The reaction of NbCl5 and TaCl5 with 7-azaindole (Haza) at room temperature in benzene or dichloromethane yielded MCl5(Haza) addition compounds. Under more severe conditions, the same compound was obtained with TaCl5. For NbCl5, some reduction to Nb(IV) was observed and NbCl5(Haza), NbCl4(Haza)2, and the (H2aza)+ ion were identified in the reaction mixture by infrared spectroscopy. Oxidative coupling of two azaindole units via N7—C6 also took place during the reaction, since the 7-(azaindol-6-yl)azaindolium cation was found as counter-ion in the crystal structures of two complex salts. In the crystals of (H2aza-aza)[NbOCl4(Haza)]•0.5CH2Cl2([Formula: see text]a = 7.255 Å, b = 12.412 Å, c = 14.277 Å, α = 89.03°, β = 85.60°, γ = 76.66°, Z = 2, R = 0.062), the anion is the roughly octahedral [NbOCl4(azaindole)]− species containing a neutral N7-coordinated azaindole trans to the Nb=O bond. The [NbOCl5]2− salt ([Formula: see text]a = 7.527 Å, b = 10.168 Å, c = 10.467 Å, α = 66.41°, β = 84.07°, γ = 85.51°, Z = 1, R = 0.037) contains the distorted octahedral [NbOCl5]2− ion disordered over two orientations. The infrared spectra suggest monomeric octahedral structures for the MCl5(Haza) and NbCl4(Haza)2 complexes. 1H NMR spectroscopy shows that NbCl5(Haza) is not dissociated in CD2Cl2.