during the molecule-to-crystal progression.

show abstract

Section: ■ Discussionmentioning

confidence: 99%

Exploring the Crystal Structure Landscape with a Heterosynthon Module: Fluorobenzoic Acid:1,2-Bis(4-pyridyl)ethylene 2:1 Cocrystals

Dubey

Desiraju

2014

Crystal Growth & Design

Self Cite

View full text Add to dashboard Cite

show abstract

“…In the investigation by Prof. Desiraju and co-workers, it was observed that the experimental crystal structure of fluorinated (mono or poly) benzoic acid was similar to the "high energy" crystal structure of benzoic acid, predicted computationally (Table 2.1). In other words, it may be concluded that substitution of fluorine on benzoic acid actually stabilized its high energy form by introducing the possibilities of different intermolecular interactions like C-H···F-C and C-F···F-C (these are present in the experimental crystal structure of fluorinated benzoic acid [94]) in the crystal packing. Moreover, in the same work, this behavior was observed to be more consistent with fluorine than with chloro or bromo substituted benzoic acid.…”

Section: Why Fluorine Is So Special?mentioning

confidence: 95%

“…This involved the study of the structural landscape of benzoic acid [94]. In this analysis, different structural landscapes (a total of 100 structures were predicted, corresponds to different rank) of benzoic acid was obtained using COMPASS26 and DREIDING force field using Material Studio (with restriction of space group to P2 1 /c and P-1 only, these being the most common in case of organic compounds).…”

Section: Why Fluorine Is So Special?mentioning

confidence: 99%

Understanding of Noncovalent Interactions Involving Organic Fluorine

Panini¹,

Chopra²

2015

Lecture Notes in Chemistry

View full text Add to dashboard Cite

Due to the unpredictable nature of organic fluorine in its participation in the formation of different supramolecular motifs which concomitantly influences the physicochemical properties of the compounds of interest, the study of noncovalent interactions involving organic fluorine will always be an expanding area of research amongst the scientific community. The participation of organic fluorine in the formation of intermolecular interactions has always been questioned. In this book chapter, we provide insights into new structural features, nature, and energetics associated with intermolecular interactions, namely C-H···F-C, C-F···F-C, C-F···X (N, O, S, halogen) from researchers across the world. The studies show that interactions involving fluorine are ubiquitous and play a central role in the existence of diversified solid state properties, namely polymorphism, crystal engineering, and cocrystallization.

show abstract

“…We examine two possible reasons for this. Sodium saccharin dihydrate belongs to a complex landscape [25][26][27][28][29] of hydrated and anhydrous forms and readily and nearly spontaneously converted into a lower hydrate, Na 3 (sac) 3 ·2H 2 O. [30].…”

Section: Resultsmentioning

confidence: 99%

Bimodal nanoindentation response of the (001) face in crystalline sodium saccharin dihydrate

Mishra

Ramamurty

Desiraju

2015

Maced. J. Chem. Chem. Eng.

Self Cite

View full text Add to dashboard Cite

The nanoindentation response of the (001) face of sodium saccharin dihydrate is examined. The structure can be demarcated into regular and irregular regions or domains. The regular domains have solid-like and the irregular ones have liquid-like characteristics. Therefore, these domains impart a microstructure to the crystal. The indent face (001) is prominently developed in this crystal and unambiguously presents the regular and irregular regions to nanoindention. Average values of elastic modulus and hardness show a distinct bimodal mechanical response. Such a response has been observed in the case of intergrown polymorphs of aspirin and felodipine. We examine two possible reasons as to why the responses could be for bimodal in this crystal. The first possibility could be that the two domains correspond to regions of the original dihydrate and a lower hydrate that is obtained by the loss of some water. The second possibility could be that these responses correspond to regular and irregular regions in the structure. Nanoindentation is a very useful technique in the characterization of molecular solids, as a complementary technique to X-ray crystallography, because it samples different length scales.Keywords: crystal engineering; microstructure; hydrate; saccharin; nanoindentation БИМОДАЛЕН НАНОВДЛАБНУВАЧКИ ОДГОВОР НА ПЛОСКАТА (001) ВО КРИСТАЛНИОТ НАТРИУМСАХАРИНАТ ДИХИДРАТИзучуван е нановдлабнувачкиот одговор на плоската (001) во кристалниот натриумсаха-ринат дихидрат. Структурата може да се разграничи преку регуларни и ирегуларни подрачја или домени. Регуларните домени имаат карактеристики на цврста состојба, а оние ирегуларните на течна состојба. Затоа овие домени ги прават кристалите микроструктурни. Плоската (001) во овој кристал е посебно развиена и недвосмислено ги презентира регуларните и ирегуларните региони на нановдлабнувањето. Средните вредности на еластичниот модул и на тврдоста покажуваат различен бимодален механички одговор. Таков одговор е забележан во случајот на сраснати полиморфи на аспирин и фелодипин. Изучени се двете можни причини зошто одговорите за овој кристал би биле бимодални. Првата можност би можела да биде дека двата домена одговараат на подрачјата на оригиналниот дихидрат и на понискиот хидрат добиен како резултат на губење на дел од водата. Втората можност би можела да биде дека овие одговори соодветствуваат на регуларните и ирегуларните подрачја во структурата. Нановдлабнувањето е многу корисна техника за карактеризирање на молекуларни цврсти супстанци, како комплементарна техника на рендгенската кристалографија, бидејќи таа опфаќа различни должински скали.

show abstract

Structural landscape of benzoic acid: using experimental crystal structures of fluorobenzoic acids as a probe

Abstract: Experimental crystal structures of mono and polyfluorinated benzoic acids correspond to high energy computed crystal structures of benzoic acid itself, thereby permitting access to its structural landscape.

Cited by 53 publications

References 23 publications

Exploring the Crystal Structure Landscape with a Heterosynthon Module: Fluorobenzoic Acid:1,2-Bis(4-pyridyl)ethylene 2:1 Cocrystals

Exploring the Crystal Structure Landscape with a Heterosynthon Module: Fluorobenzoic Acid:1,2-Bis(4-pyridyl)ethylene 2:1 Cocrystals

Understanding of Noncovalent Interactions Involving Organic Fluorine

Bimodal nanoindentation response of the (001) face in crystalline sodium saccharin dihydrate

Contact Info

Product

Resources

About