Molecular structure of dimethylcarbamyl chloride from gas-phase electron diffraction

György Schultz, I. Hargittai

Research output: Contribution to journalArticle

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Abstract

The molecular structure of dimethylcarbamyl chloride has been determined by gas-phase electron diffraction. The analysis, aided by a constraint from ab initio MO calculations, yielded the following bond lengths (rg), bond angles, and dihedral angles: C-H 1.117 ± 0.003 Å; C=O 1.202 ± 0.003 Å; (C(H3)-N)mean 1.462 ± 0.005 Å; C(O)-N 1.365 ± 0.003 Å; C-Cl 1.789 ± 0.004 Å; ∠N-C=O 126.5 ± 0.2°; ∠N-C-Cl 113.9 ± 0.3°; ∠N-C(H3)-H 110.8 ± 0.3°; ∠C-N-C(O) syn to C=O 116.0 ± 0.4°; ∠C-N-C(O) syn to C-Cl 124.8 ± 0.4°; ∠C(H3)-N-C(H3) 116.2 ± 0.3°; ∠C(H3)-N-C=Osyn 13.0 ± 2.5°; ∠C(H3)-N-C=Oanti 172.5 ± 3.6°. One of the C-H bonds attached to the O=C-N-Csyn moiety nearly eclipses the N-C(O) bond, resulting in a relatively short, 2.30 ± 0.01 Å, O⋯H distance. The bond configuration around the N atom is nearly planar. Geometrical variations in a series of simple substituted amides are compared with a conventional scheme (1) of resonance structures and another scheme (2) recently proposed by Wiberg and Laidig. Scheme 2 involves charge transfer between carbon and nitrogen rather than from nitrogen to the carbonyl oxygen of Scheme 1. According to the variations of the experimentally determined geometries, the structural consequences of substitution at the nitrogen can be well interpreted by Scheme 1, while those of substitution at the carbonyl carbon, by Scheme 2.

Original languageEnglish
Pages (from-to)11412-11416
Number of pages5
JournalJournal of Physical Chemistry
Volume99
Issue number29
Publication statusPublished - 1995

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Electron diffraction
Molecular structure
molecular structure
Nitrogen
electron diffraction
Gases
chlorides
vapor phases
nitrogen
Substitution reactions
Carbon
substitutes
carbon
Chemical bonds
Bond length
eclipses
Dihedral angle
Amides
amides
dihedral angle

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Molecular structure of dimethylcarbamyl chloride from gas-phase electron diffraction. / Schultz, György; Hargittai, I.

In: Journal of Physical Chemistry, Vol. 99, No. 29, 1995, p. 11412-11416.

