Halogenido Analogues of Structuraly Diverse Complexes With 3-Hydroxypyridine
Primož Šegedin,1,* Urška Dolničar,1 Mirzet Čuskić,1 Zvonko Jagličić,2 Amalija Golobič1 and Bojan Kozlevčar1
1 Faculty of Chemistry and Chemical Technology, University of
Ljubljana, 1000 Ljubljana, Slovenia
2 Institute of Mathematics, Physics and Mechanics & Faculty of Civil
and Geodetic Engineering, University of Ljubljana, 1000 Ljubljana, Slovenia
* Corresponding author: E-mail:
primoz.segedin@fkkt.uni-lj.si
Tel.: 00 386 1 2419 122; Fax: 00 386 1 2419 220
Abstract
Two types of bromido and chlorido complexes with 3-hydroxypyridine (3-pyOH),
namely, [CuX2(3-pyOH)4] (1, 2) type A, and [Cu(µ-X)2(3-pyOH)2]n
(3, 4) type B (X = Br, Cl) were prepared. The X-ray single crystal
structure determination of the mononuclear [CuBr2(3-pyOH)4]
1 reveals octahedral coordination with four nitrogen atoms of 3-pyOH
molecules in the equatorial plane and two bromido anions in the axial positions.
A structure of the type A chlorido analogue [Cu- Cl2(3-pyOH)4]
2 was determined by a combination of the powder and the single crystal
diffraction data. The molecular structure of the type B bromido complex [Cu(µ-Br)2(3-pyOH)2]n
3 was also determined from the single crystal XRD data. Herein, infinite
linear chains of catena-di-µ-bromidobis(3-pyOH)copper(II) are present. A
comparison of the powder diffraction data of compounds [Cu(µ-X)2(3-pyOH)2]n
3 and 4, together with their results of IR, UV-Vis and magnetic
methods show, that both compounds 3 and 4 can be assigned as the type B, due to
their probably very similar molecular structure. The magnetic susceptibility of
the type A mononuclear complexes shows a paramagnetic behaviour in the range
2–300 K with a constant χM · T value. On the other hand, a broad
maximum of the curve χM versus T below 50 K for the type B
polynuclear complexes, reveals the antiferromagnetic interaction between the
copper(II) S = ½ magnetic moments. These data were fitted by the Bonner-Fisher
curve (1D Heisenberg antiferromagnet) giving J –17 cm–1 (3),
–10 cm–1 (4). The paramagnetic behaviour of the polynuclear
complexes 3, 4, noticed from the room temperature EPR spectra, is
in agreement with the spin of copper(II), and the rhombic distortion of the spin
tensor close to the axial symmetry.
Keywords: Copper(II), halogenide, 3-hydroxypyridine, polymer, monomer, antiferromagnet