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Title: 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)

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 limitmore » in the region of 2.55 Å may be suggested.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [2];  [2]
  1. Diamond Light Source, Harwell Science and Innovation Campus, Didcot OX11 0DE, UK
  2. Department of Chemistry, University of Bath, Bath, UK
  3. School of Physical Sciences, Ingram Building, University of Kent, Canterbury, UK
  4. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, USA
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); University of Bath (United Kingdom); Diamond Light Source Ltd (United Kingdom)
OSTI Identifier:
1556802
Alternate Identifier(s):
OSTI ID: 1580928
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Published Article
Journal Name:
CrystEngComm
Additional Journal Information:
Journal Name: CrystEngComm Journal Volume: 21 Journal Issue: 35; Journal ID: ISSN 1466-8033
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Saunders, Lucy K., Nowell, Harriott, Hatcher, Lauren E., Shepherd, Helena J., Teat, Simon J., Allan, David R., Raithby, Paul R., and Wilson, Chick C. 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). United Kingdom: N. p., 2019. Web. doi:10.1039/C9CE00925F.
Saunders, Lucy K., Nowell, Harriott, Hatcher, Lauren E., Shepherd, Helena J., Teat, Simon J., Allan, David R., Raithby, Paul R., & Wilson, Chick C. 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). United Kingdom. doi:10.1039/C9CE00925F.
Saunders, Lucy K., Nowell, Harriott, Hatcher, Lauren E., Shepherd, Helena J., Teat, Simon J., Allan, David R., Raithby, Paul R., and Wilson, Chick C. Mon . "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)". United Kingdom. doi:10.1039/C9CE00925F.
@article{osti_1556802,
title = {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)},
author = {Saunders, Lucy K. and Nowell, Harriott and Hatcher, Lauren E. and Shepherd, Helena J. and Teat, Simon J. and Allan, David R. and Raithby, Paul R. and Wilson, Chick C.},
abstractNote = {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.},
doi = {10.1039/C9CE00925F},
journal = {CrystEngComm},
number = 35,
volume = 21,
place = {United Kingdom},
year = {2019},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1039/C9CE00925F

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