1-(Naphthylamino)-1-(p-chlorophenylhydrazono)-2-propanone and 2-(p-tolyldiazenyl)-[1H]-3-methylbenzo[g]indole

Crystallographic and spectroscopic elucidation of the cyclisation of an arylamidrazone

Raid J. Abdel-Jalil, Manar M. Arafeh, Musa S. Shongwe, Cäcilia Maichle-Mößmer, Gabriele Kociok-Köhn, Wolfgang Voelter

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The crystal structure of the organic compound 1-(naphthylamino)-1-(p-chlorophenylhydrazono-2-propanone, 1a, comprises two crystallographically nonequivalent independent molecules in the asymmetric unit with dispositions and relative orientations amenable to inter- and intramolecular hydrogen bonding of the type N-H⋯O. The former arises from interactions between the phenylhydrazono unit of one molecule and the acetyl group of the other in the next asymmetric unit whereas the latter occurs between the naphthylamino fragment and the acetyl group within the same molecule. The molecular framework from the phenyl to the acetyl group which incorporates an imine (CN) bond is essentially planar; however, conspicuously, the naphthyl group is twisted off this plane somewhat orthogonally, causing the formation of π-π stacked aromatic layers from interactions of alternating pairs of these groups between the hydrogen-bonding chains. The molecular structure of 2-(p-tolyldiazenyl)-[1H]-3-methylbenzo[g]indole, 2b, has not only established definitively the cyclisation of the arylamidrazone 1-(naphthylamino)-1-(p-tolylhydrazono-2-propanone, but also revealed an unprecedented oxidation of the phenylhydrazono fragment (PhNHN) to the phenylazo unit (PhNN) with polyphosphoric acid. The overall structures of 1a and 2b contrast sharply in that of the latter is virtually planar in its entirety with greater rigidity. The structures have been corroborated by vibrational and NMR spectroscopic techniques.

Original languageEnglish
Pages (from-to)307-314
Number of pages8
JournalJournal of Molecular Structure
Volume1079
DOIs
Publication statusPublished - 2015

Fingerprint

Cyclization
Acetone
Molecules
Hydrogen bonds
Imines
Organic compounds
Rigidity
Molecular structure
Crystal structure
Nuclear magnetic resonance
Oxidation
indole

Keywords

  • Arylamidrazone
  • Benzo[g]indole
  • FTIR and NMR spectroscopic techniques
  • H-bonding interactions
  • Single-crystal X-ray analyses

ASJC Scopus subject areas

  • Spectroscopy
  • Analytical Chemistry
  • Inorganic Chemistry
  • Organic Chemistry

Cite this

1-(Naphthylamino)-1-(p-chlorophenylhydrazono)-2-propanone and 2-(p-tolyldiazenyl)-[1H]-3-methylbenzo[g]indole : Crystallographic and spectroscopic elucidation of the cyclisation of an arylamidrazone. / Abdel-Jalil, Raid J.; Arafeh, Manar M.; Shongwe, Musa S.; Maichle-Mößmer, Cäcilia; Kociok-Köhn, Gabriele; Voelter, Wolfgang.

In: Journal of Molecular Structure, Vol. 1079, 2015, p. 307-314.

Research output: Contribution to journalArticle

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title = "1-(Naphthylamino)-1-(p-chlorophenylhydrazono)-2-propanone and 2-(p-tolyldiazenyl)-[1H]-3-methylbenzo[g]indole: Crystallographic and spectroscopic elucidation of the cyclisation of an arylamidrazone",
abstract = "The crystal structure of the organic compound 1-(naphthylamino)-1-(p-chlorophenylhydrazono-2-propanone, 1a, comprises two crystallographically nonequivalent independent molecules in the asymmetric unit with dispositions and relative orientations amenable to inter- and intramolecular hydrogen bonding of the type N-H⋯O. The former arises from interactions between the phenylhydrazono unit of one molecule and the acetyl group of the other in the next asymmetric unit whereas the latter occurs between the naphthylamino fragment and the acetyl group within the same molecule. The molecular framework from the phenyl to the acetyl group which incorporates an imine (CN) bond is essentially planar; however, conspicuously, the naphthyl group is twisted off this plane somewhat orthogonally, causing the formation of π-π stacked aromatic layers from interactions of alternating pairs of these groups between the hydrogen-bonding chains. The molecular structure of 2-(p-tolyldiazenyl)-[1H]-3-methylbenzo[g]indole, 2b, has not only established definitively the cyclisation of the arylamidrazone 1-(naphthylamino)-1-(p-tolylhydrazono-2-propanone, but also revealed an unprecedented oxidation of the phenylhydrazono fragment (PhNHN) to the phenylazo unit (PhNN) with polyphosphoric acid. The overall structures of 1a and 2b contrast sharply in that of the latter is virtually planar in its entirety with greater rigidity. The structures have been corroborated by vibrational and NMR spectroscopic techniques.",
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T1 - 1-(Naphthylamino)-1-(p-chlorophenylhydrazono)-2-propanone and 2-(p-tolyldiazenyl)-[1H]-3-methylbenzo[g]indole

