The reaction of di-[2]-pyridyl-disulfide (L) with diiodine in molar ratios ranging between 1 : 0.5 and 1 : 5 afforded [(HL+)(I−)·5/2I2] as the only product, containing the first example of a self-assembled infinite polyiodide pseudo-cubic 3D-network featuring distorted square pyramidal I−·5I2 moieties at the nodes.