Issue 8, 2021

Non-covalent interactions involving remote substituents influence the topologies of supramolecular chains featuring hydroxyl-O–H⋯O(hydroxyl) hydrogen bonding in crystals of (HOCH2CH2)2NC([double bond, length as m-dash]S)N(H)(C6H4Y-4) for Y = H, Me, Cl and NO2

Abstract

Crystallography shows the universal adoption of supramolecular chains featuring hydroxyl-O–H⋯O(hydroxyl) hydrogen bonding in crystals of (HOCH2CH2)2NC([double bond, length as m-dash]S)N(H)(C6H4Y-4) for Y = H (1), Me (2), Cl (3) and NO2 (4). However, distinct topologies, i.e. linear (Y = H), helical (Y = Me and Cl) and zig-zag (Y = NO2) are noted with major differences in the pitch of the polymer. Geometry-optimisation, MEP and NPA analyses show a distinct electronic structure for the Y = NO2 derivative, in particular relating to the activation of the aryl ring. An exhaustive analysis of the molecular packing (point-to-point interactions, crystal structure similarity, Hirshfeld surface analysis, NCI and QTAIM, interaction energies and energy frameworks) points to the importance of C–H⋯π(aryl) interactions in stabilising the chains but these have a considerably reduced influence in the crystal with Y = NO2 (4), where π(aryl)⋯π(aryl) interactions are important. The more open arrangement for the linear chain in 1 facilitates the formation of C–H⋯π(aryl) interactions and the more compact arrangements enable the formation of stabilising, intra-chain methylene-C–H⋯S(thione) interactions 2–4. This study highlights the role of second-tier non-covalent interactions in the arrangement of conventional hydrogen bonding interactions.

Graphical abstract: Non-covalent interactions involving remote substituents influence the topologies of supramolecular chains featuring hydroxyl-O–H⋯O(hydroxyl) hydrogen bonding in crystals of (HOCH2CH2)2NC( [[double bond, length as m-dash]] S)N(H)(C6H4Y-4) for Y = H, Me, Cl and NO2

Supplementary files

Article information

Article type
Paper
Submitted
15 12月 2020
Accepted
18 1月 2021
First published
19 1月 2021

CrystEngComm, 2021,23, 1723-1743

Non-covalent interactions involving remote substituents influence the topologies of supramolecular chains featuring hydroxyl-O–H⋯O(hydroxyl) hydrogen bonding in crystals of (HOCH2CH2)2NC([double bond, length as m-dash]S)N(H)(C6H4Y-4) for Y = H, Me, Cl and NO2

S. L. Tan and E. R. T. Tiekink, CrystEngComm, 2021, 23, 1723 DOI: 10.1039/D0CE01810D

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements