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Neutron Diffraction Study of Significant sp3 and sp2 C–H Bond Shortening in a Fluorinated Pyridinium Saccharinate

  • Norman Lu*
    Norman Lu
    Institute of Organic and Polymeric Materials, National Taipei University of Technology, Taipei 106, Taiwan, ROC
    Development Center for Smart Textile, National Taipei University of Technology, Taipei 106, Taiwan, ROC
    *[email protected]
    More by Norman Lu
    Orcidhttp://orcid.org/0000-0002-3554-6113
  • , 
  • Vijayanath Elakkat
    Vijayanath Elakkat
    Institute of Organic and Polymeric Materials, National Taipei University of Technology, Taipei 106, Taiwan, ROC
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  • , 
  • Joseph S. Thrasher*
    Joseph S. Thrasher
    Department of Chemistry, Advanced Materials Research Laboratory, Clemson University, Anderson, South Carolina 29625, United States
    *[email protected]
    More by Joseph S. Thrasher
    Orcidhttp://orcid.org/0000-0003-1479-1897
  • , 
  • Xiaoping Wang*
    Xiaoping Wang
    Neutron Scattering Division, Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
    *[email protected]
    More by Xiaoping Wang
    Orcidhttp://orcid.org/0000-0001-7143-8112
  • , 
  • Eskedar Tessema
    Eskedar Tessema
    Institute of Organic and Polymeric Materials, National Taipei University of Technology, Taipei 106, Taiwan, ROC
    More by Eskedar Tessema
  • , 
  • Ka Long Chan
    Ka Long Chan
    Institute of Organic and Polymeric Materials, National Taipei University of Technology, Taipei 106, Taiwan, ROC
    More by Ka Long Chan
  • , 
  • Rong-Jun Wei
    Rong-Jun Wei
    Institute of Organic and Polymeric Materials, National Taipei University of Technology, Taipei 106, Taiwan, ROC
    More by Rong-Jun Wei
  • , 
  • Tarek Trabelsi
    Tarek Trabelsi
    Department of Earth and Environmental Science and Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6316, United States
    More by Tarek Trabelsi
    Orcidhttp://orcid.org/0000-0001-6258-7191
  • , and 
  • Joseph S. Francisco*
    Joseph S. Francisco
    Department of Earth and Environmental Science and Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6316, United States
    *[email protected]
    More by Joseph S. Francisco
    Orcidhttp://orcid.org/0000-0002-5461-1486
Cite this: J. Am. Chem. Soc. 2021, 143, 14, 5550–5557
Publication Date (Web):March 30, 2021
https://doi.org/10.1021/jacs.1c02570
Copyright © 2021 American Chemical Society
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    Abstract

    Abstract Image

    We have experimentally shown by neutron diffraction significant shortening of both sp3- and sp2-hybridized C–H bonds to 1.092(2) and 1.081(1) Å in a hydrogen-bonded crystal of a difluorinated compound, 4-((2,2-difluoroethoxy)methyl)pyridinium saccharinate. Both MP2 and DFT calculations affirmed the C–H bond shrinkages. Sanderson’s electronegativity equalization principle provides insight into the shortening of the C–H covalent bond lengths for both sp3- and sp2-hybridized carbon atoms. To the best of our knowledge, this neutron diffraction study has revealed the largest extents of sp3 and sp2 C–H bond shrinkages with a 3-sigma rule being satisfied.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.1c02570.

    • Synthesis, characterization data, and single-crystal X-ray/neutron methods, including Figures S1–S5, Tables S1–S13, and Schemes S1 and S2 (PDF)

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    CCDC 1953916, 2003417, and 2013378 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Cited By

    This article is cited by 8 publications.

    1. T.N. Lohith, M.K. Hema, C.S. Karthik, Sandeep S, Jothi Ramalingam Rajabathar, Muthusamy Karnan, N.K. Lokanath, L. Mallesha, P. Mallu, M.A. Sridhar. Probing the hydrogen bond network in the crystal structure of a sulfonamide derivative: A quantum chemical approach. Journal of Molecular Structure 2023, 1289 , 135841. https://doi.org/10.1016/j.molstruc.2023.135841
    2. Vijayanath Elakkat, Eskedar Tessema, Chia‐Her Lin, Xiaoping Wang, Huan‐Cheng Chang, You‐Ning Zheng, Yu‐Cheng Huang, Gurumallappa, Zhong‐Yun Zhang, Ka Long Chan, Hening A. Rahayu, Joseph S. Francisco, Norman Lu. Unusual Changes of C−H Bond Lengths in Chiral Zinc Complexes Induced by Noncovalent Interactions. Angewandte Chemie International Edition 2023, 62 (6) https://doi.org/10.1002/anie.202215438
    3. Vijayanath Elakkat, Eskedar Tessema, Chia‐Her Lin, Xiaoping Wang, Huan‐Cheng Chang, You‐Ning Zheng, Yu‐Cheng Huang, Gurumallappa, Zhong‐Yun Zhang, Ka Long Chan, Hening A. Rahayu, Joseph S. Francisco, Norman Lu. Unusual Changes of C−H Bond Lengths in Chiral Zinc Complexes Induced by Noncovalent Interactions. Angewandte Chemie 2023, 135 (6) https://doi.org/10.1002/ange.202215438
    4. Gurumallappa, J. Jayashankar, M.K. Hema, C.S. Karthik, D. Suma, S.R. Kumaraswamy, N.K. Lokanath, P. Mallu, M. Nethaji, N. Lu. Enchant O H⋅⋅⋅O interactions in hydrated 6-amino-2-methoxypyrimidin-4(3H)one resembles as water flow in the channel: Crystallographic and theoretical investigations. Journal of Molecular Structure 2022, 1263 , 133098. https://doi.org/10.1016/j.molstruc.2022.133098
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    6. Md. Sajid Hasan, Abul Kashem Liton, Tahmina Haque, Mohammad Idrish Ali, Shathee Akter. An experimental and DFT computational study on Methyl 3-acetyl-2-oxo-2H-chromene-6-carboxylate. Molecular Physics 2022, 4 https://doi.org/10.1080/00268976.2022.2103468
    7. Guoping Li, Liang-Wen Feng, Subhrangsu Mukherjee, Leighton O. Jones, Robert M. Jacobberger, Wei Huang, Ryan M. Young, Robert M. Pankow, Weigang Zhu, Norman Lu, Kevin L. Kohlstedt, Vinod K. Sangwan, Michael R. Wasielewski, Mark C. Hersam, George C. Schatz, Dean M. DeLongchamp, Antonio Facchetti, Tobin J. Marks. Non-fullerene acceptors with direct and indirect hexa-fluorination afford >17% efficiency in polymer solar cells. Energy & Environmental Science 2022, 15 (2) , 645-659. https://doi.org/10.1039/D1EE03225A
    8. Eskedar Tessema, Yao-Wen Fan, Chiao-Fan Chiu, Vijayanath Elakkat, Hening Asti Rahayu, Chia-Rui Shen, Karthik Chimatahalli Shanthakumar, Norman Lu. Recoverable Low Fluorine Content Palladium Complex-Catalyzed Suzuki-Miyaura and Sonogashira Coupling Reactions Under Thermomorphic Mode. SSRN Electronic Journal 2022, 51 https://doi.org/10.2139/ssrn.4143735
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