scholarly journals Controlling Topology within Halogen-Bonded Networks by Varying the Regiochemistry of the Cyclobutane-Based Nodes

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3152
Author(s):  
Taylor J. Dunning ◽  
Daniel K. Unruh ◽  
Eric Bosch ◽  
Ryan H. Groeneman
Keyword(s):  
Halogen Bond ◽  
Molecular Networks ◽  
Halogen Bonds ◽  
Pyridyl Group

The formation of a pair of extended networks sustained by halogen bonds based upon two regioisomers of a photoproduct, namely rctt-1,3-bis(4-pyridyl)-2,4-bis(phenyl)cyclobutane (ht-PP) and rctt-1,2-bis(4-pyridyl)-3,4-bis(phenyl)cyclobutane (hh-PP), that have varied topology is reported. These networks are held together via I⋯N halogen bonds between the photoproduct and the halogen-bond donor 1,4-diiodoperchlorobenzene (C6I2Cl4). The observed topology in each solid is controlled by the regiochemical position of the halogen-bond accepting 4-pyridyl group. This paper demonstrates the ability to vary the topology of molecular networks by altering the position of the halogen bond acceptor within the cyclobutane-based node.

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.

scholarly journals "ANTI-HALOGEN" BONDS AS A FACTOR DETERMINING THE TETRAHEDRAL STRUCTURE OF COPPER IN ITS COMPLEXES WITH (5Z, 5'Z)-2,2'- (ETHANE-1,2-DIYLDISULFANYLDIYL)BIS(5-(2-PYRIDYLMETHYLENE)-3-ALLYL-3,5-DIHYDRO- 4H-IMIDAZOLE-4-ONE)

2021 ◽  
Vol 2 (74) ◽  
pp. 38-41
Author(s):  
A. Al-Khazraji ◽  
I. Dudkin ◽  
E. Ofitserov ◽  
A. Finko ◽  
E. Beloglazkina
Keyword(s):  
Electron Density ◽  
Copper Atom ◽  
Halogen Bond ◽  
Halogen Bonds ◽  
Tetrahedral Structure ◽  
Angle Of Rotation

Analysis of the valence angles of the Si and carbon atoms of the C-S bond in the obtained complexes of CiVg2 c (5Z, 5'Z)-2,2’-(ethane-1,2-diyldisulfanyldiyl)bis(5-(2-pyridylmethylene)-3-allyl-3,5-dihydro-4Нimidazole-4-one) unambiguously indicates the determinant effect of the non-valent interactions of the electron density centroids of the NEP of bromine atoms and sulfur atoms, leading to a change in the plane structure of Cu(II) towards tetrahedral with a likely change in the magnetochemical properties of the copper atom, and the angle of rotation of the planes is almost 900. This interaction is the opposite of what is commonly called a halogen bond. In this case, it is an "anti-halogen" bond.

scholarly journals Using beryllium bonds to change halogen bonds from traditional to chlorine-shared to ion-pair bonds

2015 ◽  
Vol 17 (3) ◽  
pp. 2259-2267 ◽  
Author(s):  
Ibon Alkorta ◽  
José Elguero ◽  
Otilia Mó ◽  
Manuel Yáñez ◽  
Janet E. Del Bene
Keyword(s):  
Halogen Bond ◽  
Ion Pair ◽  
Ternary Complexes ◽  
Halogen Bonds ◽  
Bond Type ◽  
Cooperative Effects ◽  
Pair Bonds

Dramatic synergistic cooperative effects between Be⋯F beryllium bonds and Cl⋯N halogen bonds in XYBe:FCl:N-base ternary complexes lead to changes in the halogen-bond type from traditional to chlorine-shared to ion-pair bonds.

scholarly journals Halogen-Bonded Guanine Base Pairs, Quartets and Ribbons

2020 ◽  
Vol 21 (18) ◽  
pp. 6571
Author(s):  
Nicholas J. Thornton ◽  
Tanja van Mourik
Keyword(s):  
Base Pair ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Dna Bases ◽  
Halogen Bonds ◽  
Base Pairs ◽  
Rich Diversity ◽  
Different Types ◽  
Guanine Base ◽  
The Stability

Halogen bonding is studied in different structures consisting of halogenated guanine DNA bases, including the Hoogsteen guanine–guanine base pair, two different types of guanine ribbons (R-I and R-II) consisting of two or three monomers, and guanine quartets. In the halogenated base pairs (except the Cl-base pair, which has a very non-planar structure with no halogen bonds) and R-I ribbons (except the At trimer), the potential N-X•••O interaction is sacrificed to optimise the N-X•••N halogen bond. In the At trimer, the astatines originally bonded to N1 in the halogen bond donating guanines have moved to the adjacent O6 atom, enabling O-At•••N, N-At•••O, and N-At•••At halogen bonds. The brominated and chlorinated R-II trimers contain two N-X•••N and two N-X•••O halogen bonds, whereas in the iodinated and astatinated trimers, one of the N-X•••N halogen bonds is lost. The corresponding R-II dimers keep the same halogen bond patterns. The G-quartets display a rich diversity of symmetries and halogen bond patterns, including N-X•••N, N-X•••O, N-X•••X, O-X•••X, and O-X•••O halogen bonds (the latter two facilitated by the transfer of halogens from N1 to O6). In general, halogenation decreases the stability of the structures. However, the stability increases with the increasing atomic number of the halogen, and the At-doped R-I trimer and the three most stable At-doped quartets are more stable than their hydrogenated counterparts. Significant deviations from linearity are found for some of the halogen bonds (with halogen bond angles around 150°).

