A comparative experimental and theoretical investigation of hydrogen-bond, halogen-bond and π–π interactions in the solid-state supramolecular assembly of 2- and 4-formylphenyl arylsulfonates

2018 ◽  
Vol 74 (7) ◽  
pp. 816-829 ◽  
Author(s):  
Hina Andleeb ◽  
Imtiaz Khan ◽  
Antonio Bauzá ◽  
Muhammad Nawaz Tahir ◽  
Jim Simpson ◽  
...  
Keyword(s):  
Solid State ◽  
Density Functional ◽  
Halogen Bond ◽  
Noncovalent Interactions ◽  
Supramolecular Assembly ◽  
Halogen Bonding ◽  
Type I ◽  
Supramolecular Architectures ◽  
Solid State Structures

To explore the operational role of noncovalent interactions in supramolecular architectures with designed topologies, a series of solid-state structures of 2- and 4-formylphenyl 4-substituted benzenesulfonates was investigated. The compounds are 2-formylphenyl 4-methylbenzenesulfonate, C14H12O4S, 3a, 2-formylphenyl 4-chlorobenzenesulfonate, C13H9ClO4S, 3b, 2-formylphenyl 4-bromobenzenesulfonate, C13H9BrO4S, 3c, 4-formylphenyl 4-methylbenzenesulfonate, C14H12O4S, 4a, 4-formylphenyl 4-chlorobenzenesulfonate, 4b, C13H9ClO4S, and 4-formylphenyl 4-bromobenzenesulfonate, C13H9BrO4S, 4c. The title compounds were synthesized under basic conditions from salicylaldehyde/4-hydroxybenzaldehydes and various aryl sulfonyl chlorides. Remarkably, halogen-bonding interactions are found to be important to rationalize the solid-state crystal structures. In particular, the formation of O...X (X = Cl and Br) and type I X...X halogen-bonding interactions have been analyzed by means of density functional theory (DFT) calculations and characterized using Bader's theory of `atoms in molecules' and molecular electrostatic potential (MEP) surfaces, confirming the relevance and stabilizing nature of these interactions. They have been compared to antiparallel π-stacking interactions that are formed between the arylsulfonates.

scholarly journals Halogen bonding stabilizes acis-azobenzene derivative in the solid state: a crystallographic study

2017 ◽  
Vol 73 (2) ◽  
pp. 227-233 ◽  
Author(s):  
Marco Saccone ◽  
Antti Siiskonen ◽  
Franisco Fernandez-Palacio ◽  
Arri Priimagi ◽  
Giancarlo Terraneo ◽  
...  
Keyword(s):  
Solid State ◽  
Density Functional ◽  
Rational Design ◽  
Halogen Bond ◽  
Phase Segregation ◽  
Halogen Bonding ◽  
Density Functional Theory Calculations ◽  
Aliphatic Chain ◽  
Molecular Arrangement

Crystals oftrans- andcis-isomers of a fluorinated azobenzene derivative have been prepared and characterized by single-crystal X-ray diffraction. The presence of F atoms on the aromatic core of the azobenzene increases the lifetime of the metastablecis-isomer, allowing single crystals of thecis-azobenzene to be grown. Structural analysis on thecis-azobenzene, complemented with density functional theory calculations, highlights the active role of the halogen-bond contact (N...I synthon) in promoting the stabilization of thecis-isomer. The presence of a long aliphatic chain on the azobenzene unit induces a phase segregation that stabilizes the molecular arrangement for both thetrans- andcis-isomers. Due to the rarity ofcis-azobenzene crystal structures in the literature, our paper makes a step towards understanding the role of non-covalent interactions in driving the packing of metastable azobenzene isomers. This is expected to be important in the future rational design of solid-state, photoresponsive materials based on halogen bonding.

scholarly journals Halogen bonding, chalcogen bonding, pnictogen bonding, tetrel bonding: origins, current status and discussion

2017 ◽  
Vol 203 ◽  
pp. 485-507 ◽  
Author(s):  
Lee Brammer
Keyword(s):  
Solid State ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Main Group ◽  
Solution Phase ◽  
Current Status ◽  
Solid State Chemistry ◽  
Main Group Elements ◽  
Past Work

The role of the closing lecture in a Faraday Discussion is to summarise the contributions made to the Discussion over the course of the meeting and in so doing capture the main themes that have arisen. This article is based upon my Closing Remarks Lecture at the 203rdFaraday Discussion meeting on Halogen Bonding in Supramolecular and Solid State Chemistry, held in Ottawa, Canada, on 10–12thJuly, 2017. The Discussion included papers on fundamentals and applications of halogen bonding in the solid state and solution phase. Analogous interactions involving main group elements outside group 17 were also examined. In the closing lecture and in this article these contributions have been grouped into the four themes: (a) fundamentals, (b) beyond the halogen bond, (c) characterisation, and (d) applications. The lecture and paper also include a short reflection on past work that has a bearing on the Discussion.

