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Isostructural trigonal-bipyramidal CuII and nominally 1% CuII-doped ZnII complexes with N5 ligation

R T Stibrany1, J A Potenza, H J Schugar

  • 1Department of Chemistry, Rutgers, State University of New Jersey, New Brunswick 08903.

Acta Crystallographica. Section C, Crystal Structure Communications
|September 15, 1993
PubMed
Summary

This study details the crystal structures of copper(II) and zinc(II) diperchlorate complexes. Axial M--N bond lengths differ significantly, with contraction in the copper complex correlating to its dz2 ground state.

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Acta crystallographica. Section C, Crystal structure communications·1995

Area of Science:

  • Coordination Chemistry
  • Inorganic Chemistry
  • Crystallography

Background:

  • Metal complexes with polyamine ligands are crucial in catalysis and bioinorganic chemistry.
  • Understanding the structural nuances of copper and zinc complexes provides insights into their electronic properties and reactivity.
  • The ligand N,N-bis(2-aminoethyl)-1,2-ethanediamine, in conjunction with 1-benzylimidazole, forms stable complexes with transition metals.

Purpose of the Study:

  • To elucidate the crystal structures of copper(II) diperchlorate (1) and a 1% Cu(II)-doped zinc(II) diperchlorate complex (2).
  • To investigate the coordination geometry and metal-ligand bond distances in these isostructural complexes.
  • To correlate structural findings, particularly axial M--N bond lengths, with the electronic ground state of the copper complex.

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Main Methods:

  • Single crystal X-ray diffraction was employed to determine the three-dimensional structures of both complexes.
  • The crystal structures were solved and refined using Mo K alpha radiation.
  • Crystallographic data, including unit cell parameters and atomic coordinates, were meticulously analyzed.

Main Results:

  • Both complexes crystallized in the monoclinic space group P2(1)/c, indicating isostructural behavior.
  • The metal ions (M = Cu(II) in (1), Zn(II) in (2)) are coordinated by five nitrogen atoms in a distorted trigonal bipyramidal geometry.
  • While equatorial M--N distances were similar, axial M--N distances exhibited significant differences between the copper and zinc complexes, with axial contraction observed in the copper complex.

Conclusions:

  • The structural analysis confirms the distorted trigonal bipyramidal coordination in both copper(II) and zinc(II) complexes.
  • The observed axial M--N bond length differences are attributed to the electronic configuration of the metal ions.
  • The axial contraction in the copper complex (1) is consistent with a dz2 ground state, providing valuable insights into its electronic structure.