scholarly journals Halogen bonds of halonium ions

2020 ◽  
Vol 49 (9) ◽  
pp. 2688-2700 ◽  
Author(s):  
Lotta Turunen ◽  
Máté Erdélyi
Keyword(s):  
Organic Chemistry ◽  
Halogen Bond ◽  
Halogen Bonds ◽  
Synthetic Organic Chemistry

Halonium ions are particularly strong halogen bond donors, and are accordingly valuable tools for a variety of fields, such as supramolecular and synthetic organic chemistry.

scholarly journals A systematic structural study of halogen bondingversushydrogen bonding within competitive supramolecular systems

IUCrJ ◽  
2015 ◽  
Vol 2 (5) ◽  
pp. 498-510 ◽  
Author(s):  
Christer B. Aakeröy ◽  
Christine L. Spartz ◽  
Sean Dembowski ◽  
Savannah Dwyre ◽  
John Desper
Keyword(s):  
Molecular Electrostatic Potential ◽  
Halogen Bond ◽  
Supramolecular System ◽  
Materials Chemistry ◽  
Halogen Bonds ◽  
X Ray Diffraction ◽  
Supramolecular Systems ◽  
X Ray ◽  
Practical Guidelines ◽  
Primary Interaction

As halogen bonds gain prevalence in supramolecular synthesis and materials chemistry, it has become necessary to examine more closely how such interactions compete with or complement hydrogen bonds whenever both are present within the same system. As hydrogen and halogen bonds have several fundamental features in common, it is often difficult to predict which will be the primary interaction in a supramolecular system, especially as they have comparable strength and geometric requirements. To address this challenge, a series of molecules containing both hydrogen- and halogen-bond donors were co-crystallized with various monotopic, ditopic symmetric and ditopic asymmetric acceptor molecules. The outcome of each reaction was examined using IR spectroscopy and, whenever possible, single-crystal X-ray diffraction. 24 crystal structures were obtained and subsequently analyzed, and the synthon preferences of the competing hydrogen- and halogen-bond donors were rationalized against a background of calculated molecular electrostatic potential values. It has been shown that readily accessible electrostatic potentials can offer useful practical guidelines for predicting the most likely primary synthons in these co-crystals as long as the potential differences are weighted appropriately.

Using one halogen bond to change the nature of a second bond in ternary complexes with P⋯Cl and F⋯Cl halogen bonds

2017 ◽  
Vol 203 ◽  
pp. 29-45 ◽  
Author(s):  
Janet E. Del Bene ◽  
Ibon Alkorta ◽  
José Elguero
Keyword(s):  
Halogen Bond ◽  
Synergistic Effects ◽  
Ternary Complexes ◽  
Binding Energies ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Halogen Bonds ◽  
Binary Complexes ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling

Ab initio MP2/aug’-cc-pVTZ calculations have been carried out to determine the effect of the presence of one halogen bond on the nature of the other in ternary complexes H2XP:ClF:ClH and H2XP:ClF:ClF, for X = F, Cl, H, NC, and CN. The P⋯Cl bonds remain chlorine-shared halogen bonds in the ternary complexes H2XP:ClF:ClH, although the degree of chlorine sharing increases relative to the corresponding binary complexes. The F⋯Cl bonds in the ternary complexes remain traditional halogen bonds. The binding energies of the complexes H2XP:ClF:ClH increase relative to the corresponding binary complexes, and nonadditivities of binding energies are synergistic. In contrast, the presence of two halogen bonds in the ternary complexes H2XP:ClF:ClF has a dramatic effect on the nature of these bonds in the four most strongly bound complexes. In these, chlorine transfer occurs across the P⋯Cl halogen bond to produce complexes represented as (H2XP–Cl)+:−(F:ClF). In the ion-pair, the cation is also halogen bonded to the anion by a Cl⋯F− halogen bond, while the anion is stabilized by an −F⋯Cl halogen bond. The central ClF molecule no longer exists as a molecule. The binding energies of the ternary H2XP:ClF:ClF complexes are significantly greater than the binding energies of the H2XP:ClF:ClH complexes, and nonadditivities exhibit large synergistic effects. The Wiberg bond indexes for the complexes H2XP:ClF, H2XP:ClF:ClH, and H2XP:ClF:ClF, and the cations (H2XP–Cl)+ reflect the changes in the P–Cl and Cl–F bonds. Similarly, EOM-CCSD spin–spin coupling constants are also consistent with the changes in these same bonds. In particular, 1xJ(P–Cl) in H2XP:ClF complexes becomes 1J(P–Cl) in the ternary complexes with chlorine-transferred halogen bonds. A plot of these coupling constants shows a change in the curvature of the trendline as chlorine-shared halogen bonds in H2XP:ClF:ClH become chlorine-transferred halogen bonds in H2XP:ClF:ClF. 1xJ(F–Cl) coupling constants also reflect changes in the nature of F⋯Cl halogen bonds.

