A systematic computational investigation was carried out to characterize the O-17, N-14 and H-2 electric field gradient, EFG, as well as O-17, N-15, C-13 and H-1 chemical shielding tensors in the anhydrous chitosan crystalline structure. To include the hydrogen-bonding effects in the calculations, the most probable interacting molecules with the target molecule in the crystalline phase were considered through a hexameric cluster. The computations were performed with the B3LYP method and 6-311++G(d,p) and 6-31++G(d,p) standard basis sets using the Gaussian 98 suite of programs. Calculated EFG and chemical shielding tensors were used to evaluate the O-17, N-14 and H-2 nuclear quadrupole resonance, NQR, and O-17, N-15, C-13 and H-1 nuclear magnetic resonance, NMR, parameters in the hexameric cluster, which are in good agreement with the available experimental data. The difference between the calculated NQR and NMR parameters of the monomer and hexamer cluster shows how much hydrogen bonding interactions affect the EFG and chemical shielding tensors of each nucleus. These results indicate that both O(3)-H(33)center dot center dot center dot O(5-3) and N-H(22)center dot center dot center dot O(6-4) hydrogen bonding have a major influence on NQR and NMR parameters. Also, the quantum chemical calculations indicate that the intra- and intermolecular hydrogen bonding interactions play an essential role in determining the relative orientation of EFG and chemical shielding principal components in the molecular frame axes.