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Spatial Separation of Covalent, Ionic, and Metallic Interactions in Mg11Rh18B8 and Mg3Rh5B3

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Alekseeva,  Anastasia M.
Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Leithe-Jasper,  Andreas
Andreas Leithe-Jasper, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Schnelle,  Walter
Walter Schnelle, Inorganic Chemistry, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Prots,  Yuri
Yuri Prots, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Grin,  Yuri
Juri Grin, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Citation

Alekseeva, A. M., Abakumov, A. M., Leithe-Jasper, A., Schnelle, W., Prots, Y., Van Tendeloo, G., et al. (2013). Spatial Separation of Covalent, Ionic, and Metallic Interactions in Mg11Rh18B8 and Mg3Rh5B3. Chemistry - A European Journal, 19, 17860-17870. doi:10.1002/chem.201301512.


Cite as: https://hdl.handle.net/11858/00-001M-0000-0017-F388-A
Abstract
The crystal structures of Mg11Rh18B8 and Mg3Rh5B3 have been investigated by using single-crystal X-ray diffraction. Mg11Rh18B8: space group P4/mbm; a=17.9949(7), c=2.9271(1)angstrom; Z=2. Mg3Rh5B3: space group Pmma; a=8.450(2), b=2.8644(6), c=11.602(2)angstrom; Z=2. Both crystal structures are characterized by trigonal prismatic coordination of the boron atoms by rhodium atoms. The [BRh6] trigonal prisms form arrangements with different connectivity patterns. Analysis of the chemical bonding by means of the electron-localizability/electron-density approach reveals covalent BRh interactions in these arrangements and the formation of BRh polyanions. The magnesium atoms that are located inside the polyanions interact ionically with their environment, whereas, in the structure parts, which are mainly formed by Mg and Rh atoms, multicenter (metallic) interactions are observed. Diamagnetic behavior and metallic electron transport of the Mg11Rh18B8 and Mg3Rh5B3 phases are in agreement with the bonding picture and the band structure.