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La2NiSb - A Ternary Ordered Version of the Bi3Ni Type with Highly Polar Bonding

MPG-Autoren
http://pubman.mpdl.mpg.de/cone/persons/resource/persons126823

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

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Zitation

Schäfer, K., Isaeva, A., Ruck, M., Gerke, B., Schwickert, C., & Poettgen, R. (2014). La2NiSb - A Ternary Ordered Version of the Bi3Ni Type with Highly Polar Bonding. Zeitschrift fur Naturforschung Section B-A Journal of Chemical Sciences, 69(11-12), 1097-1104. doi:10.5560/ZNB.2014-4135.


Zitierlink: http://hdl.handle.net/11858/00-001M-0000-0025-B773-4
Zusammenfassung
The lanthanum-rich antimonide La2NiSb was synthesized by annealing a cold-pressed pellet of the elements in a sealed silica glas tube at 1120K. La2NiSb was characterized by powder and single-crystal X-ray diffraction: ordered Bi3Ni type, Pnma, Z = 4, a = 825.6(3), b = 452.2(2), c = 1195.5(4) pm, wR= 0.0695, 856 F-2 values, 26 variables. The nickel atoms form infinite zig-zag chains (259 pm Ni-Ni) with trigonal-prismatic lanthanum coordination for each nickel atom. The antimony atoms cap the rectangular faces of the lanthanum prisms (336 pm La-Sb) and thereby coordinate also the nickel atoms (271 pm Ni-Sb). These rods run parallel to the b axis and form a herringbone pattern, similar to the FeB-type structure of GdNi. Although metallic conductivity is expected for La2NiSb from DFT-based band structure calculations, the real-space bonding analysis shows prominent localization of electrons on antimonide anions and positively charged lanthanum cations. The chain substructure is strongly bonded by polar covalent Ni-Sb and multicenter Ni-Ni interactions. The nickel atoms, which are involved in multicenter bonding with adjacent nickel and lanthanum atoms, provide a conductivity pathway along the prismatic strands. Sb-121 Mossbauer spectroscopic data at 78 K show a single signal at an isomer shift of -7.62(3) mm s(-1), supporting the antimonide character. La2NiSb shows weak paramagnetism with a susceptibility of 2.5 x 10(-3) emu mol(-1) at room temperature.