We present the synthesis and characterization of (15-crown-5)BiI3 (1) ⋅ 0.5TIE (2), a halogen bonded adduct with tetraiodoethylene (TIE), typical bond donor. Single crystal structure analysis 2 suggests bonding interaction between crown ether complex TIE. The two compounds’ thermal, optical vibrational properties are investigated in comparison, differences pointing towards notable building bloc...