The relationship between the crystal habit and the energy framework pattern: a case study involving halogen bonding on the edge of a covalent bond

Torubaev, Yu. V.; Howe, Devin; Leitus, Gregory; Rosokha, Sergiy V.

doi:10.1039/d3ce00316g

Cited by 4 publications

(10 citation statements)

References 82 publications

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“…This leads to the substantial charge transfer and ground-state stabilization of the complexes with halides. It also indicates a partially covalent character of the anion−π interaction in complexes with halides (similar to the suggested earlier covalency in the anion−π complexes of Cl – with tetracyanobenzene or flavine, as well as in the halogen-bonded and chalcogen-bonded complexes. )…”

Section: Resultssupporting

confidence: 85%

Exploring the Nature of Anion−π Interactions: Complexes of π-Acceptors with Fluoro- or Oxoanions Compared to the Associations with Halides

Odubo,

Zeller,

Rosokha

2023

J. Phys. Chem. A

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The variations in the nature and properties of the anion−π complexes with different types of anions are identified via experimental (UV–vis and X-ray crystallographic) measurements and computational analysis of the associations of tetracyanopyrazine, tetrafluoro-, or dichlorodicyano-p-benzoquinone. Co-crystals of these π-acceptors with the salts of fluoro- and oxoanions (PF6 –, BF4 –, CF3SO3 –, or ClO4 –) comprised anion−π bonded alternating chains or 1:2 complexes showing interatomic contacts of up to 15% shorter than the van der Waals separations. DFT computations confirmed that binding energies between the neutral π-acceptors and polyatomic noncoordinating oxo- and fluoroanions are comparable to those in the previously reported anion−π complexes with more nucleophilic halides. Yet, while the latter show distinct charge-transfer bands in the UV–vis range, the absorption spectra of the solutions containing oxo- and fluoroanions and the π-acceptors were close to those of the individual reactants. The natural bond orbital (NBO) analysis revealed a very small charge transfer of Δq = 0.01–0.02 e in the complexes with oxo- or fluoroanions as compared to the Δq = 0.05–0.22 e found for analogous complexes with halides. These distinctions were related to the smaller frontier orbital energy gap and better overlap in the complexes with halides (since the highest occupied orbitals of these monoatomic anions are closer in energy to the lowest unoccupied orbitals of the π-acceptors) as compared to that in the multicenter-bonded associations with polyatomic oxo- and fluoroanions. In accordance with these data, the energy decomposition analysis showed that while the complexes of neutral π-acceptors with the fluoro- and oxoanions are formed predominantly via electrostatic interaction, the associations with halides comprised significant orbital (charge-transfer) interactions and they explain their spectral and structural features.

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Section: Resultssupporting

confidence: 85%

Exploring the Nature of Anion−π Interactions: Complexes of π-Acceptors with Fluoro- or Oxoanions Compared to the Associations with Halides

Odubo,

Zeller,

Rosokha

2023

J. Phys. Chem. A

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“…32−38 Computational analysis also demonstrated that many characteristics of the bonding in complexes of DABCO with IX are close to those in the trihalide anions. 35 Similar short N−I distances were also observed in the complexes of some nucleophiles with Niodosaccharin and N-iodosuccinimide. 39−41 As such, several previous publications suggested that the interaction in the strong HaB complexes (e.g., chlorine with phosphines) can also be described as 3c−4e bonding.…”

Section: Introductionsupporting

confidence: 54%

“…Their I···N bond lengths decrease in the order I 2 > IBr > ICl, which corresponds to the increases of the maximum electrostatic potential on the surface of iodine in the IX molecules . The N···I interaction energies in these solid-state associations (which were calculated using CrystalExplorer) increase in the same order.…”

Section: Resultsmentioning

confidence: 95%

“…Their I•••N bond lengths decrease in the order I 2 > IBr > ICl, which corresponds to the increases of the maximum electrostatic potential on the surface of iodine in the IX molecules. 35 The N•••I interaction energies in these solid-state associations (which were calculated using CrystalExplorer 65 ) increase in the same order. It is also noticeable that strong halogen I•••N bonding led to about a 10% increase of the I−X bond length as 35 N-Iodo-substituted saccharine and succinimide molecules represent another type of very strong HaB donor.…”

