2‐(2′‐Pyridyl)indole acts as an N,N‐bidentate ligand when deprotonated and forms (1‐amido‐4‐imine)metallacycles with ReI, RuII, RhIII and IrIII. The crystal structures of 2‐(2′‐pyridyl)indole and the complexes [Re(C13H9N2)(CO)2(PPh3)2], [Ru(C13H9N2)(η6‐C6Me6)Cl], [Rh(C13H9N2)(η5‐C5Me5)Cl] and [Ir(C13H9N2)(η5‐C5Me5)Cl] are presented and their spectra discussed. This provides a foundation for the increased use of this ligand, which is a prototype of a monoanionic, bidentate N,N‐chelating ligand. The introduction of negatively charged N,N‐bidentate ligands can increase the possibility of synthesising complexes tailored to catalysis and other applications. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)