Parts 1 and 2 of this series described the educational value of experimental three-dimensional (3D) chemical structures determined by X-ray crystallography and retrieved from the crystallographic databases. In part 1, we described the information content of the Cambridge Structural Database (CSD) and discussed a representative teaching subset of ca. 500 CSD structures that have been selected for their educational relevance. In part 2, we exemplified the value of the CSD teaching subset by describing four worked examples of their use in a teaching context. Although the CSD teaching subset and its associated learning modules provide a major resource for chemical educators, there are many cases where the full CSD System, now covering more than 500,000 crystal structures, is essential to make an educational point. This is particularly true when introducing students to variance in real experimental observations, for example, where many hundreds of observations are required to generate statistically meaningful trends from the structural data or simply to introducing students to the search and manipulation of data that are commonly available in large chemical and biochemical databases. Here, we describe the complete CSD System and its associated software and highlight the extended range of discovery-based learning opportunities this affords. (Contains 1 table and 5 figures.) [For Part 2, see EJ918551.]