Synthesis,Crystal Structure and Spectroscopy of <Emphasis Type="Italic">catena-</Emphasis>poly-bis(azido-<Emphasis Type="Italic">N1,N1</Emphasis>)(2-Aminopyrimidine)Copper(II) |
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Authors: | Gerard A van Albada Maarten G van der Horst Ilpo Mutikainen Urho Turpeinen Jan Reedijk |
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Institution: | (1) Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands;(2) Laboratory of Inorganic Chemistry, Department of Chemistry, University of Helsinki, P.O. Box 55, A.I. Virtasen aukio 1, 00014 Helsinki, Finland |
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Abstract: | Abstract The compound Cu(ampym)(μ1,1-N3)2]n (ampym = 2-aminopyrimidine) has been synthesized and characterized by X-ray crystallography and infrared spectroscopy. In
addition, Ligand Field and powder EPR measurements have been performed. The structure is solved in space group P21/c with
a = 7.303(2), b = 19.716(4), c = 5.949(1) ?, β = 98.17(3), V = 847.9(3) ?3, Z = 2 with final R = 0.0382. The coordination geometry around the Cu(II) ion is distorted square pyramidal, with four nitrogen
atoms of four bridging azido anions in the basal plane with Cu–N distances that range from 1.998(3) to 2.069(3) ?. The apical
position is occupied by a nitrogen atom of the ampym molecule at a Cu–N distance of 2.169(3) ?. The trans-basal angles are
165.7(1) and 143.9(1)°. Weak hydrogen bonding is observed between the two amine hydrogen atoms and nitrogen of an azide anion
and the pyrimidine-ring nitrogen atom of a neighbouring molecule (N···N distances 3.174(5), 3.106(4) ?). These last hydrogen
bonds (N7···N3) are forming so-called “Watson-Crick type” hydrogen bonds. In the infrared the vibrations of the coordinated
azide anion are observed at 2,062, 1,273 and 655 cm−1, while the Cu–N vibrations are observed at 370 and 224 cm−1. Ligand-field and EPR spectra are uneventful and give spectral parameters expected in the range for such Cu(II) compounds.
Magnetic susceptibility measurements reveal a weak antiferromagnetic interaction between the Cu(II) ions.
Index Abstract A new Cu(II) compound, Cu(2-aminopyrimidine)(μ1,1-N3)2]n has been synthesized and characterized by X-ray crystallography and by IR, Ligand Field, EPR spectroscopy and magnetic susceptibility.
The coordination geometry around the Cu(II) ion is distorted square pyramidal, with four nitrogen atoms of four bridging azido
ligands in the basal plane with Cu–N distances that range from 1.998(3) to 2.069(3) ?. The apical position is occupied by
a nitrogen atom of the ampym molecule at a Cu–N distance of 2.169(3) ?. Also a very interesting hydrogen bond system occurs
between pairs of ligands in the lattice.
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Keywords: | Copper 2-Aminopyrimidine Azide Infrared Hydrogen bonding |
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