The water molecule in crystalline hydrates studied by neutron diffraction

Abstract

A survey of the geometry and environment of water molecules in crystalline hydrates is presented. Histograms and correlation analyses are based on 97 crystal structures accurately determined by neutron diffraction, and include data from 183 water molecules, each donating two hydrogen bonds. The sample is analyzed according to the nature of the hydrogen-bond acceptors and of the coordinated cations. Cases of bifurcated hydrogen bonds are also discussed. The hydrogen bonds tend to be linear and the acceptors tend to be located close to the water plane. The tendency of coordination bonds to be collinear with the direction of one of the lone pairs of the O or their bisector increases with the strength of the bonds. The length of the W-H bond, which, on average, is shorter than in the gas phase, is correlated to the strength of the donated hydrogen bond and to the nature of the acceptor as well as to the type of coordination. On average, W--H is shorter for weaker hydrogen bonds, lower electronegativity of the acceptors and a triangular (as opposed to tetrahedral) type of coordination. The H-W-H angle is, on average, about 2.5 o wider than in the gas phase; this widening is correlated to the type of coordination (larger for triangular), to the strength of the hydrogen bond, and to the A... W...A angle between acceptors. Differences between the dimensions of water molecules in gas and solid phases are shown to be effective and not due to uncorrected thermal effects.