Anomalous scattering and absolute configuration

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The concept of the carbon atom with four bonds extending in a tetrahedral fashion was put forward by van’t Hoff and Le Bel in 1874. It coincided with the realization that such an arrangement could be asymmetric if the four substituents were different, as shown in Figure 10.1a (van’t Hoff, 1874; Le Bel, 1874). Thus, for any compound containing one such asymmetric carbon atom, there are two isomers of opposite chirality (individually called enantiomers), for which threedimensional representations of their structural formulas are related by a mirror plane. Aqueous solutions of these enantiomers rotate the plane of polarized light in opposite directions. As discussed in Chapter 7, Pasteur showed that crystals of sodium ammonium tartrate had small asymmetrically located faces and that crystals with these so-called “hemihedral faces” rotated the plane of polarization of light clockwise, while crystals with similar faces in mirror-image positions rotated this plane of polarization counterclockwise. Thus the external form (that is, the morphology) of the crystals illustrated in Figure 10.1b was used to separate enantiomers (see Patterson and Buchanan, 1945). Pure enantiomers can only crystallize in noncentrosymmetric space groups unless both isomers are present. But even if the chemical formula and the three-dimensional structure of a molecule such as tartaric acid have been determined by standard X-ray diffraction methods, there is an ambiguity about the absolute configuration. Information about the absolute configuration is not contained in the diffraction pattern of the crystal as it is normally measured. Thus, although the substituents on the asymmetric carbon atoms have been identified, and even the detailed three-dimensional geometry of the molecule has been determined, it is not known which of the two enantiomers (mirror-image forms, analogous to those shown in Figure 10.1a) represents the three-dimensional structure of a particular individual molecule that has some distinguishing chiral property, such as the ability to rotate the plane of polarized light to the right. In other words, what is the absolute structure of the dextrorotatory form of the compound under study? A means of determining the absolute configurations of molecules was, however, provided by X-ray crystallographic studies.