Friday, 6 October 2006 - 4:30 PM
Endicott Ballroom (Holiday Inn Binghamton - Arena)
296

Structure and magnetic behavior of bis(2-amino-5-fluoropyridinium)tetrachlorocuprate(II)

Lixin Li1, Mark M. Turnbull1, Christopher P. Landee1, Merce Deumal2, and Juan J. Novoa2. (1) Clark University, Worcester, MA, (2) University of Barcelona, Barcelona, Spain

Abstract: The study of the mechanism for magnetic exchange has been a major area of research for more than two decades. One proposed mechanism involves non-bonding halide-halide bridges such as M-X…X-M super-exchange interaction. We have been studying compounds that exhibit this type of exchange, especially the family (5SAP)2CuX4 (where 5SAP is a 5-substituted-2-aminopyridium and X=Cl, Br). The reaction of CuCl2 with 2-amino-5-fluoro-pyridine and HCl in aqueous solution yields bis(2-amino-5-fluoropyridinium) tetrachlorocuprate(II) (5FAP)2CuCl4 (1). The complex crystallizes in the monoclinic space group P21/c, with a cell dimensions a=6.9262 Å, b=21.7306 Å, c=10.9115 Å, b=100.190°, V=1616(3) Å3;R1=0.0424 based on 2640 independent reflections. The crystal packing shows that each tetrachlorocuprate ion has three near-neighbor Cu(II) ions through three Cu-Cl…Cl-Cu potential super-exchange interactions, with one short Cl…Cl distance (a=3.657) Å and two longer Cl…Cl distance (b=4.073 Å), forming a distorted honeycomb structure. Both powder and single crystal magnetic susceptibility measurements on 1 over the temperature range of 1.8-325 K, show significant antiferromagnetic interactions. Attempts to analyze the data using a variety of models showed a best fit to the strong-rung ladder model, with Jrung =17.6 K and Jrail= 4.8 K, even though that model does not agree with the packing structure. Ab initio calculations based on the crystal structure have been performed to understand the nature of exchange in the material and the relationship between the magnetic and crystal lattices.


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