American Chemical Society
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Synthesis, Crystal Structure, and Properties of MgxB50C8 or Mgx(B12)4(CBC)2(C2)2 (x = 2.4−4)

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journal contribution
posted on 2010-10-06, 00:00 authored by Volker Adasch, Melanie Schroeder, Dominik Kotzott, Thilo Ludwig, Natascha Vojteer, Harald Hillebrecht
Single crystals of a new magnesium boride carbide MgxB50C8 (x = 2.4−4) were synthesized from the elements in a metallic melt using tantalum ampules. Crystals were characterized by single crystal X-ray diffraction and electron microprobe analysis. The variation of the Mg content results from different reaction conditions. The composition Mg∼3B50C8 is by far the most favored. It fulfills the electron counting rules of Wade and Longuet-Higgins and thus explains the light-green to yellow transparent color. The structure of Mg∼3B50C8 (C2/m, Z = 1, a = 8.9384(12) Å, b = 5.6514(9) Å, c = 9.6021(13) Å, β = 105.86(1)°) consists of B12 icosahedra. The icosahedra are interconnected by four exohedral B−B bonds to layers. The layers are connected to a three-dimensional covalent network by C2 and CBC units and further exohedral B−B bonds. The Mg sites are partially occupied. Different site occupation factors cause the various compositions and colors (Mg2.4B50C8, brown; Mg4B50C8, black). The vibrational spectra show the modes of B12 icosahedra and C2 and CBC units as well. Measurements of the microhardness according to Vickers and Knoop revealed remarkably high values of HV = 3286 (32.0 GPa) and HK = 3165 (31.5 GPa), which exceed the values of B4C. Optical spectra reveal a band gap of 2.7 eV for Mg∼3B50C8, in agreement to the observed color. This justifies an ionic description, and the formula can be written as (Mg2+)3(B122−)4(CBC+)2(C2)2.