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Bonding in phenylhydrazones: X-ray crystal structure and theoretical calculations involving (E)-acetophenone phenylhydrazone

Bindungen in Phenylhydrazonen. Röntgenstrukturanalyse und theoretische Berechnungen an (E)-Acetoxyphenon-phenylhydrazin

  • Organische Chemie Und Biochemie
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Summary

Semiempirical (PM3 type) calculations have been carried out on theE isomer of acetophenone phenylhydrazone and extended to include acetophenoneimine and phenylhydrazone. The optimized structure of acetophenone phenylhydrazone has also been compared with the solid state structure obtained from the results of an X-ray crystal structure determination. The crystals are monoclinic, space group P21/c,a=5.520(2) Å,b=8.944(3) Å,c=23.591(8) Å, β=90.28(3)°, andV=1164.7(7) Å3. The finalR value is 0.0549 for 1097 reflections withF>3σ(F). The structure possesses a planar conformation and both N atoms possess trigonal-planar geometries. Results of the theoretical calculation are in good agreement with those obtained from the crystallographic data and indicate that conjugation between the hydrazone region and the phenyl rings plays a significant role in favoring a planar molecular conformation and has a significant perturbing influence on the bond lengths and angles associated with the hydrazone C=N-N atoms. A Mulliken analysis for the structure gives bond orders of 1.77 and 1.10 for the formally double bonded C-N and single-bonded N-N atoms, respectively.

Zusammenfassung

Es wurden semiempirische PM3-Typ-Berechnungen für dasE-Isomere von Acetophenon-phenylhydrazon durchgeführt und dann auf Acetophenonimin und Phenylhydrazon ausgeweitet. Die optimierte Geometrie von Acetophenon-phenylhydrazon wurde mit der Kristallstruktur dieser Verbindung verglichen. Die Kristalle sind monoklin, Raumgruppe P21/c,a=5.520(2) Å,b=8.944(3) Å,c=23.591(8) Å, β=90.28(3)° undV=1164.7(7) Å3. Der endgültigeR-Wert für 1097 Reflexe mitF>3σ(F) war 0.0549. Die Struktur besitzt eine planare Konformation und beide N-Atome haben trigonal-planare Geometrien. Die Ergebnisse der theoretische Berechnungen sind in guter Übereinstimmung mit jenen aus den kristallographischen Daten und zeigen, daß die Konjugation zwischen dem Hydrazonteil und den Phenylringen eine signifikante Rolle bei der planaren Konformation trägt und auch einen entscheidenden Einfluß auf Störungen bei Bindungslängen und-winkel in der Hydrazongruppierung C=N-N hat. Eine Mulliken-Analyse der Struktur ergab Bindungsordnungen von 1.77 bzw. 1.10 für die formale Doppelbindung C-N bzw. die Einfachbindung N-N.

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Authors and Affiliations

  1. Department of Chemistry, University of Texas at El Paso, El Paso, Texas, USA

    L. C. Porter,  Ming-Li & F. Cervantes-Lee

  2. Exxon Research and Engineering, Annandale, NJ, USA

    H. H. Murray III

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  1. L. C. Porter
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  2. Ming-Li
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  3. F. Cervantes-Lee
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  4. H. H. Murray III
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Porter, L.C., Ming-Li, Cervantes-Lee, F. et al. Bonding in phenylhydrazones: X-ray crystal structure and theoretical calculations involving (E)-acetophenone phenylhydrazone. Monatsh Chem 124, 775–782 (1993). https://doi.org/10.1007/BF00817313

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  • DOI: https://doi.org/10.1007/BF00817313

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