Microwave spectrum and structure of the 3,5-difluoropyridine⋯CO2 van der Waals complex

Christopher T. Dewberry; Ryan D. Cornelius; Rebecca B. Mackenzie; C. J. Smith; Michael A. Dvorak; Kenneth R. Leopold

doi:10.1016/j.jms.2016.08.016

Microwave spectrum and structure of the 3,5-difluoropyridine⋯CO₂ van der Waals complex

Christopher T. Dewberry, Ryan D. Cornelius, Rebecca B. Mackenzie, C. J. Smith, Michael A. Dvorak, Kenneth R. Leopold

Chemistry (Twin Cities)

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

9 Scopus citations

Abstract

The rotational spectrum of the weakly bound complex 3,5-difluoropyridine⋯CO₂ has been observed using pulsed-nozzle Fourier transform microwave spectroscopy. Spectroscopic constants are reported for the parent and ¹³CO₂ isotopologues. The data indicate a planar structure in which the nitrogen approaches the carbon of the CO₂ with either a C₂_v or effectively C₂_v geometry in the ground vibrational state. The N⋯C van der Waals bond distance is 2.8245(16) Å and the oxygen⋯ortho-hydrogen distance is 3.091(2) Å. The N⋯C van der Waals bond length is 0.027(8) Å longer than that previously determined for pyridine–CO₂, but is still considerably shorter than the 2.998 Å distance in HCN⋯CO₂. M06-2X/6-311++G(3df,3pd) calculations place the binding energy of the complex at 4.3 kcal/mol (4.1 kcal/mol with counterpoise correction). The calculations further indicate that a secondary interaction between the ortho-hydrogens of the ring and the CO₂ oxygens account for ∼50% of the total binding energy.

Original language	English (US)
Pages (from-to)	67-72
Number of pages	6
Journal	Journal of molecular spectroscopy
Volume	328
DOIs	https://doi.org/10.1016/j.jms.2016.08.016
State	Published - Oct 1 2016

Bibliographical note

Funding Information:
This work was supported by the National Science Foundation (Grant Nos. CHE-1266320 and CHE-1563324 ), the St. Cloud State University Office of Sponsored Programs , St. Cloud State University College of Science and Engineering , and by an NSF REU Research Fellowship awarded to R.D.C. through the University of Minnesota. We are grateful to Professor Steven Kass for helpful discussions.

Publisher Copyright:
© 2016 Elsevier Inc.

Keywords

Carbon dioxide complex
Difluoropyridine
Microwave
Weakly bound complex

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title = "Microwave spectrum and structure of the 3,5-difluoropyridine⋯CO2 van der Waals complex",

abstract = "The rotational spectrum of the weakly bound complex 3,5-difluoropyridine⋯CO2 has been observed using pulsed-nozzle Fourier transform microwave spectroscopy. Spectroscopic constants are reported for the parent and 13CO2 isotopologues. The data indicate a planar structure in which the nitrogen approaches the carbon of the CO2 with either a C2v or effectively C2v geometry in the ground vibrational state. The N⋯C van der Waals bond distance is 2.8245(16) {\AA} and the oxygen⋯ortho-hydrogen distance is 3.091(2) {\AA}. The N⋯C van der Waals bond length is 0.027(8) {\AA} longer than that previously determined for pyridine–CO2, but is still considerably shorter than the 2.998 {\AA} distance in HCN⋯CO2. M06-2X/6-311++G(3df,3pd) calculations place the binding energy of the complex at 4.3 kcal/mol (4.1 kcal/mol with counterpoise correction). The calculations further indicate that a secondary interaction between the ortho-hydrogens of the ring and the CO2 oxygens account for ∼50% of the total binding energy.",

keywords = "Carbon dioxide complex, Difluoropyridine, Microwave, Weakly bound complex",

author = "Dewberry, {Christopher T.} and Cornelius, {Ryan D.} and Mackenzie, {Rebecca B.} and Smith, {C. J.} and Dvorak, {Michael A.} and Leopold, {Kenneth R.}",

note = "Funding Information: This work was supported by the National Science Foundation (Grant Nos. CHE-1266320 and CHE-1563324 ), the St. Cloud State University Office of Sponsored Programs , St. Cloud State University College of Science and Engineering , and by an NSF REU Research Fellowship awarded to R.D.C. through the University of Minnesota. We are grateful to Professor Steven Kass for helpful discussions. Publisher Copyright: {\textcopyright} 2016 Elsevier Inc.",

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T1 - Microwave spectrum and structure of the 3,5-difluoropyridine⋯CO2 van der Waals complex

AU - Dewberry, Christopher T.

AU - Cornelius, Ryan D.

AU - Mackenzie, Rebecca B.

AU - Smith, C. J.

AU - Dvorak, Michael A.

AU - Leopold, Kenneth R.

N1 - Funding Information: This work was supported by the National Science Foundation (Grant Nos. CHE-1266320 and CHE-1563324 ), the St. Cloud State University Office of Sponsored Programs , St. Cloud State University College of Science and Engineering , and by an NSF REU Research Fellowship awarded to R.D.C. through the University of Minnesota. We are grateful to Professor Steven Kass for helpful discussions. Publisher Copyright: © 2016 Elsevier Inc.

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N2 - The rotational spectrum of the weakly bound complex 3,5-difluoropyridine⋯CO2 has been observed using pulsed-nozzle Fourier transform microwave spectroscopy. Spectroscopic constants are reported for the parent and 13CO2 isotopologues. The data indicate a planar structure in which the nitrogen approaches the carbon of the CO2 with either a C2v or effectively C2v geometry in the ground vibrational state. The N⋯C van der Waals bond distance is 2.8245(16) Å and the oxygen⋯ortho-hydrogen distance is 3.091(2) Å. The N⋯C van der Waals bond length is 0.027(8) Å longer than that previously determined for pyridine–CO2, but is still considerably shorter than the 2.998 Å distance in HCN⋯CO2. M06-2X/6-311++G(3df,3pd) calculations place the binding energy of the complex at 4.3 kcal/mol (4.1 kcal/mol with counterpoise correction). The calculations further indicate that a secondary interaction between the ortho-hydrogens of the ring and the CO2 oxygens account for ∼50% of the total binding energy.

AB - The rotational spectrum of the weakly bound complex 3,5-difluoropyridine⋯CO2 has been observed using pulsed-nozzle Fourier transform microwave spectroscopy. Spectroscopic constants are reported for the parent and 13CO2 isotopologues. The data indicate a planar structure in which the nitrogen approaches the carbon of the CO2 with either a C2v or effectively C2v geometry in the ground vibrational state. The N⋯C van der Waals bond distance is 2.8245(16) Å and the oxygen⋯ortho-hydrogen distance is 3.091(2) Å. The N⋯C van der Waals bond length is 0.027(8) Å longer than that previously determined for pyridine–CO2, but is still considerably shorter than the 2.998 Å distance in HCN⋯CO2. M06-2X/6-311++G(3df,3pd) calculations place the binding energy of the complex at 4.3 kcal/mol (4.1 kcal/mol with counterpoise correction). The calculations further indicate that a secondary interaction between the ortho-hydrogens of the ring and the CO2 oxygens account for ∼50% of the total binding energy.

KW - Carbon dioxide complex

KW - Difluoropyridine

KW - Microwave

KW - Weakly bound complex

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