L-Histidine with nitric acid: A comparison of crystal structures and Hirshfeld surfaces analysis.

• L-Histidine nitrate, Crystal Structure using single crystal X-ray and neutron diffraction. • CSD to retrieve crystal structure of L-histidinium nitrate monohydrate, L-Histidinium dinitrate & DL-histidinium nitrate. • Conformation of L-histindine in L-histidinium nitrate monohydrate is gauche(+) different from other three. • Hirshfeld surface & interaction energies of the structures showed L-histidine nitrate monohydrate has maximum total energy. • Hyperpolarizabilities calculated using MOPAC2009 showed that L-histidine nitrate monohydrate has maximum average β. L-histidine crystallizes in three different crystal structure with nitric acid, i.e. L-histidinium nitrate, L-histidinium nitrate monohydrate and L-Histidinium dinitrate. Also there is DL-histidinium dinitrate. Though the structural aspects of histidinium nitrate monohydrate, L-Histidinium dinitrate and DL -histidinium nitrate are well studied, the structural studies on L-histidinium nitrate is not dealt in detail. Here we have tried to discuss in detail the crystal structure of L-histidinium nitrate using both single crystal X-ray and neutron diffraction. The crystal structure consists one L-histidine molecule which has the amino and imino groups protonated, but the carboxylic acid group is deprotonated. The nitrate ion is in anionic state ie NO3−. The conformation of histidine (N1-C2-C3-C4=64.99°) is gauche (-). Also a comparison of the structure of L-histidinium nitrate with other three available crystal structures retrieved using CSD have been carried out. It was found that L-histidine in L-histidinium nitrate monohydrate adopts gauche (+) conformation and in other three structure it is gauche (-), and L-histidinium nitrate has the lowest volume. Hirshfeld surface and interaction energies analysis of all the above structures were carried out using the x-ray data. L-histidinium nitrate monohydrate shows maximum globuarity. Interaction energy obtained from energy framework showed that L-histidinium nitrate monohydrate has maximum total energy of -41.5(kJ/Mole). The asphericity of our structure L-histidinium nitrate is 0.252 indicating prolate nature unlike the other three complexes. The percentage of H...H contacts is maximum in L-histidinium nitrate which is 27.3%. A comparison of various contacts of histidine between the x-ray and neutron structure of ours shows that the maximum change is reflected in the C...H and H...H contacts with C...H having a higher percentage and H...H having a lower percentage in the neutron structure indicating that the neutron diffraction maps shows the hydrogen bond interaction more accurately. The three complexes, except DL Histidinium dinitrate crystallizes in a non-centrosymmetric space group and hence could exhibit second-order optical non-linear properties, attempts were made to calculate heats of formation, dipole moments (D), polarizabilities (α) and first hyperpolarizabilities (β) using the semi empirical method at the PM6 level using MOPAC2009 and the packing energy as implemented in MERCURY. It was found that the average β of L-histidinium nitrate monohydrate was the highest amongst the three showing that it is more suitable for NLO material. Histidine with nitric acid in different stoichimetric ratio in presence of water crystallizes in above four crystal structures. [Display omitted] [ABSTRACT FROM AUTHOR]