Highly Interpenetrated Supramolecular Networks Supported by N⋅⋅⋅I Halogen Bonding

Abstract

Halogen bonding (XB) has been used to assemble tetrakis(4-pyridyl)pentaerythritol (tetradentate XB acceptor) with different alpha,omega-diiodoperfluoroalkanes (bidentate XB donors) or tetrakis(4-iodotetrafluorophenyl)pentaerythritol (tetradentate XB donor). The remarkable linearity of the XB formed, the rodlike character of alpha,omega-diiodoperfluoroalkanes and the mutual complementarities of pentaerythritol partners, translate the three-dimensional character of the XB acceptor into open primary networks, which interpenetrate to avoid the presence of voids and to ensure segregation of the modules. Two-dimensional (2D) square 4(4) layers (sql) with fourfold and fivefold interpenetration, as well as an eightfold diamondoid network (dia) of class Ia and a remarkable tenfold dia network of class IIIa, have been obtained.

Clusters of Ammonium Cation—Hydrogen Bond versus σ‐Hole Bond

“…[2,4,15] However, it seems that there are differences between the hydrogen bond and the other types of s-hole bonds, such as the halogen, [34] pnicogen, [35] chalcogen, [36] and tetrel bonds. [2,4,15] However, it seems that there are differences between the hydrogen bond and the other types of s-hole bonds, such as the halogen, [34] pnicogen, [35] chalcogen, [36] and tetrel bonds.…”

“…Notably, the hydrogen bond is considered to be classified as a type of s-hole bond. [2,4,15] However, it seems that there are differences between the hydrogen bond and the other types of s-hole bonds, such as the halogen, [34] pnicogen, [35] chalcogen, [36] and tetrel bonds. [17][18][19] In the case of the AÀH···B hydrogen bond, an enhancement in the positive electrostatic potential on the edge of the H atom is connected to a shift in the electron density from the H atom to the A center, whereas for the above-mentioned other s-hole bonds, the electronic charge on the Z atom (Z = group IV, V, VI, or VII atom) depends on the nature of the hybrid orbital of the Z atom that contributes to the covalent bond (NÀH bond in the case of the ammonia cation considered in this study).…”

σ‐Hole Bond Versus Hydrogen Bond: From Tetravalent to Pentavalent N, P, and As Atoms

“…[12][13][14] For example, there are various studies in which it is justified that the halogen bond is competitive to the hydrogen bond in the crystal structures. [4,[15][16][17][18] One can also mention such noncovalent interactions as for example, dihydrogen, [19] hydride, [20] chalcogen, [21] or pnicogen bonds. [22] The formation of the mentioned above interactions may be explained with the use of the s-hole concept.…”

2D parallel interpenetration of [M2(bpp)4X4] [M, Fe(II)/Co(II); bpp, 4,4′-trimethylenedipyridine; X, SCN−, SeCN− and N3−] complexes: Pseudohalide-dependent conformation of bpp

“…It is interesting to note that in this case the two interpenetrated nets are both crystallographically independent and each of them contains only one type of metal (M1 or M2), as in case of complex 1. According to the classification of interpenetration, these complexes are rare examples of non-equivalent interpenetrations and in case of 3D interpenetration only a limited number of this class has been found [43,45]. When the pseudohalide is N 3 À , bpp attains (TG, TG) conformation in case of Mn/Fe but (TT, GG 0 ) in Co showing choice of metal also influences the conformation.…”