Research output: Contribution to journalArticle

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title = "Molecular structure of dimethylcarbamyl chloride from gas-phase electron diffraction",
abstract = "The molecular structure of dimethylcarbamyl chloride has been determined by gas-phase electron diffraction. The analysis, aided by a constraint from ab initio MO calculations, yielded the following bond lengths (rg), bond angles, and dihedral angles: C-H 1.117 ± 0.003 {\AA}; C=O 1.202 ± 0.003 {\AA}; (C(H3)-N)mean 1.462 ± 0.005 {\AA}; C(O)-N 1.365 ± 0.003 {\AA}; C-Cl 1.789 ± 0.004 {\AA}; ∠N-C=O 126.5 ± 0.2°; ∠N-C-Cl 113.9 ± 0.3°; ∠N-C(H3)-H 110.8 ± 0.3°; ∠C-N-C(O) syn to C=O 116.0 ± 0.4°; ∠C-N-C(O) syn to C-Cl 124.8 ± 0.4°; ∠C(H3)-N-C(H3) 116.2 ± 0.3°; ∠C(H3)-N-C=Osyn 13.0 ± 2.5°; ∠C(H3)-N-C=Oanti 172.5 ± 3.6°. One of the C-H bonds attached to the O=C-N-Csyn moiety nearly eclipses the N-C(O) bond, resulting in a relatively short, 2.30 ± 0.01 {\AA}, O⋯H distance. The bond configuration around the N atom is nearly planar. Geometrical variations in a series of simple substituted amides are compared with a conventional scheme (1) of resonance structures and another scheme (2) recently proposed by Wiberg and Laidig. Scheme 2 involves charge transfer between carbon and nitrogen rather than from nitrogen to the carbonyl oxygen of Scheme 1. According to the variations of the experimentally determined geometries, the structural consequences of substitution at the nitrogen can be well interpreted by Scheme 1, while those of substitution at the carbonyl carbon, by Scheme 2.",
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N2 - The molecular structure of dimethylcarbamyl chloride has been determined by gas-phase electron diffraction. The analysis, aided by a constraint from ab initio MO calculations, yielded the following bond lengths (rg), bond angles, and dihedral angles: C-H 1.117 ± 0.003 Å; C=O 1.202 ± 0.003 Å; (C(H3)-N)mean 1.462 ± 0.005 Å; C(O)-N 1.365 ± 0.003 Å; C-Cl 1.789 ± 0.004 Å; ∠N-C=O 126.5 ± 0.2°; ∠N-C-Cl 113.9 ± 0.3°; ∠N-C(H3)-H 110.8 ± 0.3°; ∠C-N-C(O) syn to C=O 116.0 ± 0.4°; ∠C-N-C(O) syn to C-Cl 124.8 ± 0.4°; ∠C(H3)-N-C(H3) 116.2 ± 0.3°; ∠C(H3)-N-C=Osyn 13.0 ± 2.5°; ∠C(H3)-N-C=Oanti 172.5 ± 3.6°. One of the C-H bonds attached to the O=C-N-Csyn moiety nearly eclipses the N-C(O) bond, resulting in a relatively short, 2.30 ± 0.01 Å, O⋯H distance. The bond configuration around the N atom is nearly planar. Geometrical variations in a series of simple substituted amides are compared with a conventional scheme (1) of resonance structures and another scheme (2) recently proposed by Wiberg and Laidig. Scheme 2 involves charge transfer between carbon and nitrogen rather than from nitrogen to the carbonyl oxygen of Scheme 1. According to the variations of the experimentally determined geometries, the structural consequences of substitution at the nitrogen can be well interpreted by Scheme 1, while those of substitution at the carbonyl carbon, by Scheme 2.

AB - The molecular structure of dimethylcarbamyl chloride has been determined by gas-phase electron diffraction. The analysis, aided by a constraint from ab initio MO calculations, yielded the following bond lengths (rg), bond angles, and dihedral angles: C-H 1.117 ± 0.003 Å; C=O 1.202 ± 0.003 Å; (C(H3)-N)mean 1.462 ± 0.005 Å; C(O)-N 1.365 ± 0.003 Å; C-Cl 1.789 ± 0.004 Å; ∠N-C=O 126.5 ± 0.2°; ∠N-C-Cl 113.9 ± 0.3°; ∠N-C(H3)-H 110.8 ± 0.3°; ∠C-N-C(O) syn to C=O 116.0 ± 0.4°; ∠C-N-C(O) syn to C-Cl 124.8 ± 0.4°; ∠C(H3)-N-C(H3) 116.2 ± 0.3°; ∠C(H3)-N-C=Osyn 13.0 ± 2.5°; ∠C(H3)-N-C=Oanti 172.5 ± 3.6°. One of the C-H bonds attached to the O=C-N-Csyn moiety nearly eclipses the N-C(O) bond, resulting in a relatively short, 2.30 ± 0.01 Å, O⋯H distance. The bond configuration around the N atom is nearly planar. Geometrical variations in a series of simple substituted amides are compared with a conventional scheme (1) of resonance structures and another scheme (2) recently proposed by Wiberg and Laidig. Scheme 2 involves charge transfer between carbon and nitrogen rather than from nitrogen to the carbonyl oxygen of Scheme 1. According to the variations of the experimentally determined geometries, the structural consequences of substitution at the nitrogen can be well interpreted by Scheme 1, while those of substitution at the carbonyl carbon, by Scheme 2.

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