title: The C-Cl···π interactions inside supramolecular nanotubes of hexaethynylhexamethoxy[6]pericyclyne.
abstract: Model complexes of hexaethynylhexamethoxy[6]pericyclyne (HM6P) molecules, with or without dichloromethane (DCM) guests, have been calculated at the M05-2X/6-311G(d,p) DFT level. Analysis of nonbonding interactions shows that the cohesion of the supramolecular tubular assemblies previously observed in the crystal state, relies mainly on C-H···O hydrogen bonds between axial ethynyl and equatorial methoxy substituents of stacked HM6P C(18) macrocycles in a cyclohexane-like chair conformation. The intrinsic binding energy of one HM6P molecule with two neighbors is calculated to be more than 40 kcal mol(-1). The inner channel of the stacks (of ca. 8 Å diameter) are suitable for hosting DCM molecules. Using the Atoms In Molecules (AIM) theory, the interaction between DCM molecules and surrounding triple bonds is analyzed in terms of σ-hole-directed C-Cl···π halogen bonds. A σ-hole-directed Cl···Cl interaction between two chlorine atoms of different DCM molecules is also evidenced.
authors.affiliation: STC Institute for Single Crystals National Academy of Science of Ukraine, 60 Lenina ave., Kharkiv 61001, Ukraine. shishkin@xray.isc.kharkov.com
authors.forename: Oleg V
authors.initials: OV
authors.lastname: Shishkin
authors.forename: Roman I
authors.initials: RI
authors.lastname: Zubatyuk
authors.forename: Viktoriya V
authors.initials: VV
authors.lastname: Dyakonenko
authors.forename: Christine
authors.initials: C
authors.lastname: Lepetit
authors.forename: Remi
authors.initials: R
authors.lastname: Chauvin