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The electronic structure and bonding of the complex ceramic crystal Y 10 [SiO 4 ] 6 N 2  is studied by a first‐principles method. It is shown that this crystal is an insulator with a direct band gap of 1.3 eV. It has some unique properties related to the one‐dimensional chain structure in the   c  ‐direction and the planar N‐Y bonding in the   x  ‐  y  plane.