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.

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., I2, 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.

From weak to strong interactions: structural and electron topology analysis of the continuum from the supramolecular chalcogen bonding to covalent bonds.

The relationship between covalent and supramolecular bonding, and the criteria of the assignments of different interactions were explored via the review of selenium and tellurium containing structures in the Cambridge Structural Database and their computational analysis using Quantum Theory of Atoms in Molecules (QTAIM). This combined study revealed continuums of the interatomic Se⋯Br and Te⋯I distances, dCh⋯X, in the series of associations from the sums of the van der Waals radii of these atoms (rCh + rX) to their covalent bond lengths. The electron densities, ρ(r), at Bond Critical Points (BCPs) along the chalcogen bond paths increased gradually from about 0.01 a.u. common for the non-covalent interactions to about 0.1 a.u. typical for the covalent bonds. The log ρ(r) values fell on the same linear trend line when plotted against normalized interatomic distances, RXY = dCh⋯X/(rCh + rX). The transition from the positive to negative values of the energy densities, H(r), at the BCPs (related to a changeover of essentially non-covalent into partially covalent interactions) were observed at RXY ≈ 0.80. Synchronous changes of bonding characteristics with RXY (similar to that found earlier in the halogen-bonded systems) designated normalized interatomic separation as a critical factor determining the nature of these bondings. The uninterrupted continuums of Te⋯I and Se⋯Br bond lengths and BCPs' characteristics signified an intrinsic link between limiting types of bonding involving chalcogen atoms and between covalent and supramolecular bonding in general.

Crystals at a Carrefour on the Way through the Phase Space: A Middle Path.

Multiple supramolecular functionalities of cyclic α-alkoxy tellurium-trihalides (including Te---O, Te---X (X = Br, I) and Te---π(C=C) supramolecular synthons) afford rich crystal packing possibilities, which consequently results in polymorphism or Z' > 1 crystal structures. Example of three crystal forms of cyclohexyl-ethoxy-tellurium-trihalides, one of which combines the packing of two others, affords a unique model to observe the supramolecular synthon evolution at the early stages of crystallization, when crystals on the way find themself at a carrefour between the evolutionally close routes, but fail to choose between two energetically close packing patterns, so taking the "middle path", which incorporates both of them (and results in two crystallographically independent molecules). In general, this allows a better understanding of the existing structures, and an instrument to search for the new polymorphic forms.

Chimeric supramolecular synthons in Ph2Te2(I2)Se.

Iodination of Ph2Te2Se by molecular iodine is directed towards the Te atom and yields {diiodo[(phenyltellanyl)selanyl]-λ4-tellanyl}benzene, PhTeSeTeI2Ph or C12H10I2SeTe2. The molecule can be considered as a chimera of PhTeSeR, PhTeSeTePh and R'TeI2Ph fragments. The crystal structure features a complex interplay of the supramolecular synthons Te...π(Ph), Se...Te and I...Te, combining molecules into a three-dimensional framework. Their combination affords long-range supramolecular synthons which are fused in a way resembling the mythological chimera and could be defined as chimeric supramolecular synthons. The energies of the intermolecular interactions have also been calculated and analyzed.

Interplay of noncovalent interactions in antiseptic quaternary ammonium surfactant Miramistin.

The molecular and crystal structure of the widely used antiseptic benzyldimethyl{3-[(1-oxotetradecyl)amino]propyl}ammonium chloride monohydrate (Miramistin, MR), C26H47N2O+·Cl-·H2O, was determined by a single-crystal X-ray diffraction study and analyzed in the framework of the QTAIM (quantum theory of atoms in molecules) approach using both periodic and molecular DFT (density functional theory) calculations. The various noncovalent intermolecular interactions of different strengths were found to be realized in the hydrophilic parts of the crystal packing (i.e. O-H...Cl, N-H...Cl, C-H...Cl, C-H...O and C-H...π). The hydrophobic parts are built up exclusively by van der Waals H...H contacts. Quantification of the interaction energies using calculated electron-density distribution revealed that the total energy of the contacts within the hydrophilic and hydrophobic regions are comparable in value. The organic MR cation adopts the bent conformation with the head group tilted back to the long-chain alkyl tail in both the crystalline and the isolated state due to stabilization of this geometry by several intramolecular C-H...π, C-H...N and H...H interactions. This conformation preference is hypothesized to play an important role in the interaction of MR with biomembranes.