Crystallography of encapsulated molecules

Abstract

The crystallography of supramolecular host–guest complexes is reviewed and discussed as a part of small molecule crystallography. In these complexes, the host binds the guests through weak supramolecular interactions, such as hydrogen and halogen bonding, cation–π, anion–π, C–H–π, π–π, C–H–anion interactions and the hydrophobic effect. As the guest often shows severe disorder, large thermal motion and low occupancies, the reliable crystallographic determination of the guest can be very demanding. The analysis of host–guest interactions using tools such as Hirshfeld and cavity volume surface analysis will help to look closely at the most important host–guest interactions. The jewel in the crown of utilizing host–guest interactions in the solid-state is the recently developed Crystalline Sponge Method (CSM) by Makoto Fujita. This method, when successful, gives an accurate and unambiguous 3-D structure of the structurally unknown guest molecule from only micro- or nanogram amounts of the guest molecule. In the case of an optically pure enantiomer, its absolute configuration can be determined.