The crystal structure of the newly synthesized 4-methoxyphenyl(phenyl)iodonium thiocyanate, [PhI(4-C₆H₄OMe)](SCN), represents the first example of 16-membered cyclic heterooctamer formed by halogen bonding between the iodonium cation and SCN⁻. Results of density functional theory (DFT) calculations followed by the topological analysis of the electron density distribution within the framework of the quantum theory of atoms in molecules (QTAIM) method at the ωB97XD/DZP-DKH level of theory reveal that energies of attractive intermolecular noncovalent interactions I···S and I···N (responsible for the formation of heterooctameric supramolecular clusters {PhI(4-C₆H₄OMe)}₄·{SCN}₄ in the solid state structure of [PhI(4-C₆H₄OMe)](SCN)) vary from 0.9 to 8.5 kcal/mol.