Molecular Structure of tert-Butylazide: A Gas-Phase Electron Diffraction and Quantum Chemical Study

Annemarie MacKenzie, Thomas M. Klapötke, György Schultz, M. Hargittai

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The molecular structure of tert-butylazide has been determined by gas-phase electron diffraction and quantum chemical calculations. The HF/6-31G* and B3LYP/6-31G** calculations yielded near Cs symmetry for the tert-butyl group, anti conformation of the (C)N-N bond with respect to one of the (N)C-C(H3) bonds, and an essentially free rotation around the (C)N-N(N) bond with a 0.34 kcal/mol energy difference between syn and anti conformations of the CNNN moiety, the anti being the more stable form. The electron diffraction analysis was carried out by modeling a mixture of conformational isomers, generated by rotating the terminal nitrogen of the azide group, using a computed rotational potential. The data are consistent with Cs symmetry for the tert-butyl group. The (C)N-N bond, however, was found to be rotated out of the anti position, with respect to one of the (N)C-CH3 bonds, by 12.5(12)°. The electron diffraction analysis yielded the following bond lengths (rg) bond angles, and torsional angles: C-H 1.111(5) Å, (N-N)terminal 1.143(4) Å, (N-N)central 1.240(5) Å, N-C 1.508(5) Å, (C-C)mean 1.534(3) Å, N-N-N 171.8(20)°, N-N-C 118.6(10)°, N-C-C 102.5(6)° and 110.5(4)°, C-C-H 111.2(4)°, C-C-C 110.2(7)° and 112.6(7)°, N-N-C-C 167.5(12)°. 50.1(6)°. and -75.2(10)°.

Original languageEnglish
Pages (from-to)59-66
Number of pages8
JournalStructural Chemistry
Volume10
Issue number1
Publication statusPublished - 1999

Fingerprint

Molecular Structure
Electron diffraction
Molecular structure
molecular structure
electron diffraction
Gases
Electrons
vapor phases
Conformations
Azides
Bond length
symmetry
Isomers
Nitrogen
isomers
nitrogen
energy

Keywords

  • Ab initio calculations
  • Electron diffraction
  • Molecular structure
  • Tert-butylazide

ASJC Scopus subject areas

  • Structural Biology
  • Chemistry(all)

Cite this

Molecular Structure of tert-Butylazide : A Gas-Phase Electron Diffraction and Quantum Chemical Study. / MacKenzie, Annemarie; Klapötke, Thomas M.; Schultz, György; Hargittai, M.

In: Structural Chemistry, Vol. 10, No. 1, 1999, p. 59-66.

Research output: Contribution to journalArticle

MacKenzie, Annemarie ; Klapötke, Thomas M. ; Schultz, György ; Hargittai, M. / Molecular Structure of tert-Butylazide : A Gas-Phase Electron Diffraction and Quantum Chemical Study. In: Structural Chemistry. 1999 ; Vol. 10, No. 1. pp. 59-66.
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abstract = "The molecular structure of tert-butylazide has been determined by gas-phase electron diffraction and quantum chemical calculations. The HF/6-31G* and B3LYP/6-31G** calculations yielded near Cs symmetry for the tert-butyl group, anti conformation of the (C)N-N bond with respect to one of the (N)C-C(H3) bonds, and an essentially free rotation around the (C)N-N(N) bond with a 0.34 kcal/mol energy difference between syn and anti conformations of the CNNN moiety, the anti being the more stable form. The electron diffraction analysis was carried out by modeling a mixture of conformational isomers, generated by rotating the terminal nitrogen of the azide group, using a computed rotational potential. The data are consistent with Cs symmetry for the tert-butyl group. The (C)N-N bond, however, was found to be rotated out of the anti position, with respect to one of the (N)C-CH3 bonds, by 12.5(12)°. The electron diffraction analysis yielded the following bond lengths (rg) bond angles, and torsional angles: C-H 1.111(5) {\AA}, (N-N)terminal 1.143(4) {\AA}, (N-N)central 1.240(5) {\AA}, N-C 1.508(5) {\AA}, (C-C)mean 1.534(3) {\AA}, N-N-N 171.8(20)°, N-N-C 118.6(10)°, N-C-C 102.5(6)° and 110.5(4)°, C-C-H 111.2(4)°, C-C-C 110.2(7)° and 112.6(7)°, N-N-C-C 167.5(12)°. 50.1(6)°. and -75.2(10)°.",
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N2 - The molecular structure of tert-butylazide has been determined by gas-phase electron diffraction and quantum chemical calculations. The HF/6-31G* and B3LYP/6-31G** calculations yielded near Cs symmetry for the tert-butyl group, anti conformation of the (C)N-N bond with respect to one of the (N)C-C(H3) bonds, and an essentially free rotation around the (C)N-N(N) bond with a 0.34 kcal/mol energy difference between syn and anti conformations of the CNNN moiety, the anti being the more stable form. The electron diffraction analysis was carried out by modeling a mixture of conformational isomers, generated by rotating the terminal nitrogen of the azide group, using a computed rotational potential. The data are consistent with Cs symmetry for the tert-butyl group. The (C)N-N bond, however, was found to be rotated out of the anti position, with respect to one of the (N)C-CH3 bonds, by 12.5(12)°. The electron diffraction analysis yielded the following bond lengths (rg) bond angles, and torsional angles: C-H 1.111(5) Å, (N-N)terminal 1.143(4) Å, (N-N)central 1.240(5) Å, N-C 1.508(5) Å, (C-C)mean 1.534(3) Å, N-N-N 171.8(20)°, N-N-C 118.6(10)°, N-C-C 102.5(6)° and 110.5(4)°, C-C-H 111.2(4)°, C-C-C 110.2(7)° and 112.6(7)°, N-N-C-C 167.5(12)°. 50.1(6)°. and -75.2(10)°.

AB - The molecular structure of tert-butylazide has been determined by gas-phase electron diffraction and quantum chemical calculations. The HF/6-31G* and B3LYP/6-31G** calculations yielded near Cs symmetry for the tert-butyl group, anti conformation of the (C)N-N bond with respect to one of the (N)C-C(H3) bonds, and an essentially free rotation around the (C)N-N(N) bond with a 0.34 kcal/mol energy difference between syn and anti conformations of the CNNN moiety, the anti being the more stable form. The electron diffraction analysis was carried out by modeling a mixture of conformational isomers, generated by rotating the terminal nitrogen of the azide group, using a computed rotational potential. The data are consistent with Cs symmetry for the tert-butyl group. The (C)N-N bond, however, was found to be rotated out of the anti position, with respect to one of the (N)C-CH3 bonds, by 12.5(12)°. The electron diffraction analysis yielded the following bond lengths (rg) bond angles, and torsional angles: C-H 1.111(5) Å, (N-N)terminal 1.143(4) Å, (N-N)central 1.240(5) Å, N-C 1.508(5) Å, (C-C)mean 1.534(3) Å, N-N-N 171.8(20)°, N-N-C 118.6(10)°, N-C-C 102.5(6)° and 110.5(4)°, C-C-H 111.2(4)°, C-C-C 110.2(7)° and 112.6(7)°, N-N-C-C 167.5(12)°. 50.1(6)°. and -75.2(10)°.

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