Section: X-ray Structural Characterization Of the Solid-state Associa...mentioning

confidence: 94%

“…, 1,4-diazabicyclo[2.2.2]-octane (DABCO) are characterized by the very short I···N bonds of about 2.25–2.30 Å, which are close to that in the cationic or anionic associations comprising N–I + –N fragments [ e.g. , bis(1,4-diazabicyclo[2.2.2]octane)iodine(I), or 1,1′-iodanylbis(pyrrolidine-2,5-dione)]. − Computational analysis also demonstrated that many characteristics of the bonding in complexes of DABCO with IX are close to those in the trihalide anions . Similar short N–I distances were also observed in the complexes of some nucleophiles with N -iodosaccharin and N -iodosuccinimide. − As such, several previous publications suggested that the interaction in the strong HaB complexes ( e.g.…”

Section: Introductionmentioning

confidence: 99%

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Halogen Bonding and/or Covalent Bond: Analogy of 3c–4e N···I···X (X = Cl, Br, I, and N) Interactions in Neutral, Cationic, and Anionic Complexes

Adeniyi,

Odubo,

Zeller

et al. 2023

Inorg. Chem.

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X-ray structural measurements and computational analysis demonstrated the similarity of the geometries and electronic structures of the X−I•••N (X = Cl, Br, I, and N) bonding in strong halogen-bonded (HaB) complexes and in the anionic or cationic halonium ions. In particular, I•••N bond lengths in the solid-state associations formed by strong HaB donors (e.g., I 2 , IBr, ICl, and N-iodosuccinimide) and acceptors (e.g., quinuclidine or pyridines) were in the same range of 2.3 ± 0.1 Å as those in the halonium ions [e.g., the bis(quinuclidine)iodonium cation or the 1,1′-iodanylbis(pyrrolidine-2,5-dione) anion]. In all cases, bond lengths were much closer to those of the N−I covalent bond than to the van der Waals separations of these atoms. The strong N•••I bonding in the HaB complexes led to a substantial charge transfer, lengthening and weakening of the I•••X bonds, and polarization of the HaB donors. As a result, the central iodine atoms in the strong HaB complexes bear partial positive charges akin to those in the halonium ions. The energies and Mayer bond orders for both N•••I and I•••X bonds in such associations are also comparable to those in the halonium ions. The similarity of the bonding in such complexes and in halonium ions was further supported by the analysis of electron densities and energies at bond critical (3, −1) points in the framework of the quantum theory of atoms in molecules and by the density overlap region indicator. Overall, all these data point out the analogy of the symmetric N•••I•••N bonding in the halonium ions and the asymmetric X•••I•••N bonding in the strong HaB complexes, as well as the weakly covalent character of these 3c−4e interactions.

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Analysis of short contacts in crystals of halogenated amino acids: atom–atom interactions vs. energy frameworks

De Beer,

Jacobs,

Ntsila

et al. 2024

CrystEngComm

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The relationship between the crystal habit and the energy framework pattern: a case study involving halogen bonding on the edge of a covalent bond

Abstract: The relationship between solid-state supramolecular interactions and crystal habits is highlighted based on experimental and computational analysis of the crystal structure of strong halogen bonded (HaB) associates between iodine-containing dihalogens...

Cited by 4 publications

References 82 publications

Exploring the Nature of Anion−π Interactions: Complexes of π-Acceptors with Fluoro- or Oxoanions Compared to the Associations with Halides

Exploring the Nature of Anion−π Interactions: Complexes of π-Acceptors with Fluoro- or Oxoanions Compared to the Associations with Halides

Halogen Bonding and/or Covalent Bond: Analogy of 3c–4e N···I···X (X = Cl, Br, I, and N) Interactions in Neutral, Cationic, and Anionic Complexes

Analysis of short contacts in crystals of halogenated amino acids: atom–atom interactions vs. energy frameworks

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