The use of solid-state NMR and X-ray crystallography as complementary tools for studying molecular recognition

Abstract

Solid-state NMR is rapidly becoming available as a routine technique for studying the structure of crystalline or noncrystalline solids. This technique has an advantage over crystallography in that single crystals are not necessary, but it has the disadvantage that the information obtained does not produce a direct picture of the molecule and its environment. On the other hand, solid-state NMR can be done on mixtures, and it gives information about phase distribution in a manner similar to that of X-ray powder pattern analysis. Crystallographic effects such as polymorphism, multiple molecules per asymmetric unit, disorder and salvation can frequently be detected using NMR. Sometimes molecular point group symmetry can also be deduced based on the number of independent nuclei that are detected. The NMR method is sensitive to changes in the electronic structure of a molecule as sensed by the nuclei, and the effects are measured as changes in the isotropic chemical shift of individual nuclei. In this paper, we will give examples of the combined use of X-ray crystallography and 13CP/MAS (cross polarization/magic angle spinning) NMR for studying hostguest materials and cocrystals. We have learned how to use NMR to tell us about keto/enol composition in the solid state, to detect the presence of trapped solvent molecules, to detect hydrogen-bond formation and to evaluate molecular conformation and unusual packing pattern effects. We will also present a brief background of the 13CP/MAS NMR technique and three case studies in which solid-state NMR and X-ray crystallography are used together to understand materials' structures and properties