The density functional theory-based method with periodic boundary conditions and addition of a pair-wised empirical correction for the London dispersion energy (DFT-D) was used to study the NMR quadrupolar interaction (coupling constant CQ and asymmetry parameter ηQ) of (14)N nuclei in a homologous series of tetra-n-alkylammonium halides (C(x)H(2x+1))4N(+)X(-) (x = 1-4), (X = Br, I). These (14)N quadrupolar properties are particularly challenging for the DFT-D computations because of their very high sensitivity to tiny geometrical changes, being negligible for other spectral property calculations as, for example, NMR (14)N chemical shift. In addition, the polarization effect of the halide anions in the considered crystal mesophases combines with interactions of van der Waals type between cations and anions. Comparing experimental and theoretical results, the performance of PBE-D functional is preferred over that of B3LYP-D. The results demonstrated a good transferability of the empirical parameters in the London dispersion formula for crystals with two or more carbons per alkyl group in the cations, whereas the empirical corrections in the tetramethylammonium halides appeared to be inappropriate for the quadrupolar interaction calculation. This is attributed to the enhanced cation-anion attraction, which causes a strong polarization at the nitrogen site. Our results demonstrated that the (14)N CQ and ηQ are predominantly affected by the molecular structures of the cations, adapted to the symmetry of the anion arrangements. The long-range polarization effect of the surrounding anions at the target nitrogen site becomes more important for cells with lower spatial symmetry.