Abstract: | Red shiny crystals of [Rb(dibenzopyridino‐18‐crown‐6)2]2(I3)(I5) were obtained from a dichloromethane/ethanol solution of RbI, I2 and dibenzopyridino‐18‐crown‐6. Triclinic, , a = 1494.3(1), b = 1534.1(1), c = 2412.9(2) pm, α = 76.95(1), β = 83.58(1), γ = 68.67(1)°, V = 5016.7(7) 106·pm3, Z = 2. The crystal structure consists of [Rb(dbp18c6)2]+ cations leaving suitable three‐dimensional channels for the linear I3− and V‐shaped I5− anions which are isolated from each other. |