Pattern of covalent and non‐covalent interactions within the pentaiodide anion in the structure of (3‐HOC5H9NH2)I5

3-Hydroxypiperidinium pentaiodide was synthesized by a facile reaction in concentrated aqueous HI. Its crystal structure comprises 3-hydroxypiperidinium cations and pentaiodide anions, the latter having geometry of cis-shaped chains composed of I2 and I3− building units. The analysis of interatomic distances, Raman spectroscopy data, and results of DFT calculations, including non-covalent interaction analysis, showed that the title compound exhibits a complex pattern of covalent and non-covalent interactions. Those include I−I covalent bonds and I⋅⋅⋅I halogen bonds within the I5− anion as well as (N)H⋅⋅⋅I and (O)H⋅⋅⋅I hydrogen bonds and even weaker (C)H⋅⋅⋅I van-der-Waals interactions between the cations and anions.