Research efforts to identify new superhard phases of compounds of light elements require the use of structure prediction programs such as USPEX and CALYPSO . However, novel structures can also be identified through the application of crystal engineering rationale as presented here. In all cases, such predictions must be validated by the quantitative study of energies and the derived physical properties using first-principles calculations. Over the years, the well-established quantum mechanics framework of the density functional theory (DFT) has proven to be the most efficient.