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, CH(5)N(2) (+)·I(3) (−), crystallizes in the triclinic space group P [Image: see text] at a temperature of 110 K. The structure consists of two independent isolated triiodide ions located on inversion centers. The centrosymmetric character of I(3) (−) was additionally confirmed by the observed pronounced peaks of symmetrical oscillations of I(3) (−) 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).