13C and 19F solid-state NMR and X-ray crystallographic study of halogen-bonded frameworks featuring nitrogen-containing heterocycles

2017 ◽  
Vol 73 (3) ◽  
pp. 157-167 ◽  
Author(s):  
Patrick M. J. Szell ◽  
Shaina A. Gabriel ◽  
Russell D. D. Gill ◽  
Shirley Y. H. Wan ◽  
Bulat Gabidullin ◽  
...  
Keyword(s):  
Solid State ◽  
Density Functional ◽  
Halogen Bond ◽  
Chemical Shifts ◽  
Halogen Bonding ◽  
Structural Features ◽  
Magic Angle Spinning ◽  
Magic Angle ◽  
X Ray ◽  
Donor And Acceptor

Halogen bonding is a noncovalent interaction between the electrophilic region of a halogen (σ-hole) and an electron donor. We report a crystallographic and structural analysis of halogen-bonded compounds by applying a combined X-ray diffraction (XRD) and solid-state nuclear magnetic resonance (SSNMR) approach. Single-crystal XRD was first used to characterize the halogen-bonded cocrystals formed between two fluorinated halogen-bond donors (1,4-diiodotetrafluorobenzene and 1,3,5-trifluoro-2,4,6-triiodobenzene) and several nitrogen-containing heterocycles (acridine, 1,10-phenanthroline, 2,3,5,6-tetramethylpyrazine, and hexamethylenetetramine). New structures are reported for the following three cocrystals, all in the P21/c space group: acridine–1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C13H9N, 1,10-phenanthroline–1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C12H8N2, and 2,3,5,6-tetramethylpyrazine–1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C8H12N2. 13C and 19F solid-state magic-angle spinning (MAS) NMR is shown to be a convenient method to characterize the structural features of the halogen-bond donor and acceptor, with chemical shifts attributable to cocrystal formation observed in the spectra of both nuclides. Cross polarization (CP) from 19F to 13C results in improved spectral sensitivity in characterizing the perfluorinated halogen-bond donor when compared to conventional 1H CP. Gauge-including projector-augmented wave density functional theory (GIPAW DFT) calculations of magnetic shielding constants, along with optimization of the XRD structures, provide a final set of structures in best agreement with the experimental 13C and 19F chemical shifts. Data for carbons bonded to iodine remain outliers due to well-known relativistic effects.

Competition between hydrogen and halogen bonding in the structures of 5,10-dihydroxy-5,10-dihydroboranthrenes

2014 ◽  
Vol 70 (1) ◽  
pp. 157-171 ◽  
Author(s):  
Krzysztof Durka ◽  
Sergiusz Luliński ◽  
Katarzyna N. Jarzembska ◽  
Jaromir Smętek ◽  
Janusz Serwatowski ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Density Functional ◽  
Crystal Packing ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Structural Diversity ◽  
Interesting Case ◽  
Molecular Arrangement ◽  
Supramolecular Arrangements

