Synthesis and Characterisation of Chiral Triazole-Based Halogen-Bond Donors: Halogen Bonds in the Solid State and in Solution

2017 ◽  
Vol 23 (30) ◽  
pp. 7337-7344 ◽  
Author(s):  
Mikk Kaasik ◽  
Sandra Kaabel ◽  
Kadri Kriis ◽  
Ivar Järving ◽  
Riina Aav ◽  
...  
Keyword(s):  
Solid State ◽  
Halogen Bond ◽  
Halogen Bonds

Crystal structure and photoreactivity of a halogen-bonded cocrystal based upon 1,2-diiodoperchlorobenzene and 1,2-bis(pyridin-4-yl)ethylene

2020 ◽  
Vol 76 (6) ◽  
pp. 557-561
Author(s):  
Eric Bosch ◽  
Jessica D. Battle ◽  
Ryan H. Groeneman
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Ultraviolet Light ◽  
Halogen Bond ◽  
Cycloaddition Reaction ◽  
Solvent Free ◽  
Halogen Bonds ◽  
Face To Face ◽  
Similar Yield

The formation of a photoreactive cocrystal based upon 1,2-diiodoperchlorobenzene (1,2-C6I2Cl4 ) and trans-1,2-bis(pyridin-4-yl)ethylene (BPE) has been achieved. The resulting cocrystal, 2(1,2-C6I2Cl4 )·(BPE) or C6Cl4I2·0.5C12H10N2, comprises planar sheets of the components held together by the combination of I...N halogen bonds and halogen–halogen contacts. Notably, the 1,2-C6I2Cl4 molecules π-stack in a homogeneous and face-to-face orientation that results in an infinite column of the halogen-bond donor. As a consequence of this stacking arrangement and I...N halogen bonds, molecules of BPE also stack in this type of pattern. In particular, neighbouring ethylene groups in BPE are found to be parallel and within the accepted distance for a photoreaction. Upon exposure to ultraviolet light, the cocrystal undergoes a solid-state [2 + 2] cycloaddition reaction that produces rctt-tetrakis(pyridin-4-yl)cyclobutane (TPCB) with an overall yield of 89%. A solvent-free approach utilizing dry vortex grinding of the components also resulted in a photoreactive material with a similar yield.

Competition between hydrogen bonds and halogen bonds: a structural study

2018 ◽  
Vol 42 (13) ◽  
pp. 10539-10547 ◽  
Author(s):  
Janaka C. Gamekkanda ◽  
Abhijeet S. Sinha ◽  
John Desper ◽  
Marijana Đaković ◽  
Christer B. Aakeröy
Keyword(s):  
Hydrogen Bond ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Structural Study ◽  
Halogen Bond ◽  
Halogen Bonds ◽  
Hydrogen Bond Donors

O–H hydrogen-bond donors and R–CC–I halogen-bond donors are close competitors for suitable acceptor sites in solid-state assembly.

Probing halogen bonds with solid-state NMR spectroscopy: observation and interpretation of J(77Se,31P) coupling in halogen-bonded PSe⋯I motifs

CrystEngComm ◽  
2014 ◽  
Vol 16 (31) ◽  
pp. 7285-7297 ◽  
Author(s):  
Jasmine Viger-Gravel ◽  
Julia E. Meyer ◽  
Ilia Korobkov ◽  
David L. Bryce
Keyword(s):  
Solid State ◽  
Nmr Spectroscopy ◽  
Solid State Nmr ◽  
Halogen Bond ◽  
Molecular Orbitals ◽  
Halogen Bonds ◽  
Solid State Nmr Spectroscopy ◽  
Covalent Interaction ◽  
Localized Molecular Orbitals ◽  
Spectroscopy Observation

Intra-halogen bond J couplings measured via NMR spectroscopy and interpreted using natural localized molecular orbitals offer novel insights into this class of non-covalent interaction.

scholarly journals 5-Iodo-1-Arylpyrazoles as Potential Benchmarks for Investigating the Tuning of the Halogen Bonding

Crystals ◽  
2020 ◽  
Vol 10 (12) ◽  
pp. 1149
Author(s):  
Denisa Dumitrescu ◽  
Sergiu Shova ◽  
Isabela C. Man ◽  
Mino R. Caira ◽  
Marcel Mirel Popa ◽  
...  
Keyword(s):  
Solid State ◽  
Small Molecules ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Halogen Bonds ◽  
X Ray Diffraction ◽  
Aryl Ring ◽  
X Ray ◽  
Alkyl Groups ◽  
Hirshfeld Analysis

