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 the information needed for the deep-sea sequestration of CO2. The guest disorder and dynamics are discussed in terms of the model derived from earlier NMR data.

Structural determination of crystalline powders, especially those of complex materials, is not a trivial task. For non-stoichiometric guest-host materials, the difficulty lies in how to determine dynamical disorder and partial cage occupancies of the guest molecules without other supporting information or constraints. Here, we show how direct space methods combined with Rietveld analysis can be applied to a class of host-guest materials, in this case the clathrate hydrates. We report crystal structures in the three important hydrate crystal classes, sI, sII, and sH, for the guests CO 2 ,C 2 H 6 ,C 3 H 8 , and methylcyclohexane + CH 4 . The results obtained for powder samples are found to be in good agreement with the experimental data from single crystal X-ray diffraction and 13 C solid-state NMR spectroscopy. This method is also used to determine the guest disorder and cage occupancies of neohexane and tert-butyl methyl ether binary hydrates with CH 4 in the structure H clathrate hydrates. The results are found to be in good agreement with the results from the 13 C solid-state NMR and molecular dynamics simulations. It is demonstrated that the ab initio crystal structure determination methodology reported here is able to determine absolute cage occupancies and the dynamical disorder of guest molecules in clathrate hydrates from powdered crystalline samples.

A single crystal of a low density form of guest-free p-tert-butylcalix[4]arene can take up and release small guest molecules by controlling the temperature and pressure without changing the structure. Using NMR spectroscopy with flowing hyperpolarized xenon, we have shown that at room temperature access of xenon to the pore system is difficult, whereas it is relatively easy at 100 degrees C. There are good prospects for simple van der Waals materials such as the title material to be used as programmable zeolite mimics.

The hydrate of bromine was one of the first clathrate hydrates discovered. It has played a significant role in the development of the solid solution theory of clathrate hydrates, yet its detailed structure remains unknown. This hydrate again has become a test case for two different views of clathrates:  the solid solution model, after van der Waals and Platteeuw, that sees clathrates as unstable lattices which derive stability from a minimum degree of cage filling and thus are nonstoichiometric, and a view promoted by Dyadin and Aladko that all large cages in a hydrate structure need to be filled. In light of the latter view, existing data obtained over the last ∼160-year period on the composition and morphology of bromine hydrate would require the existence of four different hydrate structures. Our single crystal diffraction study of 16 different crystals of distinct compositions (Br2·8.62H2O to Br2·10.68H2O) and morphologies showed that there is just a single structure (tetragonal, P42/mnm, a = 23.04 Å, c = 12.07 Å, the structure originally proposed by Allen and Jeffrey) with considerable variation in the degree of occupancy of the large cages. The results favor the solid solution model for clathrates, and settle the question of long standing regarding the structure(s) of bromine hydrate. The bromine atoms occupy the large 14- and 15-hedral cages with up to 15 different crystallographically independent sites per cage and fractional occupancies from 0.19 to <∼0.01. The bromine hydrate structure is unique, so far. 129Xe NMR results suggest that when attempts were made to produce a double hydrate of bromine and xenon, a transient cubic structure II hydrate resulted, which slowly converted to the tetragonal form.

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There is interest in the role of ammonia on Saturn's moons Titan and Enceladus as the presence of water, methane, and ammonia under temperature and pressure conditions of the surface and interior make these moons rich environments for the study of phases formed by these materials. Ammonia is known to form solid hemi-, mono-, and dihydrate crystal phases under conditions consistent with the surface of Titan and Enceladus, but has also been assigned a role as water-ice antifreeze and methane hydrate inhibitor which is thought to contribute to the outgassing of methane clathrate hydrates into these moons' atmospheres. Here we show, through direct synthesis from solution and vapor deposition experiments under conditions consistent with extraterrestrial planetary atmospheres, that ammonia forms clathrate hydrates and participates synergistically in clathrate hydrate formation in the presence of methane gas at low temperatures. The binary structure II tetrahydrofuran + ammonia, structure I ammonia, and binary structure I ammonia + methane clathrate hydrate phases synthesized have been characterized by X-ray diffraction, molecular dynamics simulation, and Raman spectroscopy methods.ice | single crystal X-ray diffraction | hydrogen bonding | hydrate inhibitors | ethane A mmonia has long been seen as a key species in extraterrestrial space, both interstellar and on outer planets, moons, and comets and the interplay of ammonia, methane, and water has been the subject of a considerable number of studies and speculation (1-8). The main role assigned to ammonia has been that of an antifreeze for ice and clathrate hydrate formation, modifying the stability region of the solid ice and methane clathrate hydrate phases as a thermodynamic inhibitor (2, 5, 9). However, ammonia is a methane-sized molecule, thus based on size alone it has the potential for being a suitable guest for clathrate hydrate cages. Issues that may have prevented ammonia from being considered as a suitable clathrate guest molecule include the notion that guest species need to be hydrophobic in order to be incorporated into clathrates, and the observation of a number of stoichiometric nonclathrate phases of ammonia and water obtained upon cooling aqueous ammonia solutions (2). Previous experimental work on the water-ammonia and water-methaneammonia systems had not shown evidence for the enclathration of ammonia (5,(10)(11)(12)(13)(14)(15)(16)(17)(18)(19). Close inspection, however, shows that the low pressure ammonia dihydrate (18) and the high pressure phase II of ammonia monohydrate (19) have structural features in common with canonical clathrate and semiclathrate structures.Recent structural analysis and molecular simulations have shown that some guest molecules which form strong hydrogen bonds with the water framework of the clathrate hydrate lattice may nonetheless produce stable phases (20-23). It is therefore reasonable to consider that ammonia has potential as a clathrate guest molecule. Furthermore, previous experimental and computational studies hav...

To provide improved understanding of guest–host interactions in clathrate hydrates, we present some correlations between guest chemical structures and observations on the corresponding hydrate properties. From these correlations it is clear that directional interactions such as hydrogen bonding between guest and host are likely, although these have been ignored to greater or lesser degrees because there has been no direct structural evidence for such interactions. For the first time, single‐crystal X‐ray crystallography has been used to detect guest–host hydrogen bonding in structure II (sII) and structure H (sH) clathrate hydrates. The clathrates studied are the tert‐butylamine (tBA) sII clathrate with H2S/Xe help gases and the pinacolone + H2S binary sH clathrate. X‐ray structural analysis shows that the tBA nitrogen atom lies at a distance of 2.64 Å from the closest clathrate hydrate water oxygen atom, whereas the pinacolone oxygen atom is determined to lie at a distance of 2.96 Å from the closest water oxygen atom. These distances are compatible with guest–water hydrogen bonding. Results of molecular dynamics simulations on these systems are consistent with the X‐ray crystallographic observations. The tBA guest shows long‐lived guest–host hydrogen bonding with the nitrogen atom tethered to a water HO group that rotates towards the cage center to face the guest nitrogen atom. Pinacolone forms thermally activated guest–host hydrogen bonds with the lattice water molecules; these have been studied for temperatures in the range of 100–250 K. Guest–host hydrogen bonding leads to the formation of Bjerrum L‐defects in the clathrate water lattice between two adjacent water molecules, and these are implicated in the stabilities of the hydrate lattices, the water dynamics, and the dielectric properties. The reported stable hydrogen‐bonded guest–host structures also tend to blur the longstanding distinction between true clathrates and semiclathrates.