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Synthesis, Crystal Structure, and EPR Studies of the Five-Coordinate [CuCl3(H2O)2]- Complex in (dabcoH2)2Cl3[CuCl3(H2O)2]·H2O

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journal contribution
posted on 23.10.1996, 00:00 by Mingyi Wei, Roger D. Willett
The compound (dabcoH2)2Cl3[CuCl3(H2O)2]·H2O, where dabco = 1,4-diazabicyclo[2.2.2]octane, has been synthesized, its structure has been determined by single-crystal structural analysis, and its properties have been investigated by powder and single-crystal EPR spectroscopy. The compound crystallizes in space group Pnma at room temperature with unit cell dimensions of a = 15.227(1) Å, b = 7.467(1) Å, and c = 20.166(2) Å with Z = 4. The structure was solved by the Patterson method and refined by full-matrix least-squares to R = 4.3% for 1681 observed reflections (I > 2σ(I)). The [CuCl3(H2O)2]- anion exists with a slightly distorted trigonal bipyramidal geometry in which the three Cl atoms lie in equatorial positions and the two water molecules are in axial positions. The distortion appears to be driven by the presence of N−H···Cl hydrogen bonds. The EPR spectra are also consistent with the presence of only a small distortion from trigonal bipyramidal geometry since g1g2 > g3 ≈ 2.0. Analysis of the geometry indicates the distortion consists primarily of a “negative” C2v type. Analysis of the thermal parameters supports the supposition that the observed geometry corresponds to disorder over two “positive” C2v distortions.