Issue 1, 2021

Experimental and computational evidence for a stabilising C–Cl(lone-pair)⋯π(chelate-ring) interaction

Abstract

In addition to a variety of conventional non-covalent intermolecular interactions such as C–H⋯π (arene), C–H⋯Cl and π(arene)⋯π(chelate-ring) contacts, the molecular packing in the crystal of an organotin dithiocarbamate compound, [SnCl(4-ClC6H4)2{S2CN(i-Pr)2}], exhibits evidence for a C–Cl⋯π(chelate-ring) interaction. These interactions occur via a side-on approach of the chloride atom to the chelate-ring and therefore are characterised as C–Cl(lone-pair)⋯π(chelate-ring) interactions, are shown to be attractive by NCI plots and QTAIM analysis, and are apparent in the calculated Hirshfeld surfaces. Theory suggests the energy of association provided by the C–Cl⋯π(chelate-ring) interactions to be about 3–4 kcal mol−1, a value greater than for analogous C–Cl⋯π(arene) and C–H⋯π(arene) interactions. A survey of the literature for related structures suggests that these interactions are not common. The newly described C–Cl(lone-pair)⋯π(chelate-ring) interactions add to the variety of intermolecular interactions able to be formed by chelate-rings in the supramolecular chemistry of metal complexes.

Graphical abstract: Experimental and computational evidence for a stabilising C–Cl(lone-pair)⋯π(chelate-ring) interaction

Supplementary files

Article information

Article type
Paper
Submitted
08 okt 2020
Accepted
02 noy 2020
First published
02 noy 2020

CrystEngComm, 2021,23, 119-130

Experimental and computational evidence for a stabilising C–Cl(lone-pair)⋯π(chelate-ring) interaction

S. L. Tan, S. M. Lee, K. M. Lo, A. Otero-de-la-Roza and E. R. T. Tiekink, CrystEngComm, 2021, 23, 119 DOI: 10.1039/D0CE01478H

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