T2 - Crystallographic and spectroscopic elucidation of the cyclisation of an arylamidrazone

AU - Abdel-Jalil, Raid J.

AU - Arafeh, Manar M.

AU - Shongwe, Musa S.

AU - Maichle-Mößmer, Cäcilia

AU - Kociok-Köhn, Gabriele

AU - Voelter, Wolfgang

PY - 2015

Y1 - 2015

N2 - The crystal structure of the organic compound 1-(naphthylamino)-1-(p-chlorophenylhydrazono-2-propanone, 1a, comprises two crystallographically nonequivalent independent molecules in the asymmetric unit with dispositions and relative orientations amenable to inter- and intramolecular hydrogen bonding of the type N-H⋯O. The former arises from interactions between the phenylhydrazono unit of one molecule and the acetyl group of the other in the next asymmetric unit whereas the latter occurs between the naphthylamino fragment and the acetyl group within the same molecule. The molecular framework from the phenyl to the acetyl group which incorporates an imine (CN) bond is essentially planar; however, conspicuously, the naphthyl group is twisted off this plane somewhat orthogonally, causing the formation of π-π stacked aromatic layers from interactions of alternating pairs of these groups between the hydrogen-bonding chains. The molecular structure of 2-(p-tolyldiazenyl)-[1H]-3-methylbenzo[g]indole, 2b, has not only established definitively the cyclisation of the arylamidrazone 1-(naphthylamino)-1-(p-tolylhydrazono-2-propanone, but also revealed an unprecedented oxidation of the phenylhydrazono fragment (PhNHN) to the phenylazo unit (PhNN) with polyphosphoric acid. The overall structures of 1a and 2b contrast sharply in that of the latter is virtually planar in its entirety with greater rigidity. The structures have been corroborated by vibrational and NMR spectroscopic techniques.

AB - The crystal structure of the organic compound 1-(naphthylamino)-1-(p-chlorophenylhydrazono-2-propanone, 1a, comprises two crystallographically nonequivalent independent molecules in the asymmetric unit with dispositions and relative orientations amenable to inter- and intramolecular hydrogen bonding of the type N-H⋯O. The former arises from interactions between the phenylhydrazono unit of one molecule and the acetyl group of the other in the next asymmetric unit whereas the latter occurs between the naphthylamino fragment and the acetyl group within the same molecule. The molecular framework from the phenyl to the acetyl group which incorporates an imine (CN) bond is essentially planar; however, conspicuously, the naphthyl group is twisted off this plane somewhat orthogonally, causing the formation of π-π stacked aromatic layers from interactions of alternating pairs of these groups between the hydrogen-bonding chains. The molecular structure of 2-(p-tolyldiazenyl)-[1H]-3-methylbenzo[g]indole, 2b, has not only established definitively the cyclisation of the arylamidrazone 1-(naphthylamino)-1-(p-tolylhydrazono-2-propanone, but also revealed an unprecedented oxidation of the phenylhydrazono fragment (PhNHN) to the phenylazo unit (PhNN) with polyphosphoric acid. The overall structures of 1a and 2b contrast sharply in that of the latter is virtually planar in its entirety with greater rigidity. The structures have been corroborated by vibrational and NMR spectroscopic techniques.

KW - Arylamidrazone

KW - Benzo[g]indole

KW - FTIR and NMR spectroscopic techniques

KW - H-bonding interactions

KW - Single-crystal X-ray analyses

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JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

SN - 0022-2860

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