Structure determination of methyl nicotinate and methyl picolinate by gas electron diffraction combined with ab initio calculations

Hajime Kiyono, Ryosuke Tatsunami, Teruyo Kurai, Hiroshi Takeuchi, Toru Egawa, Shigehiro Konaka

Research output: Contribution to journalArticle

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Abstract

The molecular structures of isomers, methyl nicotinate and methyl picolinate, have been studied by gas electron diffraction. The samples were heated to 341-343 K by using a high-temperature nozzle to get enough vapor pressure. HF/6-31G* ab initio calculations were carried out, and structural constraints were taken from their results. Vibrational amplitudes and shrinkage corrections were calculated from the harmonic force constants given by normal coordinate analyses. The principal structural parameters of the s-trans conformer of methyl nicotinate are as follows (angle brackets mean averaged values): 〈rg(N-C)〉 = 1.337(7) Å; 〈rg(C-C)ring〉 = 1.402(3) Å; rg(Cring-C(=O)) = 1.480(12) Å; rg(C=O) = 1.199(7) Å; 〈rg(C-O)〉 = 1.380(11) Å; ∠αCNC = 119.0(14)°; 〈∠αNCC) = 122.8(11)°; ∠α(N=)C-Cring-C(=O) = 118.3(12)°; ∠αCring-C=O = 121.5(12)°; ∠αCring-C-O = 115.6(10)°. Those of the s-trans conformer of methyl picolinate are as follows: 〈rg(N-C)〉 = 1.344(7) Å; 〈rg(C-C)ring〉 = 1.398(4) Å; rg(Cring-C(=O)) = 1.497(11) Å; rg(C=O) = 1.209(7) Å; 〈rg(C-O)〉 = 1.380(11) Å; ∠αCNC = 117.2(12)°; 〈∠αNCC〉 = 123.9(12)°; ∠αN-C-C(=O) = 115.1(10)°; ∠αCring-C=O = 121.0(12)°; ∠αCring-C-O = 115.1(12)°. The structural parameters of the two isomers and methyl isonicotinate have been compared and their similarity and differences have been discussed.

Original languageEnglish
Pages (from-to)1405-1411
Number of pages7
JournalJournal of Physical Chemistry A
Volume102
Issue number8
Publication statusPublished - 1998 Feb 19
Externally publishedYes

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Electron diffraction
Isomers
isomers
electron diffraction
rings
brackets
Vapor pressure
shrinkage
gases
Molecular structure
vapor pressure
nozzles
Nozzles
molecular structure
harmonics
Temperature
methyl nicotinate
picolinic acid

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Structure determination of methyl nicotinate and methyl picolinate by gas electron diffraction combined with ab initio calculations. / Kiyono, Hajime; Tatsunami, Ryosuke; Kurai, Teruyo; Takeuchi, Hiroshi; Egawa, Toru; Konaka, Shigehiro.

In: Journal of Physical Chemistry A, Vol. 102, No. 8, 19.02.1998, p. 1405-1411.

Research output: Contribution to journalArticle

Kiyono, Hajime ; Tatsunami, Ryosuke ; Kurai, Teruyo ; Takeuchi, Hiroshi ; Egawa, Toru ; Konaka, Shigehiro. / Structure determination of methyl nicotinate and methyl picolinate by gas electron diffraction combined with ab initio calculations. In: Journal of Physical Chemistry A. 1998 ; Vol. 102, No. 8. pp. 1405-1411.
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title = "Structure determination of methyl nicotinate and methyl picolinate by gas electron diffraction combined with ab initio calculations",
abstract = "The molecular structures of isomers, methyl nicotinate and methyl picolinate, have been studied by gas electron diffraction. The samples were heated to 341-343 K by using a high-temperature nozzle to get enough vapor pressure. HF/6-31G* ab initio calculations were carried out, and structural constraints were taken from their results. Vibrational amplitudes and shrinkage corrections were calculated from the harmonic force constants given by normal coordinate analyses. The principal structural parameters of the s-trans conformer of methyl nicotinate are as follows (angle brackets mean averaged values): 〈rg(N-C)〉 = 1.337(7) {\AA}; 〈rg(C-C)ring〉 = 1.402(3) {\AA}; rg(Cring-C(=O)) = 1.480(12) {\AA}; rg(C=O) = 1.199(7) {\AA}; 〈rg(C-O)〉 = 1.380(11) {\AA}; ∠αCNC = 119.0(14)°; 〈∠αNCC) = 122.8(11)°; ∠α(N=)C-Cring-C(=O) = 118.3(12)°; ∠αCring-C=O = 121.5(12)°; ∠αCring-C-O = 115.6(10)°. Those of the s-trans conformer of methyl picolinate are as follows: 〈rg(N-C)〉 = 1.344(7) {\AA}; 〈rg(C-C)ring〉 = 1.398(4) {\AA}; rg(Cring-C(=O)) = 1.497(11) {\AA}; rg(C=O) = 1.209(7) {\AA}; 〈rg(C-O)〉 = 1.380(11) {\AA}; ∠αCNC = 117.2(12)°; 〈∠αNCC〉 = 123.9(12)°; ∠αN-C-C(=O) = 115.1(10)°; ∠αCring-C=O = 121.0(12)°; ∠αCring-C-O = 115.1(12)°. The structural parameters of the two isomers and methyl isonicotinate have been compared and their similarity and differences have been discussed.",
author = "Hajime Kiyono and Ryosuke Tatsunami and Teruyo Kurai and Hiroshi Takeuchi and Toru Egawa and Shigehiro Konaka",
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T1 - Structure determination of methyl nicotinate and methyl picolinate by gas electron diffraction combined with ab initio calculations

