Noncovalent interactions (NCIs) can influence the stability and chemical properties of pentavalent and hexavalent actinyl (AnO2+/2+) compounds. In this work, the impact of NCIs (actinyl-hydrogen and actinyl-cation interactions) on the enthalpy of formation (ΔHf) and vibrational features was evaluated using Np(VI) tetrachloro compounds as the model system. We calculated the ΔHf values of these solid-state compounds through density functional theory+ thermodynamics (DFT+ T) and validated the results against experimental ΔHf values obtained through isothermal acid calorimetry. Three structural descriptors were evaluated to develop predictors for ΔHf, finding a strong link between ΔHf and hydrogen bond energy (EHtotal) for neptunyl-hydrogen interactions and total electrostatic attraction energy (Eelectrostatictotal) for neptunyl-cation interactions. Finally, we used Raman spectroscopy together with bond order analysis to probe Np=O bond perturbation due to NCIs. Our results showed a strong correlation between the degree of NCIs by axial oxygen and red-shifting of Np=O symmetrical stretch (ν1) wavenumbers and quantitatively demonstrated that NCIs can weaken the Np=O bond. These properties were then compared to those of related U(VI) and Np(V) phases to evaluate the effects of subtle differences in the NCIs and overall properties. In general, the outcomes of our study demonstrated the role of NCIs in stabilizing actinyl solid materials, which consequently governs their thermochemical behaviors and vibrational signatures.