Hydrogen Bonding in Phosphonium Iodide: A Neutron-Diffraction Study

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Abstract
A three-dimensional single-crystal neutron-diffraction study of phosphonium iodide, PH4I, has confirmed the presence of weak P–H···I hydrogen bonds in this system. Each iodine is surrounded by four hydrogen atoms at a normal van der Waals contact distance of 3.35 Å and four others at a hydrogen-bond distance of 2.87 Å. The P–H bond length is 1.414 Å (σ0.008 Å), and the P–H···I angle is 171.6°. The thermal motion parameters derived from the diffraction study lead to a predicted librational frequency of 246 cm−1 in comparison with a value of 335 cm−1 observed by Rush in a neutron-inelastic-scattering experiment. This agreement may be considered good in view of the fact that crystal energy calculations reported here indicate that the barrier to rotation is possibly extremely anharmonic with a very high barrier height. That the potential curve is dominated by the repulsive term rather than the electrostatic term is strong evidence that the hydrogen bond is weak.