Fourteen crystal structures, mostly from good-quality datasets but including some marginal and twinned exemplars, from a series of novel polycyclic benzo- and naphtho-fused organic nitriles are presented and accurately described, including some related structures of a bromo-substituted and partially hydrogenated analogues. These structures represent a considerable increase in the number of published structures within their archetypes. This work highlights the significant advancement in structural refinement software proffered by NoSpherA2, which enables Hirshfeld Atom Refinement (HAR) of the structures within Olex2 v1.5. This results in the determination of C-H bond lengths with near to neutron diffraction accuracies at far lower experimental cost, and with an average improvement in C-C bond precision of 42% compared to Independent Atom Model refinements. H-atoms (apart from disordered components) refined well with anisotropic displacement parameters. Nonclassical H-bonding (C-H···N≡C) in this series is analyzed, and dipolar nitrile-nitrile interactions (C≡N···C≡N) in three major motifs described by (Wood, P. A. Acta Cryst. B, 2008, 64, 393-396) are found in 9 out of 13 nitrile-containing compounds of this series, a much higher proportion than the global average of 21% of nitrile-containing compounds. The HAR/NoSpherA2 approach shows increasing benefits with better data quality without apparent discontinuities.