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The crystal structures, magnetic and electrical properties of two polymeric chlorocuprate(II) compounds

Journal of the Chemical Society, Dalton Transactions, ISSN: 1472-7773, Issue: 2, Page: 265-271
1988
  • 30
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Metrics Details

  • Citations
    30
    • Citation Indexes
      30
  • Captures
    7

Article Description

The crystal structures of piperidinium trichlorocuprate(II) [Hpip][CuCl], and piperazinium hexachlorodicuprate(II), [Hpipz][CuCl], have been determined by X-ray diffraction techniques. [Hpip][CuCl] is monoclinic, space group C2/c, with a = 18.385(7), b = 8.439(4), c = 11.878(5) Å, and β = 103.63(5)° while [Hpipz][CuCl] is triclinic, P1, with a = 7.984(4), b = 7.054(4), c = 6.104(3) Å, α = 111.23(8), β = 99.95(9), γ = 81.26(7)°. Both salts contain infinite chains of [CuCl] dimers. The [CuCl] dimers show significant distortions from planarity due to formation of semi-co-ordinate bonds between adjacent dimers, with a larger distortion for the Hpip salt. This bifold distortion gives each copper(II) ion a (4 + 1) co-ordination geometry. The chains have slightly different configurations. In the Hpipz salt, adjacent dimers are related by unit-cell translations, while in the Hpip salt they are related by a c-glide operation. Magnetic susceptibility measurements show that the Hpipz salt is an alternating antiferromagnetic chain with J/k = -13.35(7) K and J′/k = -7.6(3) K, while the Hpip salt is an alternating ferro- antiferro-magnetic chain with J/k = 26(3) K and J′/k = -0.24(1) K. Thus, the intradimer coupling (J) becomes less antiferromagnetic as the distortion from planarity increases. Comparison with other bifolded dimers confirms correlation of J with the bifold angle, both experimentally and theoretically. Electrical measurements reveal the presence of an activated process for electrical conduction with activation parameters of 0.44 eV for [Hpip][CuCl] and 0.34 eV for [Hpipz][CuCl]. The charge carriers are proposed to be the protons in N-H ⋯ Cl hydrogen bonds.

Bibliographic Details

Luigi Pietro Battaglia; Anna Bonamartini Corradi; Urs Geiser; Roger D. Willett; Antonio Motori; Franco Sandrolini; Luciano Antolini; Tiziano Manfredini; Ledi Menabue; Gian Carlo Pellacani

Royal Society of Chemistry (RSC)

Chemistry

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