Crystal Structure and Cationic Motion of o-Toluidinium Chloranilate and m-Toluidinium Chloranilate Studied by X-ray Diffraction and 1H NMR

Takeo Fukunaga, Naoki Kumagae, Hiroyuki Ishida

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9 Citations (Scopus)

Abstract

The crystal structure of o-toluidinium chloranilate and m-toluidinium chloranilate, 2CH3C6H4-NH3 + · C6O4Cl22-, was determined by single crystal X-ray diffraction at room temperature. It was found that o-toluidinium chloranilate (I) is monoclinic, P21/n (#14), Z = 2, a = 5.2184(14), b = 7.825(2), c = 22.840(5) Å, and β = 92.015(19)°, and m-toluidinium chloranilate (II) is monoclinic, P2 1/c (#14), Z = 2, a = 11.214(2), b = 5.4844(10), c = 16.379(6) Å, and β = 105.21(2)°. In these salts, the cations are connected with the anions by N-H... O hydrogen bonds to form 2:1 units of 2CH 3C6H4NH3+ · C 6C4Cl22- that are located on inversion centers. The 2CH3C6H4NH 3+ · C6O4Cl2 2- units in both salts are connected by other N-H... O hydrogen bonds to build a three-dimensional hydrogen-bond network. Motions of the toluidinium ions in solid (I) and (II) were studied by 1H NMR spin-lattice relaxation time measurements. Reorientations of the NH 3+ group about the C-N bond axis and the CH3 group about the C-C bond axis were observed, and their motional parameters were evaluated. The internal rotational barriers of the NH3+ and CH3 groups of an isolated o-toluidinium ion were estimated from ab initio molecular orbital calculations at HF/6-31G(d,p), MP2/6-31G(d,p), and B3LYP/6-31G(d,p) levels of theory.

Original languageEnglish
Pages (from-to)631-637
Number of pages7
JournalZeitschrift fur Naturforschung - Section A Journal of Physical Sciences
Volume58
Issue number11
Publication statusPublished - Nov 2003

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Hydrogen Bonds
Crystal Structure
X-ray Diffraction
Hydrogen bonds
Crystal structure
Nuclear magnetic resonance
hydrogen bonds
Salt
X ray diffraction
nuclear magnetic resonance
crystal structure
Motion
Salts
diffraction
Ions
salts
Orbital calculations
Unit
x rays
Spin-lattice relaxation

Keywords

  • Cationic Motion
  • Crystal Structure
  • Hydrogen Bond
  • MO Calculation
  • X-ray Diffraction

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

@article{2c20ced2329649648269b3f8184d0629,
title = "Crystal Structure and Cationic Motion of o-Toluidinium Chloranilate and m-Toluidinium Chloranilate Studied by X-ray Diffraction and 1H NMR",
abstract = "The crystal structure of o-toluidinium chloranilate and m-toluidinium chloranilate, 2CH3C6H4-NH3 + · C6O4Cl22-, was determined by single crystal X-ray diffraction at room temperature. It was found that o-toluidinium chloranilate (I) is monoclinic, P21/n (#14), Z = 2, a = 5.2184(14), b = 7.825(2), c = 22.840(5) {\AA}, and β = 92.015(19)°, and m-toluidinium chloranilate (II) is monoclinic, P2 1/c (#14), Z = 2, a = 11.214(2), b = 5.4844(10), c = 16.379(6) {\AA}, and β = 105.21(2)°. In these salts, the cations are connected with the anions by N-H... O hydrogen bonds to form 2:1 units of 2CH 3C6H4NH3+ · C 6C4Cl22- that are located on inversion centers. The 2CH3C6H4NH 3+ · C6O4Cl2 2- units in both salts are connected by other N-H... O hydrogen bonds to build a three-dimensional hydrogen-bond network. Motions of the toluidinium ions in solid (I) and (II) were studied by 1H NMR spin-lattice relaxation time measurements. Reorientations of the NH 3+ group about the C-N bond axis and the CH3 group about the C-C bond axis were observed, and their motional parameters were evaluated. The internal rotational barriers of the NH3+ and CH3 groups of an isolated o-toluidinium ion were estimated from ab initio molecular orbital calculations at HF/6-31G(d,p), MP2/6-31G(d,p), and B3LYP/6-31G(d,p) levels of theory.",
keywords = "Cationic Motion, Crystal Structure, Hydrogen Bond, MO Calculation, X-ray Diffraction",
author = "Takeo Fukunaga and Naoki Kumagae and Hiroyuki Ishida",
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T1 - Crystal Structure and Cationic Motion of o-Toluidinium Chloranilate and m-Toluidinium Chloranilate Studied by X-ray Diffraction and 1H NMR

