Sigma-hole interactions in the molecular and crystal structures of <i>N</i>-boryl benzo-2,1,3-selenadiazoles

Lee, Jiwon; Lee, Lucia Myongwon; Arnott, Z. L.; Jenkins, Hilary A.; Britten, James F.; Vargas‐Baca, Ignacio

doi:10.1039/c8nj00553b

Cited by 22 publications

(19 citation statements)

References 55 publications

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“…In each of 37 [82], 38 [83], shown in Fig. 7a, and 39 [82], the familiar four-membered {SeN … }2 synthon noted in the previous section (3.2) sustains the two-molecule aggregate, despite the presence of substituents on the non-participating nitrogen atoms; the molecule in 39 has mirror symmetry encompassing the fused-ring system. The molecules in 40 [84] and 41 [85] feature pyridyl-nitrogen atoms in the six-membered ring fused to the selenadiazole ring.…”

Section: Two-molecule Aggregates Featuring Two Se … N Interactions: Selenadiazole Ringsmentioning

confidence: 88%

“…In 39 [82], where the fused-ring system is located on a mirror plane, and 48 [91], the aggregate has 2-fold symmetry. In the crystal of 41 [85], two independent molecules comprise the asymmetric-unit and one of these self-associates about a centre of inversion to form the aggregate.…”

Section: Two-molecule Aggregates Featuring Two Se … N Interactions: Selenadiazole Ringsmentioning

confidence: 99%

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Supramolecular aggregation patterns featuring Se⋯N secondary-bonding interactions in mono-nuclear selenium compounds: A comparison with their congeners

Tiekink

2021

Coordination Chemistry Reviews

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An evaluation of the Cambridge Structural Database for crystals containing Se … N secondary--bonding interactions was conducted. The presence of Se … N secondary-bonding interactions has been established in nearly 9% of crystals of mono-nuclear selenium compounds where such interactions can potentially form, that is, having at least one nitrogen atom. The Se … N interactions feature in 71 zero-dimensional, usually di-nuclear aggregates, 63 one-dimensional chains and tapes, and smaller numbers of two-and three-dimensional arrays, that is seven and one, respectively. Selenium(II) compounds form the majority of the dataset with only eight selenium(IV) compounds included in the survey. In most cases (112 out of 142), the selenium centre forms a single Se … N contact with 26 aggregates having a selenium atom forming two contacts and four examples where three Se … N contacts are evident. The great propensity of selenadiazole rings (75%) and selenocyanates (50%) to form Se … N secondary-bonding interactions in their crystals is particularly noteworthy.

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Section: Two-molecule Aggregates Featuring Two Se … N Interactions: Selenadiazole Ringsmentioning

confidence: 88%

Section: Two-molecule Aggregates Featuring Two Se … N Interactions: Selenadiazole Ringsmentioning

confidence: 99%

Supramolecular aggregation patterns featuring Se⋯N secondary-bonding interactions in mono-nuclear selenium compounds: A comparison with their congeners

Tiekink

2021

Coordination Chemistry Reviews

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“…Dimeric benzoselenadiazoles, and benzotelluradiazoles have been well-studied. [7][8][9][10] It has been found that the strongest chalcogen-bonding interactions are at least as strong as the conventional H-bonds, but unlike H-bonds, they are surprisingly not solvent dependent. [11] Te forms the strongest chalcogen bonding interactions compared to the other chalcogens, which can reach up to 7 kcal/mol.…”

Section: Introductionmentioning

confidence: 99%

“…Typically, chalcogen bonding occurs between the electron deficient Group VI elements (S, Se, Te) and nucleophile sites i. e., electron donor species. Dimeric benzoselenadiazoles, and benzotelluradiazoles have been well‐studied . It has been found that the strongest chalcogen‐bonding interactions are at least as strong as the conventional H‐bonds, but unlike H‐bonds, they are surprisingly not solvent dependent .…”

Section: Introductionmentioning

confidence: 99%

Aromaticity and Chemical Bonding of Chalcogen‐Bonded Capsules Featuring Enhanced Magnetic Anisotropy

et al. 2020

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We present a theoretical study of chalcogen bonded container capsules (A X + A X) where X=O, S, Se, and Te, and their encapsulation complexes with n-C 9 H 20 (n-C 9 H 20 @A X + A X). Both Se and Te encapsulation complexes have significant experimental and computed binding energies, analogous to the hydrogen bonded counterparts, while the S and O capsules and their encapsulation complexes show only weak binding energies, which are attributed to different types of bonding: chalcogen S•••N bonds for S-capsules and π-π stacking and weak hydrogen bonds for the O case. All A X + A X and C 9 H 20 @A X + A X present unusually high magnetic anisotropies in their interiors. The 1 H NMR spectra of the encapsulation complexes display the proton signals of the encapsulated n-nonane highly upfield shifted, in agreement with the available experimental data for the Se capsule. We found that different factors contribute to the observed magnetic anisotropy of the capsule's interior: for the Te capsule the most important factor is Te's large polarizability; for the O analogue the inductive effects produced by the electronegative nature of the O and N heteroatoms; and for the S and Se capsules, the polarizability of the heteroatoms combines with electric field effects.

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“…The pnicogen bond is a case in point. It has been reasonably widely examined [34,[61][62][63][64][65][66][67][68][69][70][71][72][73][74], but little has been determined in terms of competing configurations of a given pair of molecules. For example, the complexes PH 2 R•••BrCl (R = H, F, OH, OCH 3 , CH 3 ) were studied at the MP2 level [74], focusing on two possible σ-hole arrangements: halogen-bonded vs pnicogen-bonded.…”

Section: Introductionmentioning

confidence: 99%

On the ability of pnicogen atoms to engage in both σ and π-hole complexes. Heterodimers of ZF2C6H5 (Z = P, As, Sb, Bi) and NH3

et al. 2019

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When bound to a pair of F atoms and a phenyl ring, a pyramidal pnicogen (Z) atom can form a pnicogen bond wherein an NH 3 base lies opposite one F atom. In addition to this σ-hole complex, the ZF 2 C 6 H 5 molecule can distort in such a way that the NH 3 approaches on the opposite side to the lone pair on Z, where there is a so-called π-hole. The interaction energies of these π-hole dimers are roughly 30 kcal/mol, much larger than the equivalent quantities for the σ-hole complexes, which are only 4-13 kcal/ mol. On the other hand, this large interaction energy is countered by the considerable deformation energy required for the Lewis acid to adopt the geometry necessary to form the π-hole complex. The overall energetics of the complexation reaction are thus more exothermic for the σ-hole dimers than for the π-hole dimers.

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Sigma-hole interactions in the molecular and crystal structures of N-boryl benzo-2,1,3-selenadiazoles

Abstract: Crystallography and DFT reveal competition between chalcogen bonding and other intermolecular interactions.

Cited by 22 publications

References 55 publications

Supramolecular aggregation patterns featuring Se⋯N secondary-bonding interactions in mono-nuclear selenium compounds: A comparison with their congeners

Supramolecular aggregation patterns featuring Se⋯N secondary-bonding interactions in mono-nuclear selenium compounds: A comparison with their congeners

Aromaticity and Chemical Bonding of Chalcogen‐Bonded Capsules Featuring Enhanced Magnetic Anisotropy

On the ability of pnicogen atoms to engage in both σ and π-hole complexes. Heterodimers of ZF2C6H5 (Z = P, As, Sb, Bi) and NH3

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