Molecular structure of nicotine as studied by gas electron diffraction combined with theoretical calculations

Tsuguhide Takeshima, Risaku Fukumoto, Toru Egawa, Shigehiro Konaka

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Abstract

The molecular structure of nicotine was determined by means of gas electron diffraction. The nozzle temperature was about 116 °C. The results of RHF, MP2, and DFT calculations were used as supporting information. The electron diffraction data were well reproduced by assuming the mixture of two conformers where both the methyl group and the pyridine ring are in the equatorial positions of the pyrrolidine ring. The determined structural parameters (rg and ∠α) are as follows: 〈r(C-N)pyrrol〉 = 1.462(4) Å; 〈r(C-C)pyrrol〉 = 1.541(4) Å; 〈r(C-N)pyrid〈 = 1.345(2) Å; 〈r(C-C)pyrid〉 = 1.397 Å (d.p.); r(Cpyrrol-Cpyrid) = 1.502 Å (d.p.); 〈r(C-H)pyrrol〉 = 1.116(4) Å; 〈r(C-H)pyrid〉 = 1.106 Å (d.p.); ∠C-N-Cpyrrol = 108.4(15)°; ∠N-C-Cpyrrol〉 = 102.4° (d.p.); 〈∠C-C-Cpyrrol〉 = 108.2(33)°; ∠C-N-Cpyrid = 116.8(2)°; 〈∠N-C-Cpyrid〉 = 124.1° (d.p.); 〈∠C-C-Cpyrid〉 = 118.3° (d.p.); ∠Npyrrol-Cpyrrol-Cpyrid = 116.8(10)°; ∠Cpyrrol-Cpyrrol-Cpyrid = 115.8(20)°; 〈∠H-C-H〉 = 111.9(41)°; α = 45.7(25)°; β = 32.9(38)°; ø = -87.7(74)°. Angle brackets denote averaged values, values in parentheses are 3 times the estimated standard errors referring to the last significant digit, and d.p. denotes dependent parameters. Angle α is the methyl out-of-plane angle, and β is the puckering angle of the pyrrolidine ring. Angle ø is the dihedral angle between the planes of pyrrolidine and pyridine rings. The distances between the two N atoms are determined to be 4.885 ± 0.006 and 4.275 ± 0.007 Å for the two conformers. By comparing these values with the distance between the N and carbonyl O atoms of acetylcholine, a strong nicotinic agonist, it is concluded that among the two conformers of nicotine, only the one with the longer N⋯N distance has the nicotinic activity.

Original languageEnglish (US)
Pages (from-to)8734-8740
Number of pages7
JournalJournal of Physical Chemistry A
Volume106
Issue number37
DOIs
Publication statusPublished - Sep 19 2002

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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