Halogen‐Bonding Interactions with π Systems: CCSD(T), MP2, and DFT Calculations

Forni, Alessandra; Pieraccini, Stefano; Rendine, Stefano; Gabas, F.

doi:10.1002/cphc.201200605

Cited by 55 publications

(72 citation statements)

References 90 publications

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“…R-X···π interactions are generally slightly weaker than their R-X···Y counterparts, with binding energies whose magnitudes are typically 10-25% lower [20,25,29]. The SAPT characteristics of R-X···π interactions are similar to those of R-X···Y interactions, however, the former tend to have larger relative contributions from dispersion, which is to be expected given the large size and polarizabilities of both halogens and phenyl groups [25,29].…”

Section: Introductionmentioning

confidence: 90%

“…Traditionally, electronegative Lewis bases have been considered the primary halogen bond accepting group, as is true in hydrogen bonding [12][13][14][15][16]. More recently, π-bonding and aromatic moieties have been shown to be effective halogen bond acceptors, leading to a subclass of interactions, sometimes called R-X···π (or C-X···π) interactions [19][20][21][22][23][24][25].…”

Section: Introductionmentioning

confidence: 99%

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Strength and Character of R–X···π Interactions Involving Aromatic Amino Acid Sidechains in Protein-Ligand Complexes Derived from Crystal Structures in the Protein Data Bank

Riley

Tran

2017

Crystals

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Abstract:Here, we investigate the strengths of R-X···π interactions, involving both chlorine and bromine, in model systems derived from protein-ligand complexes found in the PDB. We find that the strengths of these interactions can vary significantly, with binding energies ranging from −2.01 to −3.60 kcal/mol. Symmetry adapted perturbation theory (SAPT) analysis shows that, as would be expected, dispersion plays the largest role in stabilizing these R-X···π interactions, generally accounting for about 50% to 80% of attraction. R-Br···π interactions are, for the most part, found to be stronger than R-Cl···π interactions, although the relative geometries of the interacting pair and the halogen's chemical environment can also have a strong impact. The two factors that have the strongest impact on the strength of these R-X···π interactions is the distance between the halogen and the phenyl plane as well as the size of the halogen σ-hole.

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Section: Introductionmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

Strength and Character of R–X···π Interactions Involving Aromatic Amino Acid Sidechains in Protein-Ligand Complexes Derived from Crystal Structures in the Protein Data Bank

Riley

Tran

2017

Crystals

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“…For the Sonogashira-Hagihara cross-coupling reaction, see: Sonogashira et al (1975). For IÁ Á Á contacts, see: Forni et al (2012). For C-HÁ Á Á interactions, see: Nishio et al (2009 Table 1 Hydrogen-bond geometry (Å , ).…”

Section: Related Literaturementioning

confidence: 99%

“…Instead, the presence of a weak C-H···π-interaction [H17···Cg(C1, C10) 2.87 Å] is assumed (Nishio et al 2009). In the crystal of the title compound, the packing is furthermore consolidated by a remarkable I···π-interaction (Forni et al 2012) [I1···Cg(C11, C12) 3.34 Å, 173.3°].…”

Section: S1 Commentmentioning

confidence: 99%

Crystal structure of 1-iodo-3-{[4-(tert-butylsulfanyl)phenyl]ethynyl}azulene

2015

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The title compound, C20H19IS, features a 1,3-disubstituted azulene involving an ethynylene elongated 4-(tert-butylsulfanyl)phenyl sidearm and an iodine atom as the substituents. The azulene ring system is almost planar (r.m.s. deviation = 0.012 Å) and subtends a dihedral angle of 35.7 (1)° with the benzene ring. As a result of the inherent dipole character of the azulene core, a supramolecular π–π dimer [separation between the centroids of the five- and seven-membered rings = 3.7632 (10) Å] with antiparallel orientated molecules can be observed in the crystal. The packing is consolidated by an unusual I⋯π(acetylene) contact [I⋯Cg = 3.34 Å, C—I⋯Cg = 173.3°], and a very weak C—H⋯π interaction is also found in the structure, with the azulene five-membered ring as the acceptor.

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“…Most notably, it has been recognized that aromatic species can serve as halogen bond acceptors, with the resulting interaction often referred to as R-X…π interactions (analogous to R-H…π interactions). 22, 24, 25 …”

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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Halogen‐Bonding Interactions with π Systems: CCSD(T), MP2, and DFT Calculations

Cited by 55 publications

References 90 publications

Strength and Character of R–X···π Interactions Involving Aromatic Amino Acid Sidechains in Protein-Ligand Complexes Derived from Crystal Structures in the Protein Data Bank

Strength and Character of R–X···π Interactions Involving Aromatic Amino Acid Sidechains in Protein-Ligand Complexes Derived from Crystal Structures in the Protein Data Bank

Crystal structure of 1-iodo-3-{[4-(tert-butylsulfanyl)phenyl]ethynyl}azulene

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

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