A small library of 1:1 cocrystals formed on halogen bonding driven self-assembly of α,ω-diiodoperfluoroalkanes with pyridine derivatives is synthesized and characterized through single crystal X-ray analyses. A strict correlation exists between the metrics of the starting tectons and the metrics of the self-assembled architectures. The pitch along the infinite chains, formed on XB driven self-assembly, and the thickness of the fluorocarbon layers, formed due to perfluorocarbon/hydrocarbon segregation, both correlate with the number of difluoromethylene groups in diiodoperfluoroalkanes.