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Structure of hexaaquacopper(II) bromate.

A C Blackburn1, J C Gallucci, R E Gerkin

  • 1Department of Chemistry, Ohio State University, Columbus 43210.

Acta Crystallographica. Section C, Crystal Structure Communications
|October 15, 1991
PubMed
Summary
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This study reveals a unique copper(II) structure that contradicts the Jahn-Teller theorem, suggesting a dynamic effect. Hydrogen bonding interactions were also detailed in the crystal structure.

Area of Science:

  • Inorganic Chemistry
  • Crystallography
  • Solid-State Chemistry

Background:

  • The Jahn-Teller theorem predicts Jahn-Teller distortions in high-symmetry transition metal complexes.
  • Copper(II) complexes typically exhibit distorted octahedral coordination due to the static Jahn-Teller effect.
  • Understanding deviations from predicted behavior is crucial for advancing coordination chemistry.

Purpose of the Study:

  • To determine the crystal structure of hexaaquacopper(II) bromate, [Cu(H2O)6](BrO3)2.
  • To investigate the coordination geometry of the copper(II) ion and its implications for the Jahn-Teller theorem.
  • To analyze the structure of the bromate anion and hydrogen bonding within the crystal lattice.

Main Methods:

  • Single-crystal X-ray diffraction was employed to solve the crystal structure.

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  • The crystal structure was refined to a residual R-factor of 0.038 for 336 unique reflections.
  • Analysis included bond lengths, bond angles, and positional parameters of hydrogen atoms.

    • Main Results:

    • The crystal structure of [Cu(H2O)6](BrO3)2 was determined to be cubic with space group Pa3.
    • The copper(II) ion exhibits a virtually regular octahedral coordination by six water molecules, inconsistent with a static Jahn-Teller effect.
    • Evidence supports the presence of a dynamic Jahn-Teller effect, and detailed hydrogen bonding between water oxygen atoms and bromate groups was observed.

    Conclusions:

    • This study presents the sixth example of a copper(II) static structure that is inconsistent with the Jahn-Teller theorem.
    • The findings suggest a dynamic Jahn-Teller effect is operative in this complex.
    • The crystal structure provides insights into the interplay between coordination geometry, electronic effects, and hydrogen bonding.