The arsenides LnPd{sub 3}As{sub 2} (Ln = La-Nd, Sm, Gd) and structure refinement of CePd{sub 2-x}As{sub 2} with the ThCr{sub 2}Si{sub 2} structure
- Universitaet Muenster (Germany)
The title compounds were prepared in well-crystallized form by annealing the corresponding binary arsenides in a NaCl/KCl flux. The compounds LnPd{sub 3}As{sub 2} crystallize with a new monoclinic structure type, which was determined from single-crystal X-ray data of GdPd{sub 3}As{sub 2}: C2/m, a = 1656.3(6) pm, b = 404.6(2) pm, c = 993.7(4) pm, {beta} = 107.85(2){degrees}, Z = 6, R = 0.025 for 1728 structure factors and 58 variable parameters. These arsenides belong to a large structural family with a metal to metalloid ratio of 2:1. Somewhat unusual features in the structure of GdPd{sub 3}As{sub 2} are the (distorted) octahedral coordination of one gadolinium site and the square-planar coordination of arsenic atoms around two palladium sites. All of these, however, are also observed for the corresponding atoms in the previously reported, closely related structure of Th{sub 5}Fe{sub 19}P{sub 12}. CePd{sub 2-x}As{sub 2} has the tetragonal ThCr{sub 2}Si{sub 2} structure (a = 425.1(2) pm, c = 1026.1(6)pm, R = 0.023 for 244 F values and 11 variables) with an As-As distance of 247.1(1) pm. The refinement of the occupancy parameter of the palladium position resulted in a value of 87.9(2)% corresponding to the formula CePd{sub 1.758(4)}As{sub 2}. It is argued that the formation of these defects reduces antibonding (destabilizing) Pd-Pd interactions.
- OSTI ID:
- 508675
- Journal Information:
- Journal of Solid State Chemistry, Vol. 115, Issue 1; Other Information: PBD: 15 Feb 1995
- Country of Publication:
- United States
- Language:
- English
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