A new type of intramolecular H ⋯ H ⋯ H interaction involving N–H ⋯ H(Ir)⋯ H–N atoms. Crystal and molecular structure of [IrH(η 1 -SC 5 H 4 NH) 2 (η 2 -SC 5 H 4 N)(PCy 3 )]BF 4 ·0.72CH 2 Cl 2

The iridium complexes, [Ir[graphic omitted])2(η2-SC5H4N)(PCy3)](BF4), 1, and [Ir[graphic omitted])2(η1-SC5H4NH)2(PCy3)](BF4)2, 2, [Cy = cyclohexyl] in the solid state and in CD2Cl2 solution contain a new type of intramolecular H ⋯ H ⋯ H interaction contained in ten-membered bicyclic rings S–C–N–H ⋯ H(Ir)⋯ H–N–C–S defined by the two-2-pyridiniumthiolate ligands coordinated in a monodentate fashion via sulfur to an iridium atom.