Crystal structure of new formamidinium triiodide jointly refined by single-crystal XRD, Raman scattering spectroscopy and DFT assessment of hydrogen-bond network features

A novel triiodide phase of the formamidinium cation, CH₅N₂ ⁺·I₃ ⁻, crystallizes in the triclinic space group P\overline{1} at a temperature of 110 K. The structure consists of two independent isolated triiodide ions located on inversion centers. The centrosymmetric character of I₃ ⁻ was additionally confirmed by the observed pronounced peaks of symmetrical oscillations of I₃ ⁻ at 115–116 cm⁻¹ in Raman scattering spectra. An additional structural feature is that each terminal iodine atom is connected with three neighboring planar formamidinium cations by N—H...I hydrogen bonding with the N—H...I bond length varying from 2.81 to 3.08 Å, forming a deformed two-dimensional framework of hydrogen bonds. A Mulliken population analysis showed that the calculated charges of hydrogen atoms correlate well with hydrogen-bond lengths. The crystal studied was refined as a three-component twin with domain ratios of 0.631 (1):0.211 (1):0.158 (1).