The subtle balance of weak supramolecular interactions: The hierarchy of halogen and hydrogen bonds in haloanilinium and halopyridinium salts

Raatikainen, Kari; Cametti, Massimo; Rissanen, Kari

doi:10.3762/bjoc.6.4

Cited by 52 publications

(51 citation statements)

References 47 publications

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“…Several types of halogen bonds, such as the halogen bond of nitro-iodo-benzenes, halopyridiniums and haloamides and imides, have been reported. [49][50][51] The structures of complexes formed by halogen bonds in the gas phase have been studied by microwave spectroscopy. [30][31][32] Halogen bonds in crystals have been studied by X-ray diffraction and by statistical analysis of the crystal structure database.…”

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confidence: 99%

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C₆F₅X and C₆H₅X (X=I, Br, Cl and F) with Pyridine

Tsuzuki

Wakisaka

Ono

et al. 2011

Chemistry A European J

123

118

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The geometries and interaction energies of complexes of pyridine with C6F5X, C6H5X (X=I, Br, Cl, F and H) and RFI (RF=CF3, C2F5 and C3F7) have been studied by ab initio molecular orbital calculations. The CCSD(T) interaction energies (Eint) for the C6F5X–pyridine (X=I, Br, Cl, F and H) complexes at the basis set limit were estimated to be −5.59, −4.06, −2.78, −0.19 and −4.37 kcal mol−1, respectively, whereas the Eint values for the C6H5X–pyridine (X=I, Br, Cl and H) complexes were estimated to be −3.27, −2.17, −1.23 and −1.78 kcal mol−1, respectively. Electrostatic interactions are the cause of the halogen dependence of the interaction energies and the enhancement of the attraction by the fluorine atoms in C6F5X. The values of Eint estimated for the RFI–pyridine (RF=CF3, C2F5 and C3F7) complexes (−5.14, −5.38 and −5.44 kcal mol−1, respectively) are close to that for the C6F5I–pyridine complex. Electrostatic interactions are the major source of the attraction in the strong halogen bond although induction and dispersion interactions also contribute to the attraction. Short‐range (charge‐transfer) interactions do not contribute significantly to the attraction. The magnitude of the directionality of the halogen bond correlates with the magnitude of the attraction. Electrostatic interactions are mainly responsible for the directionality of the halogen bond. The directionality of halogen bonds involving iodine and bromine is high, whereas that of chlorine is low and that of fluorine is negligible. The directionality of the halogen bonds in the C6F5I– and C2F5I–pyridine complexes is higher than that in the hydrogen bonds in the water dimer and water–formaldehyde complex. The calculations suggest that the CI and CBr halogen bonds play an important role in controlling the structures of molecular assemblies, that the CCl bonds play a less important role and that CF bonds have a negligible impact.

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confidence: 99%

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C₆F₅X and C₆H₅X (X=I, Br, Cl and F) with Pyridine

Tsuzuki

Wakisaka

Ono

et al. 2011

Chemistry A European J

123

118

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“…These modes are very broad at room temperature suggesting appreciable motion of anilinium stretching vibrations, due to hydrogen bonding. The comparatively lower frequency of the R-NH þ 3 stretching band in the spectra of anilinium chloride over its saturated annilium analogue (cyclohexylammonium chloride at 2980 cm À1 ), suggest that the hydrogen bonding is stronger in anilinium chloride [22]. Surprisingly, these modes completely vanish as the temperature is increased to 350 K. That means there is one more phase transition between 300 and 350 K in this complex.…”

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confidence: 85%

Temperature‐dependent Raman spectroscopy of anilinium chloride near phase transition

Vishwakarma

Ghalsasi

2011

Physica Status Solidi (b)

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The existence of various solid phases of organic ammonium halides, due to the presence of hydrogen bonding, has long been established but is limited to alkyl ammonium halides. On the other hand, the presence of such phase transitions was eluded in case of anilinium chloride. In the present work, we have undertaken a systematic temperature dependent Raman spectroscopic study on anilinium chloride, in the range 300–100–350 K. Spectral variation in the low frequency (100–400 cm−1) and high frequency (2500–3700 cm−1) regions around 350 and 260 K shows the signature of the phase transitions in this compound. These phase transitions were reversible in nature. The latter transition is in agreement with DSC measurements.magnified image

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“…1–9 These noncovalent interactions have been observed in protein-ligand complexes, 9–13 crystal structures of neutral molecules, 14–16 and crystals composed of molecular ions. 17, 18 A halogen bond is an interaction of the type RX…YZ, where X is a halogen (chlorine, bromine, or iodine) that is part of the molecule, or molecular ion, RX, and YZ is a Lewis base. Most commonly Y is an atom, such as oxygen, nitrogen, or sulfur, that has a lone pair.…”

Section: Introductionmentioning

confidence: 99%

“…Halogen bonds have been used in the design of several new salts in which the halogen is contained within the molecular cation structure. 17, 18 As an example, Rissanen and coworkers, developed several crystal structures composed of haloanilinium and halopyridinium cations along with chloride, bromide, and dihidrogen phosphate anions. 17 Here our goal is to use computational techniques to characterize the properties of halogen bonds involving cationic halogen bond donors and the chloride anion, which serves as the simplest anion commonly found in these types of salts.…”

Section: Introductionmentioning

confidence: 99%

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

Riley

Tran

2017

Faraday Discuss.

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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.

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The subtle balance of weak supramolecular interactions: The hierarchy of halogen and hydrogen bonds in haloanilinium and halopyridinium salts

Cited by 52 publications

References 47 publications

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C₆F₅X and C₆H₅X (X=I, Br, Cl and F) with Pyridine

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C₆F₅X and C₆H₅X (X=I, Br, Cl and F) with Pyridine

Temperature‐dependent Raman spectroscopy of anilinium chloride near phase transition

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

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The subtle balance of weak supramolecular interactions: The hierarchy of halogen and hydrogen bonds in haloanilinium and halopyridinium salts

Cited by 52 publications

References 47 publications

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C6F5X and C6H5X (X=I, Br, Cl and F) with Pyridine

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C6F5X and C6H5X (X=I, Br, Cl and F) with Pyridine

Temperature‐dependent Raman spectroscopy of anilinium chloride near phase transition

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

Contact Info

Product

Resources

About

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C₆F₅X and C₆H₅X (X=I, Br, Cl and F) with Pyridine

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C₆F₅X and C₆H₅X (X=I, Br, Cl and F) with Pyridine