X-ray crystallographic and computational studies are reported for a series of boranthrenes, substituted with halogen atoms. The role of competitive hydrogen (O—H...O, O—H...F, C—H...O) and halogen (Cl...Cl, O...Br, F...F) bonding interactions on the molecular arrangement in the crystal structures is discussed. The structural analysis and calculations reveal that the O—H...O hydrogen bond in the unsubstituted derivative 5,10-dihydroxy-5,10-dihydroboranthrene, C12H10B2O2, is of moderate strength (ca−20 kJ mol−1), but weaker than that in the related thiophene derivative 4,8-dihydro-4,8-dihydroxy-p-diborino[2,3-b:5,6-b]dithiophene, C8H6B2O2S2(ca−40 kJ mol−1). This is due to shielding of the OH group by the H atoms in the β-position of the boranthrene unit. Structural diversity derived from the flexibility of the O—H...O hydrogen bond facilitates the occurrence of other competitive interactions. For instance, in the 1,6-difluoro derivative, C12H8B2F2O2, the crystal packing results from O—H...F and F...F interactions. In turn, the 1,6-dibromo derivative, C12H8B2Br2O2, is dominated by Br...O halogen-bond interactions. In the most interesting case, the 1,6-dichloro derivative, C12H8B2Cl2O2, molecular disorder leads to the formation of two different supramolecular arrangements co-existing in the crystal lattice, one based on the Cl...Cl and C—H...O bonds, and the other stabilized by O—H...O hydrogen bonds. Calculations performed with density-functional theory (DFT;CRYSTAL09) andPIXELmethodologies show that both lattices are characterized by similar energy values (ca−100 kJ mol−1). A mixed arrangement with random or short-range-ordered molecular orientations can also be expected.

scholarly journals Role of Halogen Substituents on Halogen Bonding in 4,5-DiBromohexahydro-3a,6-Epoxyisoindol-1(4H)-ones

Crystals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 112
Author(s):  
Atash V. Gurbanov ◽  
Dmitriy F. Mertsalov ◽  
Fedor I. Zubkov ◽  
Maryana A. Nadirova ◽  
Eugeniya V. Nikitina ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Halogen Bonds ◽  
Intermolecular Hydrogen Bonds ◽  
3D Structures ◽  
Supramolecular Architectures

A series of 4,5-dibromo-2-(4-substituted phenyl)hexahydro-3a,6-epoxyisoindol-1(4H)-ones were synthesized by reaction of the corresponding 2-(4-substituted phenyl)-2,3,7,7a-tetrahydro-3a,6-epoxyisoindol-1(6H)-ones with [(Me2NCOMe)2H]Br3 in dry chloroform under reflux for 3−5 h. In contrast to the 4-F and 4-Cl substituents, one of the bromine atoms of the isoindole moiety behaves as a halogen bond donor in the formation of intermolecular halogen bonding in the 4-H, 4-Br and 4-I analogues. Not only intermolecular hydrogen bonds, but also Ha⋯Ha and Ha⋯π types of halogen bonds in the 4-H, 4-Br, and 4-I compounds, contribute to the formation of supramolecular architectures leading to 2D or 3D structures.

scholarly journals A survey of interactions in crystal structures of pyrazine-based compounds

2019 ◽  
Vol 75 (3) ◽  
pp. 231-247 ◽  
Author(s):  
Fatemeh Taghipour ◽  
Masoud Mirzaei
Keyword(s):  
Magnetic Properties ◽  
Hydrogen Bonding ◽  
Solid State ◽  
Organic Compounds ◽  
Coordination Polymers ◽  
Noncovalent Interactions ◽  
Metal Organic Framework ◽  
Supramolecular Architectures ◽  
Metal Organic

The important role of pyrazine (pz) and its derivatives in fields such as biochemistry and pharmacology, as well as in the study of magnetic properties, is surveyed. Recognition of these properties without extensive investigations into their structural properties is not possible. This review summarizes interactions that exist between these organic compounds by themselves in the solid state, as well as those in coordination polymers with metal ions and in polyoxometalate-based hybrids. Complexes based on pyrazine ligands can generate metal–organic framework (MOF) structures that bind polyoxometalates (POMs) through covalent and noncovalent interactions. Some biological and magnetic properties involving these compounds are considered and the effect of hydrogen bonding on their supramolecular architectures is highlighted.

An insight to the noncovalent interactions in two triamine based mononuclear iron(III) Schiff base complexes with special emphasis on the formation of Br•••π halogen bonding

CrystEngComm ◽  
2021 ◽  
Author(s):  
Shouvik Chattopadhyay ◽  
Tanmoy Basak ◽  
Antonio Frontera
Keyword(s):  
Schiff Base ◽  
Solid State ◽  
Noncovalent Interactions ◽  
Halogen Bonding ◽  
Schiff Base Complexes ◽  
X Ray ◽  
Mononuclear Iron

Two mononuclear iron(III) complexes, [FeL1Cl]∙CH3CN (1) and [FeL2(N3)] (2) {H2L1= N,N′-bis(5-chlorosalicylidene)diethylenetriamine and H2L2= N,N′-bis(5-bromosalicylidene)diethylenetriamine}, have been synthesized and characterized by X-ray crystallographic studies. In the solid state, there are strong...

