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.

scholarly journals New approaches to organocatalysis based on C–H and C–X bonding for electrophilic substrate activation

2016 ◽  
Vol 12 ◽  
pp. 2834-2848 ◽  
Author(s):  
Pavel Nagorny ◽  
Zhankui Sun
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Recent Progress ◽  
Halogen Bonds ◽  
Hydrogen Bond Donor ◽  
New Approaches ◽  
Substrate Activation ◽  
Non Covalent Interactions ◽  
Covalent Interactions ◽  
Hydrogen Bond Donors

Hydrogen bond donor catalysis represents a rapidly growing subfield of organocatalysis. While traditional hydrogen bond donors containing N–H and O–H moieties have been effectively used for electrophile activation, activation based on other types of non-covalent interactions is less common. This mini review highlights recent progress in developing and exploring new organic catalysts for electrophile activation through the formation of C–H hydrogen bonds and C–X halogen bonds.

Halogen bonding directed supramolecular assembly in bromo-substituted trezimides and tennimides

CrystEngComm ◽  
2014 ◽  
Vol 16 (10) ◽  
pp. 1893-1903 ◽  
Author(s):  
Pavle Mocilac ◽  
John F. Gallagher
Keyword(s):  
Hydrogen Bond ◽  
Solid State ◽  
Crystal Structures ◽  
Supramolecular Assembly ◽  
Halogen Bonding ◽  
Strong Hydrogen Bond ◽  
Aggregation Process ◽  
Halogen Bonds ◽  
State Aggregation ◽  
Hydrogen Bond Donors

The imide-based trezimide and tennimide macrocycle crystal structures typically aggregate as 1-D chains through C–Br⋯OC/N/π(arene) halogen bonds (withNc≤ 0.90) that dominate the solid-state aggregation process in the absence of classical strong hydrogen bond donors.

Finding a single-molecule receptor for citramalic acid through supramolecular chelation

2015 ◽  
Vol 93 (8) ◽  
pp. 822-825 ◽  
Author(s):  
Christer B. Aakeröy ◽  
Michelle Smith ◽  
John Desper
Keyword(s):  
Hydrogen Bond ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Single Molecule ◽  
Conformational Flexibility ◽  
State Structure ◽  
Hydrogen Bond Acceptor ◽  
Solid State Structure ◽  
Face To Face ◽  
Hydrogen Bond Donors

We have demonstrated that the tritopic hydrogen-bond acceptor 1,3,5-(5,6-dimethylbenzimidazol-1-yl)-2,4,6-trimethylbenzene can act as a perfectly complementary receptor for citramalic acid. The solid-state structure of the cocrystal of the two components show that they form 1:1 pairs where each pair is held together by three near-linear O–H···N hydrogen bonds in a converging manner. The conformational flexibility of both species is apparently no hindrance to the formation of discrete dimeric “cups” wherein each species presents three hydrogen-bond donors/acceptors in a face-to-face orientation.

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.

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.

Halogen Bonding Organocatalysis Enhanced through Intramolecular Hydrogen Bonds

2022 ◽  
Author(s):  
Asia Marie S Riel ◽  
Daniel Adam Decato ◽  
Jiyu Sun ◽  
Orion Berryman
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Halogen Bond ◽  
Direct Interaction ◽  
Halogen Bonding ◽  
Intramolecular Hydrogen Bonds ◽  
Intramolecular Hydrogen

Recent results indicate a halogen bond donor is strengthened through direct interaction with a hydrogen bond to the electron-rich belt of the halogen. Here, this Hydrogen Bond enhanced Halogen Bond...

scholarly journals 1-[N-Methyl-N-(Phenyl)amino]-3- (4-Methylphenyl)Thiourea

Molbank ◽  
10.3390/m1052 ◽  
2019 ◽  
Vol 2019 (1) ◽  
pp. M1052 ◽  
Author(s):  
Chien Yeo ◽  
Edward Tiekink
Keyword(s):  
Hydrogen Bond ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Single Crystal ◽  
Elemental Analysis ◽  
Title Compound ◽  
Molecular Conformation ◽  
Phenyl Hydrazine ◽  
X Ray ◽  
X Ray Crystallography

The title compound, 1-[N-methyl-N-(phenyl)amino]-3-(4-methylphenyl)thiourea (1), was synthesized by the reaction of 1-methyl-1-phenyl hydrazine and 4-tolyl isothiocyanate, and was characterized by spectroscopy (1H and 13C{1H} NMR, IR, and UV), elemental analysis as well as by single crystal X-ray crystallography. In the solid state, the molecule exists as the thioamide tautomer and features an anti-disposition of the thioamide–N–H atoms; an intramolecular N–H⋯N hydrogen bond is noted. The molecular conformation resembles that of the letter L. In the molecular packing, thioamide-N1–H⋯S1(thione) hydrogen bonds lead to centrosymmetric eight-membered {⋯HNCS}2 synthons. The dimers are assembled into a supramolecular layer in the bc-plane by phenyl- and methyl-C–H⋯π(phenyl) interactions.

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.

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