Noncovalent Interactions in Crystalline Picolinic Acid N-Oxide: Insights from Experimental and Theoretical Charge Density Analysis

Abstract

This study provides a detailed description of noncovalent interactions of different types and strengths in the title crystal using a combined experimental and theoretical study of the charge density distribution. The nature of the noncovalent interactions is visualized using information theory and through the superposition of the gradient fields in the electron density and electrostatic potential. The energy of the intramolecular O–H···O bond, intermolecular C–H···O bonds, and π-stacking interactions, E int, are evaluated from empirical correlations between E int and geometrical and electron-density bond critical point parameters. The complete set of noncovalent interactions including the strong intramolecular O–H···O (E int > 90 kJ/mol) and weak C–H···O (E int < 10 kJ/mol) hydrogen bonds, and π-stacking interactions (E int < 4 kJ/mol) is quantitatively described. The results from the experimental charge density analysis are compared with periodic quantum calculations using density functional theory with the Grimme dispersion correction. It was found that the Grimme dispersion correction did not provide a good simultaneous description of both weak and strong noncovalent interactions in the studied crystal. It is shown that the obtained energies of noncovalent interactions lead to a reasonable value of the lattice energy. The latter is treated as the total intermolecular interaction energy.

Interplay between non-covalent interactions in complexes and crystals with halogen bonds

“…Two functionals with correction for dispersion interactions, namely, M06-2X and oB97XD, were recommended. It was found that the hydrogen bond lengths 102 and halogen bond lengths 101 calculated using the Grimme empirical dispersion corrections 94 are often underestimated, which reduces the accuracy of calculations.…”

Influence of Secondary Interactions on the Structure, Sublimation Thermodynamics, and Solubility of Salicylate:4-Hydroxybenzamide Cocrystals. Combined Experimental and Theoretical Study

“…were not considered in present work, as their value is too small for determination by existing experimental and computational methods [35,36]. The energy of the particular single non-covalent interaction E int was estimated as [37]: 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60…”

“…(1). The latter approach provides reasonable values for singlecomponent [37,40] and two-component [24,46] It is assumed that the E latt energy corresponds to the sublimation enthalpy ∆H 0 subl , extrapolated to 0 K. According to [47], the value of the sublimation enthalpy at given temperature T can be written as:…”

Improving approximate determination of the noninteracting electronic kinetic energy density from electron density

“…All this interactions are weak and electron density of a single molecule reconstructed from X‐ray diffraction experiment using the multipole‐model can be removed from a crystal with only slight distortions on its periphery. We used the electron density and its derivatives derived from accurate high‐resolution X‐ray diffraction data measured at 100 K . WinXPRO program has been used in these computations.…”

“…In the quantum‐topological theory of atoms in molecules and crystals (QTAIMC), the KED and the electronic potential energy density at the bond critical points (BCPs) are used to identify the type of atomic interactions . In addition, a correlation between the electronic KED at BCPs and the energy of hydrogen bonds and halogen–halogen bonds have been established for the molecular clusters and crystals …”