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The Periodate-Based Double Perovskites M2NaIO6 (M = Ca, Sr, and Ba)

Author:
Kubel, Frank  Wandl, Nicole  Pantazi, Mariana  D'Anna, Vincenza  Hagemann, Hans  


Journal:
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE


Issue Date:
2013


Abstract(summary):

The crystal structures of the M2NaIO6 series (M = Ca, Sr, Ba), prepared at 650 degrees C by ceramic methods, were determined from conventional laboratory X-ray powder diffraction data. Synthesis and crystal growth were made by oxidizing I with O2(air) to I7+ followed by crystal growth in the presence of NaF as mineralizator, or by the reaction of the alkali-metal periodate with the alkaline-earth metal hydroxide. All three compounds are insoluble and stable in water. The barium compound crystallizes in the cubic space group Fm3m (no. 225) with lattice parameters of a = 8.3384(1) angstrom, whereas the strontium and calcium compounds crystallize in the monoclinic space group P21/c (no. 14) with a = 5.7600(1) angstrom, b = 5.7759(1) angstrom, c = 9.9742(1) angstrom, = 125.362(1)degrees and a = 5.5376(1) angstrom, b = 5.7911(1) angstrom, c = 9.6055(1) angstrom, = 124.300(1)degrees, respectively. The crystal structure consists of either symmetric (for Ba) or distorted (for Sr and Ca) perovskite superstructures. Ba2NaIO6 contains the first perfectly octahedral [IO6]5 unit reported. The compounds of the ortho-periodates are stable up to 800 degrees C. Spectroscopic measurements as well as DFT calculations show a reasonable agreement between calculated and observed IR- and Raman-active vibrations.


Page:
892---898


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