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1H MAS, 13C CP/MAS, and 2H NMR spectra studies of piperidinium \({\emph{p}}\)-chlorobenzoate

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Abstract

Anomalous H/D isotope effects were detected in the 1H MAS NMR spectra of piperidinium p-chlorobenzoate (C5H10NH\(_{2}{^{+}}\cdot \)ClC6H4COO − ) upon deuterium substitution of hydrogen atoms which form two kinds of N-H⋯O H-bonds in the crystal; in contrast to these spectra, only slight chemical shifts were recorded in 13C CP/MAS NMR spectra. 2H NMR spectrum of the deuterated sample show quadrupole coupling constants of 148 and 108 kHz, and reveal that there are a few motions contributing to the electric-field modulation of the 2H nucleus. The 1H MAS NMR spectra of piperidinium p-chlrobenzoate-d 16 (C5D10ND\(_{2}{^{+}}\cdot \)ClC6D4COO − ) and -d 14 (C5D10NH\(_{2}{^{+}}\cdot \)ClC6D4COO − ) revealed that the change in the envelope is caused by chemical shifts of each signal upon deuteration. Calculations based on the density-functional-theory showed that the N-H distance along the crystallographic a-axis mainly contributes to the anomalous isotope effects on 1H MAS NMR envelopes.

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Authors and Affiliations

  1. Graduate School of Integrated Science, Yokohama City University, Kanazawa-ku, Yokohama, 236–0027, Japan

    Ryo Nakano, Hisashi Honda & Sumiko Noro

  2. Graduate School of Nanobioscience, Yokohama City University, Kanazawa-ku, Yokohama, 236–0027, Japan

    Hisashi Honda

  3. Department of Green and Sustainable Chemistry, Tokyo Denki University, Adachi-ku, Tokyo, 120–8551, Japan

    Shin’ichi Ishimaru

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  1. Ryo Nakano
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  2. Hisashi Honda
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  3. Shin’ichi Ishimaru
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  4. Sumiko Noro
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Correspondence to Hisashi Honda.

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Nakano, R., Honda, H., Ishimaru, S. et al. 1H MAS, 13C CP/MAS, and 2H NMR spectra studies of piperidinium \({\emph{p}}\)-chlorobenzoate. Hyperfine Interact 222, 43–54 (2013). https://doi.org/10.1007/s10751-012-0671-y

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