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Molecular structure and internal rotation of CH2Cl group of chloropropanone oxime: gas electron diffraction, microwave spectroscopy, and quantum chemical calculation studies

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Abstract

The molecular structure of chloropropanone oxime [ClCH2C(CH3)=NOH] has been determined by gas electron diffraction (GED), microwave spectroscopy (MW) and quantum chemical calculations. Potential energy curves for the internal rotation of CH2Cl group in (E)- and (Z)-isomers as well as the optimized geometries and force constants for four conformations have been calculated by the quantum chemical calculations. Combined data analysis of the GED and MW data revealed the conformational mixture of 68(4) % (E)-anticlinal and 32 % (Z)-synclinal conformers. The principal values of geometrical parameters of the E-anticlinal conformer are: r g(ClH2C–C) = 1.499(2) Å, r g(C–CH3) = 1.503(2) Å, r g(C=N) = 1.276(4) Å, r g(C–Cl) = 1.805(3) Å, r g(N–O) = 1.398(4) Å, ∠αC–C=N = 113.2(16)°, ∠αC–C–Cl = 111.1°(5), ∠αH3C–C=N = 127.0°(13), ϕ(NCCCl) = 121.1°(21). Numbers in parentheses are three times standard deviations of the data fit.

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Acknowledgments

NK thank Prof. Shinkoh Nanbu and members of the Laboratory for Theory-Aided Molecular Design (Department of Materials and Life Sciences, Sophia University) for the use of their computing server for the quantum chemical calculations. This work was supported by JSPS KAKENHI Grant 25410026.

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Authors and Affiliations

  1. Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioi-cho, Chiyoda-ku,Tokyo, 102-8554, Japan

    Nobuhiko Kuze

  2. Department of Chemistry, Faculty of Science and Technology, Sophia University, 7-1 Kioi-cho, Chiyoda-ku, Tokyo, 102-8554, Japan

    Nobuhiko Kuze, Takashi Watado, Yuri Takahashi, Takeshi Sakaizumi & Osamu Ohashi

  3. Department of Chemistry, Faculty of Science, Shizuoka University, Oya, Shizuoka, 422-8529, Japan

    Minako Kiuchi & Kinya Iijima

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  1. Nobuhiko Kuze
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  2. Takashi Watado
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  3. Yuri Takahashi
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  4. Takeshi Sakaizumi
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  5. Osamu Ohashi
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Correspondence to Nobuhiko Kuze.

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Dedicated to Professor Magdolna Hargittai on the occasion of her 70th birthday.

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Kuze, N., Watado, T., Takahashi, Y. et al. Molecular structure and internal rotation of CH2Cl group of chloropropanone oxime: gas electron diffraction, microwave spectroscopy, and quantum chemical calculation studies. Struct Chem 26, 1241–1257 (2015). https://doi.org/10.1007/s11224-015-0649-x

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