5-Iodo-1-arylpyrazoles are interesting templates for investigating the halogen bond propensity in small molecules other than the already well-known halogenated molecules such as tetrafluorodiiodobenzene. Herein, we present six compounds with different substitution on the aryl ring attached at position 1 of the pyrazoles and investigate them in the solid state in order to elucidate the halogen bonding significance to the crystallographic landscape of such molecules. The substituents on the aryl ring are generally combinations of halogen atoms (Br, Cl) and various alkyl groups. Observed halogen bonding types spanned by these six 5-iodopyrazoles included a wide variety, namely, C–I⋯O, C–I⋯π, C–I⋯Br, C–I⋯N and C–Br⋯O interactions. By single crystal X-ray diffraction analysis combined with the descriptive Hirshfeld analysis, we discuss the role and influence of the halogen bonds among the intermolecular interactions.

Competition and selectivity in supramolecular synthesis: structural landscape around 1-(pyridylmethyl)-2,2′-biimidazoles

2017 ◽  
Vol 203 ◽  
pp. 371-388 ◽  
Author(s):  
C. A. Gunawardana ◽  
J. Desper ◽  
A. S. Sinha ◽  
M. Ðaković ◽  
C. B. Aakeröy
Keyword(s):  
Hydrogen Bond ◽  
Solid State ◽  
Proton Transfer ◽  
Halogen Bond ◽  
Crystal Formation ◽  
Halogen Bonds ◽  
Supramolecular Architectures ◽  
Hydrogen Bond Interactions ◽  
Structure Extension ◽  
The Impact

Three isomeric forms of 1-(pyridylmethyl)-2,2′-biimidazole, A1–A3, have been synthesized and subjected to systematic co-crystallizations with selected hydrogen- and halogen-bond donors in order to explore the impact of electrostatics and geometry on the resulting supramolecular architectures. The solid-state supramolecular behavior of A1–A3 is largely consistent in halogen-bonded co-crystals. Only two types of primary interactions, the N–H⋯N/N⋯H–N homomeric hydrogen-bond interactions responsible for the pairing of biimidazole moieties and the I⋯N(pyridine) halogen bonds responsible for the co-crystal formation and structure extension, are present in these systems. The co-crystallizations with hydrogen-bond donors (carboxylic acids), however, lead to multiple possible structural outcomes because of the presence of the biimidazole–acid N–H⋯OC/N⋯H–O heterosynthon that can compete with biimidazole–biimidazole N–H⋯N/N⋯H–N homosynthon. In addition, the somewhat unpredictable nature of proton transfer makes the hydrogen-bonded co-crystals structurally less consistent than their halogen-bonded counterparts.

Ethynyl hydrogen bonds and iodoethynyl halogen bonds: a case of synthon mimicry

CrystEngComm ◽  
2017 ◽  
Vol 19 (1) ◽  
pp. 11-13 ◽  
Author(s):  
Christer B. Aakeröy ◽  
Dhanushi Welideniya ◽  
John Desper
Keyword(s):  
Solid State ◽  
Hydrogen Bonds ◽  
Crystal Engineering ◽  
Halogen Bond ◽  
Supramolecular Assemblies ◽  
Halogen Bonds ◽  
The Common ◽  
Synthetic Crystal

The common electrostatic features of ethynyl and iodoethynyl hydrogen- and halogen-bond donors, respectively, lead to synthon mimicry which can be employed in synthetic crystal engineering for the construction of identical supramolecular assemblies in the solid-state.

scholarly journals Tautomeric Equilibrium of an Asymmetric β-Diketone in Halogen-Bonded Cocrystals with Perfluorinated Iodobenzenes

Crystals ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 699
Author(s):  
Valentina Martinez ◽  
Nikola Bedeković ◽  
Vladimir Stilinović ◽  
Dominik Cinčić
Keyword(s):  
Solid State ◽  
Hydrogen Atom ◽  
Crystal Structures ◽  
Crystal Packing ◽  
Halogen Bond ◽  
Tautomeric Equilibrium ◽  
Hydroxyl Group ◽  
Halogen Bonds ◽  
Pyridyl Nitrogen

