Structures of Fe(II) spin-crossover complexes from synchrotron powder-diffraction data
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Published on: August 22, 2017
Eva Dova1, René Peschar, Makoto Sakata
1University of Amsterdam, Faculty of Science, van 't Hoff Institute for Molecular Sciences, Laboratory for Crystallography, Nieuwe Achtergracht 166, NL-1018 WV Amsterdam, The Netherlands. eva@science.uva.nl
Abstract:
Crystal structure determination and analysis have been carried out for the two spin-crossover compounds [Fe(teeX)(6)](BF(4))(2) (teeX is haloethyltetrazole; X = I: teei; X = Br: teeb), in both their high-spin (near 300 K) and their low-spin states (T = 90 K), using high-resolution powder-diffraction data collected at the ESRF (Grenoble, France) and SPring8 (Japan) synchrotron radiation facilities. The structures of teei have been solved using various direct-space structure determination techniques (grid search, genetic algorithm and parallel tempering) and refined with the Rietveld method using geometrical restraints. In the case of teeb, a structural model was found but a full refinement was not successful because of the presence of a significant amount of an amorphous component. Analysis of the structures (space group P2(1)/c, Z = 2) and diffraction data, and the absence of phase transitions, show the overall structural similarity of these compounds and lead to the conclusion that the gradual spin-crossovers are likely to be accompanied by small structural changes only.
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