Neutron Diffraction Study of Significant sp3and sp2C-H Bond Shortening in a Fluorinated Pyridinium Saccharinate

Norman Lu; Vijayanath Elakkat; Joseph S. Thrasher; Xiaoping Wang; Eskedar Tessema; Ka Long Chan; Rong Jun Wei; Tarek Trabelsi; Joseph S. Francisco

doi:10.1021/jacs.1c02570

Neutron Diffraction Study of Significant sp³and sp²C-H Bond Shortening in a Fluorinated Pyridinium Saccharinate

Norman Lu, Vijayanath Elakkat, Joseph S. Thrasher, Xiaoping Wang, Eskedar Tessema, Ka Long Chan, Rong Jun Wei, Tarek Trabelsi, Joseph S. Francisco

Single Crystal Diffraction

Research output: Contribution to journal › Article › peer-review

13 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	5550-5557
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	143
Issue number	14
DOIs	https://doi.org/10.1021/jacs.1c02570
State	Published - Apr 14 2021

Funding

Notice: This manuscript has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the U.S. Department of Energy (DOE). The U.S. government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for U.S. government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). N.L. gratefully acknowledges both the Ministry of Science and Technology (MOST 106-2113-M-027-001) and NSRRC in Taiwan for the funding (N-2018-R-017). N.L. thanks Dr. Y.-S. Wen from Academia Sinica in Taiwan for X-ray work on compound 1 . The research at ORNL’s Spallation Neutron Source (TOPAZ beamline) has been sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. This manuscript has been coauthored by UT-Battelle LLC under DOE contract no. DE-AC05-00OR22725.

Funders	Funder number
NSRRC in Taiwan	N-2018-R-017
Scientific User Facilities Division
U.S. Department of Energy	DE-AC05-00OR22725
Basic Energy Sciences
Oak Ridge National Laboratory
UT-Battelle
Ministry of Science and Technology, Taiwan	106-2113-M-027-001

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10.1021/jacs.1c02570

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title = "Neutron Diffraction Study of Significant sp3and sp2C-H Bond Shortening in a Fluorinated Pyridinium Saccharinate",

abstract = "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) {\AA} 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.",

author = "Norman Lu and Vijayanath Elakkat and Thrasher, {Joseph S.} and Xiaoping Wang and Eskedar Tessema and Chan, {Ka Long} and Wei, {Rong Jun} and Tarek Trabelsi and Francisco, {Joseph S.}",

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T1 - Neutron Diffraction Study of Significant sp3and sp2C-H Bond Shortening in a Fluorinated Pyridinium Saccharinate

AU - Lu, Norman

AU - Elakkat, Vijayanath

AU - Thrasher, Joseph S.

AU - Wang, Xiaoping

AU - Tessema, Eskedar

AU - Chan, Ka Long

AU - Wei, Rong Jun

AU - Trabelsi, Tarek

AU - Francisco, Joseph S.

PY - 2021/4/14

Y1 - 2021/4/14

N2 - 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.

AB - 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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Neutron Diffraction Study of Significant sp³and sp²C-H Bond Shortening in a Fluorinated Pyridinium Saccharinate

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