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New Calcium Hydride Halides with Familiar Structures. Syntheses and Crystal Structures of Ca7

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New Calcium Hydride Halides with Familiar Structures.

Syntheses and Crystal Structures of Ca

7

H

12

Cl

2

and Ca

2

H

3

Br

Olaf Reckeweg and Francis J. DiSalvo

Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853-1301, USA

Reprint requests to Dr. Olaf Reckeweg. Fax: +1-607-255-4137. E-mail: or22@cornell.edu Z. Naturforsch.2010,65b,493 – 498; received December 10, 2009

Single crystals of Ca7H12Cl2and Ca2H3Br were obtained by reacting stoichiometric amounts of CaH2 and CaX2 (X = Cl, Br) at 1300 K in the presence of surplus Ca metal for 13 h in silica- jacketed Nb ampoules. The crystal structures of the new compounds were determined by means of single-crystal X-ray diffraction. Ca7H12Cl2crystallizes isotypical to Ba7Cl2F12and Sr7H12Cl2in the hexagonal space groupP¯6 (no. 174) withthe lattice parametersa= 936.51(8),c= 368.65(2) pm, while Ca2H3Br crystallizes in a stuffedanti-CdI2structure isotypical to Ba2H3Cl and therefore adopts the space groupP¯3m1 (no. 164) withthe lattice parametersa= 391.37(6) andc= 697.04(13) pm. The structural results are corroborated by EUTAXcalculations on the title compounds and the compar- ison of these results to those for CaH2, CaX2and CaHX(X = Cl, Br). Similar calculations on the hypothetical compound “Ca7H12Br2” give a possible explanation for the preferred formation of the compound Ca2H3Br.

Key words:Calcium, Halide, Hydride, Structure Elucidation, EUTAXCalculations

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