Diamond and BN have common relatively soft precursor structures that are hexagonal. Electronic structure calculations have now revealed subtle energy differences between the two materials. Another hard material, stishovite, also has a relatively soft precursor phase, quartz, and here again electronic structure calculations have given insight into the nature of the phase transformation. On the other hand, with boron-related materials, the main focus is to connect basic icosahedra structures to produce a hard material. The structural aspects of these materials are examined and possible consequences for low- and high-coordination ultrahard nitrides considered.