The dicationic indazole salt 5be was isolated in 30% yield and the benzyl-bridged, seven-membered salt 5bf could not be obtained under our optimized reaction conditions. Single crystal structures of selected salts were obtained to gain a better understanding of the bonding situation and the coordination states in these novel azoiodazinium salts (Figure ). An N4-I1 distance of 2.540 Å with a typical T-shape structure (N4-I1-C1 angle 185.74°) implies a significant interaction between the N-heterocycle and the iodine atom for the ortho-pyrazole substituted derivate 5bb. However, the orthomethyl group significantly disturbs the triflate coordination to the other iodine σ-hole, which results in a C15-I1-O5 angle of 145.50°. In contrast to other cyclic iodonium salts, this molecule is nearly in plane with an I1-C1-C15-N4 dihedral angle of 2.03°. For the dicationic salt 5av, we observe a coordination of the triflates along the C-I axis with 2.705 Å (I1-O1) and 2.898 Å (I1-O5). For the ortho-methyl-protected analogous 5ax, no halogen bonding to the triflates was observed, indicating an effective steric protection of the σ-holes. Instead, there were only two weak interactions with one of the triflates (I1-O3: 3.354 Å, I1-O5, 3.078 Å).