Due to the weak oxidative force of N2 , nitrides are only typically formed with the less electronegative metals. Meeting this challenge, we here present Pb2 Si5 N8 , the first nitridosilicate containing highly electron-affine cations of a metal from the right side of the Zintl border. By using advanced synchrotron X-ray diffraction, the crystal structure was determined from a tiny single crystal of 1×3×3 μm3 in size, revealing a significantly different bonding situation compared to all other nitridosilicates known so far. Indeed, DFT calculations confirm distinct amounts of covalency not only between Pb and N but also between formal Pb2+ cations. Thus, unprecedented cationic Pb2 dumbbells with a stretching vibration at 117 cm-1 were found in Pb2 Si5 N8 , the first representative of a crystallographically elucidated lead nitride, stabilized by high amounts of covalency.
Keywords: X-ray diffraction; density functional calculations; lead; nitrides; raman spectroscopy.
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