Ligand-driven formation of halogen bonds involving Au(i) complexes

2018 ◽  
Vol 42 (13) ◽  
pp. 10529-10538 ◽  
Author(s):  
Ferdinand Groenewald ◽  
Jan Dillen ◽  
Catharine Esterhuysen
Keyword(s):  
Theoretical Investigation ◽  
Halogen Bond ◽  
Halogen Bonds

A theoretical investigation shows that the Au(i) centre in a variety of complexes can behave as a halogen bond acceptor.

scholarly journals Noncovalent Interactions between 1,3,5-Trifluoro-2,4,6-triiodobenzene and a Series of 1,10-Phenanthroline Derivatives: A Combined Theoretical and Experimental Study

Crystals ◽  
2019 ◽  
Vol 9 (3) ◽  
pp. 140 ◽  
Author(s):  
Yu Zhang ◽  
Jian-Ge Wang ◽  
Weizhou Wang
Keyword(s):  
Crystal Structure ◽  
Crystal Structures ◽  
Quantum Chemical ◽  
Halogen Bond ◽  
Noncovalent Interactions ◽  
Stacking Interactions ◽  
Halogen Bonds ◽  
Π Stacking ◽  
Π Stacking Interaction ◽  
Structural Competition

How many strong C−I⋯N halogen bonds can one 1,3,5-trifluoro-2,4,6-triiodobenzene molecule form in a crystal structure? To answer this question, we investigated in detail the noncovalent interactions between 1,3,5-trifluoro-2,4,6-triiodobenzene and a series of 1,10-phenanthroline derivatives by employing a combined theoretical and experimental method. The results of the quantum chemical calculations and crystallographic experiments clearly show that there is a structural competition between a C−I⋯N halogen bond and π⋯π stacking interaction. For example, when there are much stronger π⋯π stacking interactions between two 1,10-phenanthroline derivative molecules or between two 1,3,5-trifluoro-2,4,6-triiodobenzene molecules in the crystal structures, then one 1,3,5-trifluoro-2,4,6-triiodobenzene molecule forms only one C−I⋯N halogen bond with one 1,10-phenanthroline derivative molecule. Another example is when π⋯π stacking interactions in the crystal structures are not much stronger, one 1,3,5-trifluoro-2,4,6-triiodobenzene molecule can form two C−I⋯N halogen bonds with two 1,10-phenanthroline derivative molecules.

scholarly journals Strength, character, and directionality of halogen bonds involving cationic halogen bond donors

2017 ◽  
Vol 203 ◽  
pp. 47-60 ◽  
Author(s):  
Kevin E. Riley ◽  
Khanh-An Tran
Keyword(s):  
Potential Energy ◽  
Halogen Bond ◽  
Model System ◽  
Potential Energy Curves ◽  
Chloride Salt ◽  
Halogen Bonds ◽  
Charged Species ◽  
Implicit Solvation Model ◽  
The Stability

Halogen bonds involving cationic halogen bond donors and anionic halogen bond acceptors have recently been recognized as being important in stabilizing the crystal structures of many salts. Theoretical characterization of these types of interactions, most importantly in terms of their directionality, has been limited. Here we generate high-quality symmetry adapted perturbation theory potential energy curves of a H3N–CC–Br+⋯Cl− model system in order to characterize halogen bonds involving charged species, in terms of contributions from electrostatics, exchange, induction, and dispersion, with special emphasis on analyzing contributions that are most responsible for the directionality of these interactions. It is found that, as in the case of neutral halogen bonds, exchange forces are important contributors to the directionality of charged halogen bonds, however, it is also found that induction effects, which contribute little to the stability and directionality of neutral halogen bonds, play a large role in the directionality of halogen bonds involving charged species. Potential energy curves based on the ωB97X-D/def2-TZVP/C-PCM method, which includes an implicit solvation model in order to mimic the effects of the crystal medium, are produced for both the H3N–CC–Br+⋯Cl− model system and for the 4-bromoanilinium⋯Cl− dimer, which is based on the real 4-bromoanilinium chloride salt, whose crystal structure has been determined experimentally. It is found that, within a crystal-like medium, charged halogen bond are significantly weaker than in the gas phase, having optimum interaction energies up to approximately −20 kcal mol−1.

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