Molecular crystals example

Molecular Crystals Examples of molecular crystals include Ij and ICl. Small, discrete molecules are held together by relatively weak intermolecular forces of the types discussed in Section 15.3. Molecular crystals are typically soft, low-melting, and generally (but not always) insoluble in water. They usually dissolve in nonpolar or... 

This chapter will deal with both types of processes, namely reactions between solids and reactions between solids and gases. In the first section we will discuss examples of gas-solid reactions between molecular solids (operatively taken as crystals formed by neutral molecules or molecular ions) and vapours of small molecules, while the second section will deal with solid-solid reactions between molecular crystals to yield co-crystals. Even though examples will come mainly from our own work with organometallic molecules, coverage of the work of many scientists in the field will be attempted. The reader should be warned, however, that this chapter has no review-type ambitions. 

Chemical reactions in the sohd state have intrinsic features different from those for reactions performed in solution or in the gaseous state. For example, sohd-state organic reactions often provide a high regio- or stereoselectivity because the reactions and the structiue of a product are determined by the crystal structure of the reactant, i.e., the reaction proceeds under crystaUine lattice control [1-8]. When the reactant molecules are themselves crystalhne (molecular crystals) or are included in host crystals (inclusion compounds), the rate and selectivity of the reaction are different from those obtained in an isotropic reaction medium. 

Examples of molecular crystals are found throughout organic, organometallic, and inorganic chemistry. Low melting and boiling temperatures characterize the crystals. We will look at just two examples, carbon dioxide and water (ice), both familiar, small, covalently bonded molecules. 

Organic solids have received much attention in the last 10 to 15 years especially because of possible technological applications. Typically important aspects of these solids are superconductivity (of quasi one-dimensional materials), photoconducting properties in relation to commercial photocopying processes and photochemical transformations in the solid state. In organic solids formed by nonpolar molecules, cohesion in the solid state is mainly due to van der Waals forces. Because of the relatively weak nature of the cohesive forces, organic crystals as a class are soft and low melting. Nonpolar aliphatic hydrocarbons tend to crystallize in approximately close-packed structures because of the nondirectional character of van der Waals forces. Methane above 22 K, for example, crystallizes in a cubic close-packed structure where the molecules exhibit considerable rotation. The intermolecular C—C distance is 4.1 A, similar to the van der Waals bonds present in krypton (3.82 A) and xenon (4.0 A). Such close-packed structures are not found in molecular crystals of polar molecules. 

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