AU - Kiyono, Hajime

AU - Tatsunami, Ryosuke

AU - Kurai, Teruyo

AU - Takeuchi, Hiroshi

AU - Egawa, Toru

AU - Konaka, Shigehiro

PY - 1998/2/19

Y1 - 1998/2/19

N2 - The molecular structures of isomers, methyl nicotinate and methyl picolinate, have been studied by gas electron diffraction. The samples were heated to 341-343 K by using a high-temperature nozzle to get enough vapor pressure. HF/6-31G* ab initio calculations were carried out, and structural constraints were taken from their results. Vibrational amplitudes and shrinkage corrections were calculated from the harmonic force constants given by normal coordinate analyses. The principal structural parameters of the s-trans conformer of methyl nicotinate are as follows (angle brackets mean averaged values): 〈rg(N-C)〉 = 1.337(7) Å; 〈rg(C-C)ring〉 = 1.402(3) Å; rg(Cring-C(=O)) = 1.480(12) Å; rg(C=O) = 1.199(7) Å; 〈rg(C-O)〉 = 1.380(11) Å; ∠αCNC = 119.0(14)°; 〈∠αNCC) = 122.8(11)°; ∠α(N=)C-Cring-C(=O) = 118.3(12)°; ∠αCring-C=O = 121.5(12)°; ∠αCring-C-O = 115.6(10)°. Those of the s-trans conformer of methyl picolinate are as follows: 〈rg(N-C)〉 = 1.344(7) Å; 〈rg(C-C)ring〉 = 1.398(4) Å; rg(Cring-C(=O)) = 1.497(11) Å; rg(C=O) = 1.209(7) Å; 〈rg(C-O)〉 = 1.380(11) Å; ∠αCNC = 117.2(12)°; 〈∠αNCC〉 = 123.9(12)°; ∠αN-C-C(=O) = 115.1(10)°; ∠αCring-C=O = 121.0(12)°; ∠αCring-C-O = 115.1(12)°. The structural parameters of the two isomers and methyl isonicotinate have been compared and their similarity and differences have been discussed.

AB - The molecular structures of isomers, methyl nicotinate and methyl picolinate, have been studied by gas electron diffraction. The samples were heated to 341-343 K by using a high-temperature nozzle to get enough vapor pressure. HF/6-31G* ab initio calculations were carried out, and structural constraints were taken from their results. Vibrational amplitudes and shrinkage corrections were calculated from the harmonic force constants given by normal coordinate analyses. The principal structural parameters of the s-trans conformer of methyl nicotinate are as follows (angle brackets mean averaged values): 〈rg(N-C)〉 = 1.337(7) Å; 〈rg(C-C)ring〉 = 1.402(3) Å; rg(Cring-C(=O)) = 1.480(12) Å; rg(C=O) = 1.199(7) Å; 〈rg(C-O)〉 = 1.380(11) Å; ∠αCNC = 119.0(14)°; 〈∠αNCC) = 122.8(11)°; ∠α(N=)C-Cring-C(=O) = 118.3(12)°; ∠αCring-C=O = 121.5(12)°; ∠αCring-C-O = 115.6(10)°. Those of the s-trans conformer of methyl picolinate are as follows: 〈rg(N-C)〉 = 1.344(7) Å; 〈rg(C-C)ring〉 = 1.398(4) Å; rg(Cring-C(=O)) = 1.497(11) Å; rg(C=O) = 1.209(7) Å; 〈rg(C-O)〉 = 1.380(11) Å; ∠αCNC = 117.2(12)°; 〈∠αNCC〉 = 123.9(12)°; ∠αN-C-C(=O) = 115.1(10)°; ∠αCring-C=O = 121.0(12)°; ∠αCring-C-O = 115.1(12)°. The structural parameters of the two isomers and methyl isonicotinate have been compared and their similarity and differences have been discussed.

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