Exploring short strong hydrogen bonds engineered in organic acid molecular crystals for temperature dependent proton migration behaviour using single crystal synchrotron X-ray diffraction (SCSXRD)

Saunders, Lucy K., Nowell, Harriott, Hatcher, Lauren E. ORCID: https://orcid.org/0000-0002-1549-9727, Shepherd, Helena J., Teat, Simon J., Allan, David R., Raithby, Paul R. and Wilson, Chick C. 2019. Exploring short strong hydrogen bonds engineered in organic acid molecular crystals for temperature dependent proton migration behaviour using single crystal synchrotron X-ray diffraction (SCSXRD). CrystEngComm 21 (35) 10.1039/C9CE00925F

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Abstract

Seven multi-component molecular crystals containing O–H⋯O/O+–H⋯O− and N+–H⋯O− short strong hydrogen bonds (SSHBs) have been engineered by combining substituted organic acids with hydrogen bond acceptor molecules N,N-dimethylurea and isonicotinamide. In these materials, the shortest of the SSHBs are formed in the N,N-dimethylurea set for the ortho/para nitro-substituted organic acids whilst a twisted molecular approach favours the shorter SSHBs N+–H⋯O− in the isonicotinamide set. Temperature dependent proton migration behaviour has been explored in these systems using single crystal synchrotron X-ray diffraction (SCSXRD). By using a protocol which considers a combination of structural information when assessing the hydrogen atom (H-atom) behaviour, including refined H-atom positions alongside heavy atom geometry and Fourier difference maps, temperature dependent proton migration is indicated in two complexes (2: N,N-dimethylurea 2,4-dinitrobenzoic acid 1 : 1 and 5: isonicotinamide phthalic acid 2 : 1). We also implement Hirshfeld atom refinement for further confidence in this observation; this highlights the importance of having corroborating trends when applying the SCSXRD technique in these studies. Further insights into the SSHB donor–acceptor distance limit for temperature dependent proton migration are also revealed. For the O–H⋯O/O+–H⋯O− SSHBs, the systems here support the previously proposed maximum limit of 2.45 Å whilst for the charge assisted N+–H⋯O− SSHBs, a limit in the region of 2.55 Å may be suggested.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	Royal Society of Chemistry
ISSN:	1466-8033
Date of First Compliant Deposit:	19 March 2020
Date of Acceptance:	29 July 2019
Last Modified:	17 Nov 2024 12:15
URI:	https://orca.cardiff.ac.uk/id/eprint/130515

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