Structure, Composition, and Thermal Expansion of CO2 Hydrate from Single Crystal X-ray Diffraction Measurements†

The structure and composition of CO2 hydrate were determined from single-crystal X-ray diffraction data at 173 K for a crystal grown over heavy water and liquid CO2. Superior diffraction data allowed the derivation of a structural model of unprecedented quality for the hydrate, giving the location of the disordered CO2 molecules in the two cages. In the large cage, the guests are shown to be off-center, with a bimodal distribution of out-of-plane orientations for the long axis of the molecule (173 K). Also, the absolute cage occupancies were determined from the structural model, thus allowing a reliable and direct evaluation of the hydrate composition for this crystal, CO2·6.20(15) D2O. The temperature dependence of the lattice parameters for the single crystal was measured between 123 and 223 K and found to be in good agreement with recent neutron powder diffraction results, and data from all sources were fit to a single polynomial function. The hydrate composition and density are discussed in terms of t...