Issue 29, 2023

High-pressure induced switching between halogen and hydrogen bonding regimes in 1,4-dioxane iodine monochloride

Abstract

The structure of the complex formed between 1,4-dioxane and iodine monochloride has been studied as a function of pressure using neutron powder diffraction. Initial compression was accompanied by a decrease in the O⋯I halogen bond length together with an increase in the intramolecular I–Cl bond length. Two phase transitions were observed at ∼2.8 and ∼4.5 GPa. The transient intermediate phase coexists with the ambient pressure phase during the initial phase transition and with the final high-pressure phase at the second phase transition, before its disappearance. The driving force for the first phase transition is a shearing motion of the complex causing a reduction in the dipolar interaction of two I–Cl moieties. The formation of the highest pressure phase is accompanied by a net reduction of 2 C–H⋯Cl hydrogen bonds per formula unit. From these changes we conclude that Cl⋯Cl halogen bonds are favoured over C–H⋯Cl hydrogen bonds at high pressures.

Graphical abstract: High-pressure induced switching between halogen and hydrogen bonding regimes in 1,4-dioxane iodine monochloride

Supplementary files

Article information

Article type
Paper
Submitted
13 Apr 2023
Accepted
21 Jun 2023
First published
03 Jul 2023
This article is Open Access
Creative Commons BY license

CrystEngComm, 2023,25, 4146-4156

High-pressure induced switching between halogen and hydrogen bonding regimes in 1,4-dioxane iodine monochloride

R. H. Jones, C. L. Bull, K. S. Knight and W. G. Marshall, CrystEngComm, 2023, 25, 4146 DOI: 10.1039/D3CE00362K

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