Cationic Pb 2 Dumbbells Stabilized in the Highly Covalent Lead Nitridosilicate Pb 2 Si 5 N 8

Due to the weak oxidative force of N 2 , nitrides are only typically formed with the less electronegative metals. Meeting this challenge, we here present Pb 2 Si 5 N 8 , 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 μm 3 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 Pb 2+ cations. Thus, unprecedented cationic Pb 2 dumbbells with a stretching vibration at 117 cm −1 were found in Pb 2 Si 5 N 8 , the first representative of a crystallographically elucidated lead nitride, stabilized by high amounts of covalency.