The Effects of Electronegativity of X and Hybridization of C on the X−C⋅⋅⋅O Interactions: A Statistical Analysis on Tetrel Bonding

Abstract

Cone and distance‐cone corrected statistical analyses have been performed on X−C⋅⋅⋅O (X=H, B, C, N, O and F; the C atom is sp2 and sp3 hybridized) tetrel bonds. The sp3‐C and sp2‐C prefer to form the interactions through σ‐hole (∠XCO≈180°) and π‐hole (∠XCO≈90°), respectively. With the increase in electronegativity of X, the preference for the particular angles of the respective geometries increases and the C⋅⋅⋅O distance becomes shorter. The angular preference is found to be more prominent in the cases of π‐hole interactions than that in the σ‐hole interactions. A similar distance‐cone corrected statistical analysis on O=C⋅⋅⋅O interaction also suggests that the preferred ∠OCO angle is ∼90° and the preferred C⋅⋅⋅O distance is around the sum of van der Waals radii (3.22 Å) of the C and O atoms. However, a cone‐corrected statistical analysis on X−Si⋅⋅⋅O interactions suggests that the preference for linearity in this case is much higher than that for the X−C⋅⋅⋅O σ‐hole interactions.

Complementary, Cooperative Ditopic Halogen Bonding and Electron Donor-Acceptor π-π Complexation in the Formation of Cocrystals

“…The C∙∙∙O separations are 89 and 94% of the sum of the van der Waals radii. These results are in accord with the statistical analysis of tetrel interactions between O and sp 3 -C bonded to N where more linear O-C-N angles correlated to shorter C∙∙∙O separations [ 19 ].…”

Preferred Geometry and Nature of NO2···NO2 Interactions: A Statistical Survey and Theoretical Study

“…The population distribution for different ranges of φ angle has been further subjected to cone correction. Cone-corrected population has been calculated as n /sin φ, where n is the number of hits within the angle range φ ± 5°. ,,− When % population (cone-corrected) is plotted against θ and φ, the highest population is found in the interplanar angle range θ = 80–90° and φ = 0–5° (Figure b). This implies that the most favorable geometry for a NO 2 dimer with θ ≠ 0° is obtained when the two NO 2 planes are perpendicular to each other and the interacting O­(A) atom sits on the interacting N­(B) atom to involve in an n → π* interaction.…”

“…Moreover, as this analysis is performed on a large sample of experimentally determined crystal structures, it is a highly effective and reliable technique to understand the favorable geometry of a supramolecular interaction. Surprisingly, even though there are abundant statistical analyses on several other supramolecular interactions, such as hydrogen bonds, π···π interactions, halogen···halogen interactions, halogen bonds, chalcogen bonds, pnicogen bonds, tetrel bonds, etc., − a similar approach is glaringly missing in the case of NO 2 ···NO 2 interaction. Theoretical calculation of this interaction is also very limited. , …”

Crystal Structure Survey and Theoretical Analysis of Bifurcated Halogen Bonds

“…On the other hand, there is a statistical bias toward smaller angles since the cone encompassing a given angle grows larger as θ diminishes from 180°. This bias can be erased by a so-called cone correction invoking the sinθ function. − The corrected heat plot presented in Figure b shows that the preferred angle moves much closer to linearity, with the maximum proportion of hits between 170° and 175°.…”