scholarly journals Adenine as a Halogen Bond Acceptor: A Combined Experimental and DFT Study

Crystals ◽  
2019 ◽  
Vol 9 (4) ◽  
pp. 224 ◽  
Author(s):  
Yannick Roselló ◽  
Mónica Benito ◽  
Elies Molins ◽  
Miquel Barceló-Oliver ◽  
Antonio Frontera
Keyword(s):  
Density Functional ◽  
Halogen Bond ◽  
Lone Pair ◽  
Halogen Bonding ◽  
Density Functional Theory Calculations ◽  
Functional Theory ◽  
Adenine Ring ◽  
Bonding Interaction ◽  
Donor Ability ◽  
Adenine Derivative

In this work, we report the cocrystallization of N9-ethyladenine with 1,2,4,5-tetrafluoro-3,6-diiodobenzene (TFDIB), a classical XB donor. As far as our knowledge extends, this is the first cocrystal reported to date where an adenine derivative acts as a halogen bond acceptor. In the solid state, each adenine ring forms two centrosymmetric H-bonded dimers: one using N1···HA6–N6 and the other N7···HB6–N6. Therefore, only N3 is available as a halogen bond acceptor that, indeed, establishes an N···I halogen bonding interaction with TFDIB. The H-bonded dimers and halogen bonds have been investigated via DFT (Density Functional Theory) calculations and the Bader’s Quantum Theory of Atoms In Molecules (QTAIM) method at the B3LYP/6-311+G* level of theory. The influence of H-bonding interactions on the lone pair donor ability of N3 has also been analyzed using the molecular electrostatic potential (MEP) surface calculations.

scholarly journals Computational study on the mechanism of metal-free photochemical borylation of aryl halides

2021 ◽  
Author(s):  
Chenhao Tu ◽  
Nana Ma ◽  
Qingli Xu ◽  
Wenyue Guo ◽  
Lanxin Zhou ◽  
...  
Keyword(s):  
Density Functional ◽  
Uv Light ◽  
Computational Study ◽  
Halogen Bond ◽  
Bond Cleavage ◽  
Aryl Halides ◽  
Homolytic Cleavage ◽  
Functional Theory ◽  
Aryl Radicals

C-radical borylation is an significant approach for the construction of carbon−boron bond. Photochemical borylation of aryl halides successfully applied this strategy. However, precise mechanisms, such as the generation of aryl radicals and the role of base additive(TMDAM) and water, remain controversy in these reactions. In this study, photochemical borylation of aryl halides has been researched by density functional theory (DFT) calculations. Indeed, the homolytic cleavage of the C−X bond under irradiation with UV-light is a key step for generation of aryl radicals. Nevertheless, the generation of aryl radicals may also undergo the process of single electron transfer and the heterolytic carbon-halogen bond cleavage sequence, and the latter is favorable during the reaction.

scholarly journals Halogen Bonding: An Underestimated Player in Membrane–drug Interactions

2020 ◽  
Author(s):  
Rafael Nunes ◽  
Diogo Vila Viçosa ◽  
Paulo J. Costa
Keyword(s):  
Drug Discovery ◽  
Chemical Space ◽  
Noncovalent Interactions ◽  
Halogen Bonding ◽  
Lewis Bases ◽  
Protein Ligand Interactions ◽  
Biochemical Systems ◽  
Ligand Interactions ◽  
Dynamics Simulations

<div>Halogen bonds (HaBs) are noncovalent interactions where halogen atoms act as electrophilic species interacting with Lewis bases. These interactions are relevant in biochemical systems being increasingly explored in drug discovery, mainly to modulate protein–ligand interactions. In this work, we report evidence for the existence of HaB-mediated halogen–phospholipid recognition phenomena as our molecular dynamics simulations support the existence of favorable interactions between halobenzene derivatives and both phosphate (PO) or ester (CO) oxygen acceptors from model phospholipid bilayers, thus providing insights into the role of HaBs in driving the permeation of halogenated drug like molecules across biological membranes. This represents a relevant molecular mechanism, previously overlooked, determining the pharmacological activity of halogenated molecules with implications in drug discovery and development, a place where halogenated molecules account for a significant part of the chemical space. Our data also shows that, as the ubiquitous hydrogen bond, HaBs should be accounted for in the development of membrane permeability models.</div>

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