In order to study the effect of halogen bond on tautomerism in β-diketones in the solid-state, we have prepared a series of cocrystals derived from an asymmetric β-diketone, benzoyl-4-pyridoylmethane (b4pm), as halogen bond acceptor and perfluorinated iodobenzenes: iodopentaflourobenzene (ipfb), 1,2-, 1,3- and 1,4-diiodotetraflorobenzene (12tfib, 13tfib and 14tfib) and 1,3,5-triiodo-2,4,6-trifluorobenzene (135titfb). All five cocrystals are assembled by I···N halogen bonds involving pyridyl nitrogen and iodoperfluorobenzene iodine resulting in 1:1 (four compounds) or 1:2 (one compound) cocrystal stoichiometry. Tautomer of b4pm in which hydrogen atom is adjacent to the pyridyl fragment was found to be more stable in vacuo than tautomer with a benzoyl hydroxyl group. This tautomer is also found to be dominant in the majority of crystal structures, somewhat more abundantly in crystal structures of cocrystals in which additional I···O halogen bond with the benzoyl oxygen has been established. Attempts have also been made to prepare an equivalent series of cocrystals using a closely related asymmetric β-diketone, benzoyl-3-pyridoylmethane (b3pm); however, all attempts were unsuccessful, which is attributed to more effective crystal packing of b3pm isomer compared to b4pm, which reduced the probability of cocrystal formation.

scholarly journals Convenient Access to Functionalized Non-Symmetrical Atropisomeric 4,4′-Bipyridines

Compounds ◽  
2021 ◽  
Vol 1 (2) ◽  
pp. 58-74
Author(s):  
Emmanuel Aubert ◽  
Emmanuel Wenger ◽  
Paola Peluso ◽  
Victor Mamane
Keyword(s):  
Solid State ◽  
Intermolecular Interactions ◽  
Medicinal Chemistry ◽  
Crystal Packing ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Halogen Bonds ◽  
Cross Coupling Reactions ◽  
Cyano Groups ◽  
Post Functionalization

Non-symmetrical chiral 4,4′-bipyridines have recently found interest in organocatalysis and medicinal chemistry. In this regard, the development of efficient methods for their synthesis is highly desirable. Herein, a series of non-symmetrical atropisomeric polyhalogenated 4,4′-bipyridines were prepared and further functionalized by using cross-coupling reactions. The desymmetrization step is based on the N-oxidation of one of the two pyridine rings of the 4,4′-bipyridine skeleton. The main advantage of this methodology is the possible post-functionalization of the pyridine N-oxide, allowing selective introduction of chlorine, bromine or cyano groups in 2- and 2′-postions of the chiral atropisomeric 4,4′-bipyridines. The crystal packing in the solid state of some newly prepared derivatives was analyzed and revealed the importance of halogen bonds in intermolecular interactions.

Intermolecular binding preferences of haloethynyl halogen-bond donors as a function of molecular electrostatic potentials in a family of N-(pyridin-2-yl)amides

2021 ◽  
Author(s):  
Amila M. Abeysekera ◽  
Boris B. Averkiev ◽  
Pierre Le Magueres ◽  
Christer B. Aakeröy
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Halogen Bond ◽  
Electrostatic Potentials ◽  
Halogen Bonds ◽  
Molecular Electrostatic Potentials

The roles played by halogen bonds and hydrogen bonds in the crystal structures of N-(pyridin-2-yl)amides were evaluated and rationalised in the context of calculated molecular electrostatic potentials.

A kinetic study of mechanochemical halogen bond formation by in situ31P solid-state NMR spectroscopy

2017 ◽  
Vol 53 (71) ◽  
pp. 9930-9933 ◽  
Author(s):  
Yijue Xu ◽  
Lysiane Champion ◽  
Bulat Gabidullin ◽  
David L. Bryce
Keyword(s):  
Activation Energy ◽  
Solid State ◽  
Nmr Spectroscopy ◽  
Kinetic Study ◽  
Solid State Nmr ◽  
Halogen Bond ◽  
Bond Formation ◽  
Nmr Studies ◽  
Solid State Nmr Spectroscopy

In situ 31P solid-state NMR studies of mechanochemical halogen bond formation provide insights into the cocrystallisation process and an estimate of the activation energy.

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