Clathrate molecules

HjO, showing the zigzag chains of clathrated molecules K and L and the zigzag stacking of the framework molecules A-J. All twelve TMA molecules are crystallographioally independent. The view is along c with a vertical (taken from Ref. 

Hydrates are solid structures composed of water molecules joined as crystals that have a system of cavities. The structure is stable only if at least one part of the cavities contains molecules of small molecular size. These molecules interact weakly with water molecules. Hydrates are not chemical compounds rather, they are clathrates . 

Clathrate (Section 2 5) A mixture of two substances in which molecules of the minor component are held by van der Waals forces within a framework of molecules of the major component... 

Fig. 26. Clathrate receptor chemistry (a) a chiroselective crystalline host compound (clathrand) (b) a typical guest molecule to be included in the specified configuration and (c) the crystal stmcture of the respective clathrate (A and B denote host and C the guest species) (169).

Urea has the remarkable property of forming crystalline complexes or adducts with straight-chain organic compounds. These crystalline complexes consist of a hoUow channel, formed by the crystallized urea molecules, in which the hydrocarbon is completely occluded. Such compounds are known as clathrates. The type of hydrocarbon occluded, on the basis of its chain length, is determined by the temperature at which the clathrate is formed. This property of urea clathrates is widely used in the petroleum-refining industry for the production of jet aviation fuels (see Aviation and other gas-TURBINE fuels) and for dewaxing of lubricant oils (see also Petroleum, refinery processes). The clathrates are broken down by simply dissolving urea in water or in alcohol. 

A wide variety of guest molecules may be trapped by the Wemer-type crystalline host lattice, ranging, eg, from noble gases to condensed aromatic hydrocarbons. These clathrates may be formed from solution or by sorption. Kinetics of sorption—desorption have been studied (83). 

Fig. 17. Prototypical host molecules based on more recent clathrate strategies.

Fig. 18. Crystal structures of recent clathrate design (a) coordinatoclathrate between host (39) (Fig. 17) and / -butanol (host—guest hydrogen bonding in the shaded area) (b) perspective view of the hehcal inclusion channel formed by diol host (43) (Fig. 17 all except one host molecule are represented...

Shielding and Stabilization. Inclusion compounds may be used as sources and reservoirs of unstable species. The inner phases of inclusion compounds uniquely constrain guest movements, provide a medium for reactions, and shelter molecules that self-destmct in the bulk phase or transform and react under atmospheric conditions. Clathrate hosts have been shown to stabiLhe molecules in unusual conformations that can only be obtained in the host lattice (138) and to stabiLhe free radicals (139) and other reactive species (1) similar to the use of matrix isolation techniques. Inclusion compounds do, however, have the great advantage that they can be used over a relatively wide temperature range. Cyclobutadiene, pursued for over a century has been generated photochemicaHy inside a carcerand container (see (17) Fig. 5) where it is protected from dimerization and from reactants by its surrounding shell (140). 

Analytically, the inclusion phenomenon has been used in chromatography both for the separation of ions and molecules, in Hquid and gas phase (1,79,170,171). Peralkylated cyclodextrins enjoy high popularity as the active component of hplc and gc stationary phases efficient in the optical separation of chiral compounds (57,172). Chromatographic isotope separations have also been shown to occur with the help of Werner clathrates and crown complexes (79,173). 

Glathrate Formation. Ethylene oxide forms a stable clathrate with water (20). It is non stoichiometric, with 6.38 to 6.80 molecules of ethylene oxide to 46 molecules of water iu the unit cell (37). The maximum observed melting poiat is 11.1°C. An x-ray stmcture of the clathrate revealed that it is a type I gas hydrate, with six equivalent tetrakaidecahedral (14-sided) cavities fully occupied by ethylene oxide, and two dodecahedral cavities 20—34% occupied (38). 

Iodide and iodate ions react under the influence of protons to yield iodine molecules which react with amylose to yield a blue clathrate complex ... 

FIGURE 2.5 Formation of a clathrate structure by water molecules surrouudiug a hydrophobic solute. 

Probably the most familiar of all clathrates are those formed by Ar, Kr and Xe with quinol, l,4-C6H4(OH)2, and with water. The former are obtained by crystallizing quinol from aqueous or other convenient solution in the presence of the noble gas at a pressure of 10-40 atm. The quinol crystallizes in the less-common -form, the lattice of which is held together by hydrogen bonds in such a way as to produce cavities in the ratio 1 cavity 3 molecules of quinol. Molecules of gas (G) are physically trapped in these cavities, there being only weak van der Waals interactions between... 

Molecular as well as ionic substances can form hydrates, but of an entirely different nature. In these crystals, sometimes referred to as clathrates, a molecule (such as CFI4, CHCI3) is quite literally trapped in an ice-like cage of water molecules. Perhaps the best-known molecular hydrate is that of chlorine, which has the approximate composition Cl2- 7.3H20. This compound was discovered by the great... 

An example is the complex with argon which can be kept indefinitely in an ordinary bottle, although the equilibrium pressure of argon over the crystal amounts to several atmospheres at room temperature. Powell31 named these complexes "clathrate compounds, which according to him are those compounds "in which two or more components are associated without ordinary chemical union but through complete enclosure of one set of molecules in a suitable structure formed by another. ... 

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