Section 10.2.1.1. Enantiomorphism, enantiomerism, chirality, dissymmetry

These terms refer to the same symmetry restriction, the absence of improper rotations (rotoinversions, rotoreflections) in a crystal or in a molecule. This implies in particular the absence of a centre of symmetry, , and of a mirror plane, , but also of a axis. As a consequence, such chiral crystals or molecules can occur in two different forms, which are related as a right and a left hand; hence, they are called right-handed and left-handed forms. These two forms of a molecule or a crystal are mirror-related and not superimposable (not congruent). Thus, the only symmetry operations that are allowed for chiral objects are proper rotations. Such objects are also called dissymmetric, in contrast to asymmetric objects, which have no symmetry.

The terms enantiomerism and chirality are mainly used in chemistry and applied to molecules, whereas the term enantiomorphism is preferred in crystallography if reference is made to crystals.

Enantiomorphic crystals, as well as solutions or melts containing chiral molecules of one handedness, exhibit optical activity (cf. Section 10.2.4.2). Crystals and molecules of the other handedness show optical activity with the opposite sense of rotation. For this reason, two molecules of opposite chirality are also called optical isomers.

Chiral molecules form enantiomorphic crystals of the corresponding handedness. The crystals belong, therefore, to one of the 11 crystal classes allowing enantiomorphism (Table 10.2.1.1). Racemic mixtures (containing equal amounts of molecules of each chirality), however, may crystallize in non-enantiomorphic or even centrosymmetric crystal classes. Racemization (i.e. the switching of molecules from one chirality to the other) of an optically active melt or solution can occur in some cases during crystallization, leading to non-enantiomorphic crystals.

Enantiomorphic crystals can also be built up from achiral molecules or atom groups. In these cases, the achiral molecules or atom groups form chiral configurations in the structure. The best known examples are quartz and NaClO₃. For details, reference should be made to Rogers (1975).