AU - Fukunaga, Takeo

AU - Kumagae, Naoki

AU - Ishida, Hiroyuki

PY - 2003/11

Y1 - 2003/11

N2 - The crystal structure of o-toluidinium chloranilate and m-toluidinium chloranilate, 2CH3C6H4-NH3 + · C6O4Cl22-, was determined by single crystal X-ray diffraction at room temperature. It was found that o-toluidinium chloranilate (I) is monoclinic, P21/n (#14), Z = 2, a = 5.2184(14), b = 7.825(2), c = 22.840(5) Å, and β = 92.015(19)°, and m-toluidinium chloranilate (II) is monoclinic, P2 1/c (#14), Z = 2, a = 11.214(2), b = 5.4844(10), c = 16.379(6) Å, and β = 105.21(2)°. In these salts, the cations are connected with the anions by N-H... O hydrogen bonds to form 2:1 units of 2CH 3C6H4NH3+ · C 6C4Cl22- that are located on inversion centers. The 2CH3C6H4NH 3+ · C6O4Cl2 2- units in both salts are connected by other N-H... O hydrogen bonds to build a three-dimensional hydrogen-bond network. Motions of the toluidinium ions in solid (I) and (II) were studied by 1H NMR spin-lattice relaxation time measurements. Reorientations of the NH 3+ group about the C-N bond axis and the CH3 group about the C-C bond axis were observed, and their motional parameters were evaluated. The internal rotational barriers of the NH3+ and CH3 groups of an isolated o-toluidinium ion were estimated from ab initio molecular orbital calculations at HF/6-31G(d,p), MP2/6-31G(d,p), and B3LYP/6-31G(d,p) levels of theory.

AB - The crystal structure of o-toluidinium chloranilate and m-toluidinium chloranilate, 2CH3C6H4-NH3 + · C6O4Cl22-, was determined by single crystal X-ray diffraction at room temperature. It was found that o-toluidinium chloranilate (I) is monoclinic, P21/n (#14), Z = 2, a = 5.2184(14), b = 7.825(2), c = 22.840(5) Å, and β = 92.015(19)°, and m-toluidinium chloranilate (II) is monoclinic, P2 1/c (#14), Z = 2, a = 11.214(2), b = 5.4844(10), c = 16.379(6) Å, and β = 105.21(2)°. In these salts, the cations are connected with the anions by N-H... O hydrogen bonds to form 2:1 units of 2CH 3C6H4NH3+ · C 6C4Cl22- that are located on inversion centers. The 2CH3C6H4NH 3+ · C6O4Cl2 2- units in both salts are connected by other N-H... O hydrogen bonds to build a three-dimensional hydrogen-bond network. Motions of the toluidinium ions in solid (I) and (II) were studied by 1H NMR spin-lattice relaxation time measurements. Reorientations of the NH 3+ group about the C-N bond axis and the CH3 group about the C-C bond axis were observed, and their motional parameters were evaluated. The internal rotational barriers of the NH3+ and CH3 groups of an isolated o-toluidinium ion were estimated from ab initio molecular orbital calculations at HF/6-31G(d,p), MP2/6-31G(d,p), and B3LYP/6-31G(d,p) levels of theory.

KW - Cationic Motion

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KW - Hydrogen Bond

KW - MO Calculation

KW - X-ray Diffraction

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