Home Crystal structure of Ga0.47(1)Sb0.53(1)Pd2
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Crystal structure of Ga0.47(1)Sb0.53(1)Pd2

  • Oksana Matselko EMAIL logo , Ulrich Burkhardt , Yuri Grin and Roman Gladyshevskii
Published/Copyright: November 21, 2017

Abstract

Ga0.47(1)Sb0.53(1)Pd2, hexagonal, P6̄2m (no. 189), a = 7.0374(3) Å, c = 3.3194(2) Å, V = 142.37(2) Å3, Z = 3, Rp = 0.0269, Rwp = 0.0417, T = 295 K.

CSD no.: 433695

Table 1:

Data collection and handling.

Sample, setting:Grey powder, transmission geometry
Wavelength, μ:Cu 1 radiation, (1.54056 Å), 213.8 mm−1
Diffractometer, scan mode:Huber Guinier G670, fixed (0.005°)
2θ range / data points:24°–100.3°, 15261
Profile function:Pseudo-Voigt
No(hkl), N(param):44, 20
Programs:WinCSD [7], Diamond [8]
Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

AtomxyzBiso*/Beq
Pd10.2698(4)001.89(10)
Pd20.6163(5)00.51.79(9)
Ga1a000.52.4(2)
Sb1b000.52.4(2)
Ga2c0.333330.6666602.00(12)
Sb2d0.333330.6666602.00(12)
  1. aOccupancy: 0.72(2), bOccupancy: 0.28(2), cOccupancy: 0.35(2), dOccupancy: 0.65(2).

Source of materials

Ga0.47(1)Sb0.53(1)Pd2 was synthesized from elemental palladium (granules, ChemPur, 99.95%), gallium (pellets, ChemPur, 99.9999%) and antimony (shots, ChemPur, 99.9999%) by arc melting in a glove box (Ar atmosphere; O2 and H2O content below 1 ppm). Placed in an alumina crucible and evacuated in a quartz glass tube, the sample with a nominal composition Ga15Sb18Pd67 was annealed at 1123 K (48 h) and then at 773 K (408 h). According to XRPD analysis, the main phase in the annealed and quenched from 773 K sample was identified like a new ternary one.

Experimental details

The crystal structure of Ga0.47(1)Sb0.53(1)Pd2 was refined from XRPD data.

Comment

The new ternary compound Ga0.47(1)Sb0.53(1)Pd2 crystallizes in the Fe2P-type of structure [1]. Isostructural Pd-containing phases are known in the systems with phosphorous – Pd2Al0.5P0.5 and Pd2Ga0.4P0.6 [2], while the phases Pd2Al0.33As0.67, and Pd2Ga0.45As0.55, Pd2In0.33As0.67, Pd2Tl0.45As0.55 [3] are solid solutions of Al, Ga, In, and Tl in the binary Pd2As (high-temperature modification; Fe2P-type of structure) [4]. Preliminary information about this substance was reported in [5].

In the structure of Ga0.47(1)Sb0.53(1)Pd2 palladium atoms are located in the sites occupied by iron in the prototype structure, whereas gallium and antimony atoms are situated in the positions of phosphorous.

The crystal structure of the new ternary compound is built up by two types of linked trigonal prisms Pd6 that form columns along the [001] crystallographic direction and are centered by Ga and Sb atoms.

Taking into account the atomic environment of the palladium atoms (the shortest contacts are to the Ga and Sb atoms and the closest Pd–Pd distances, in comparison with elemental palladium, are increased significantly (2.919(2) Å and 2.74 Å, respectively), the title compound, in analogy to the binary Ga–Pd compounds [6], is a potential candidate for the catalytic application in the selective semi-hydrogenation of acetylene in the excess of ethylene.

Acknowledgements

We gratefully acknowledge Dr. Horst Borrmann, Dr. Yurii Prots, and Mr. Steffen Hückmann for XRPD experiments. OM is thankful to Dr. Lev Akselrud for help during crystal structure refinement.

References

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Received: 2017-6-23
Accepted: 2017-10-18
Published Online: 2017-11-21
Published in Print: 2018-1-26

©2018 Oksana Matselko et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 License.

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