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Bi2Pt(hP9) by Low-Temperature Reduction of Bi13Pt3I7: Reinvestigation of the Crystal Structure and Chemical Bonding Analysis

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Baranov,  Alexey I.
Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Ruck,  M.
Michael Ruck, Max Planck Fellow, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Citation

Kaiser, M., Baranov, A. I., & Ruck, M. (2014). Bi2Pt(hP9) by Low-Temperature Reduction of Bi13Pt3I7: Reinvestigation of the Crystal Structure and Chemical Bonding Analysis. Zeitschrift für anorganische und allgemeine Chemie, 640(14), 2742-2746. doi:10.1002/zaac.201400331.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0024-9C07-7
Abstract
Bi2Pt(hP9) or -Bi2Pt is a high-temperature modification, which is metastable below 420 degrees C. We obtained Bi2Pt(hP9) by reducing the layered bismuth subiodide Bi13Pt3I7 with a high excess of n-butyllithium at 70 degrees C. The crystals endure the heterogeneous reaction and the enormous mass loss. X-ray diffraction on a small single-crystal revealed that Bi2Pt(hP9) crystallizes in the acentric trigonal space group P31m (no. 157) with a = 657.30(7) pm and c = 616.65(7) pm. Although structure and stacking of the layers of edge-sharing [PtBi6/3] octahedra resemble the 1H-polytype of CdI2, Pt-Pt bonding interactions cause distortions that introduce polarity to the structure. Quantum chemical calculations followed by real-space bonding analysis reveal polar covalent bonding between bismuth and platinum atoms that is not limited to nearest neighbor atoms but is essentially delocalized. The Pt-Pt bond strength in Bi2Pt(hP9) is not much weaker than in the element.