CrystalExplorermodel energies and energy frameworks: extension to metal coordination compounds, organic salts, solvates and open-shell systems

Abstract

The application domain of accurate and efficient CE-B3LYP and CE-HF model energies for intermolecular interactions in molecular crystals is extended by calibration against density functional results for 1794 molecule/ion pairs extracted from 171 crystal structures. The mean absolute deviation of CE-B3LYP model energies from DFT values is a modest 2.4 kJ mol À1 for pairwise energies that span a range of 3.75 MJ mol À1. The new sets of scale factors determined by fitting to counterpoise-corrected DFT calculations result in minimal changes from previous energy values. Coupled with the use of separate polarizabilities for interactions involving monatomic ions, these model energies can now be applied with confidence to a vast number of molecular crystals. Energy frameworks have been enhanced to represent the destabilizing interactions that are important for molecules with large dipole moments and organic salts. Applications to a variety of molecular crystals are presented in detail to highlight the utility and promise of these tools.

Boron–Nitrogen Double Tweezers Comprising Arylboronic Esters and Diamines: Self‐Assembly in Solution and Adaptability as Hosts for Aromatic Guests in the Solid State

“…[a] Interaction energies were computed using the CE‐B3LYP energy model as implemented in CrystalExplorer . The total interaction energy is the sum of scaled energy components according to equation E tot =1.057 E ele +0.74 E pol + 0.871 E dis + 0.618 E rep , as optimized by the Spackman group . Individual energy components due to electrostatics, polarization, dispersion and repulsion were not scaled.…”

Molecular Structure, DFT, Vibrational Spectra with Fluorescence Effect, Hirshfeld Surface, Docking Simulation and Antioxidant Activity of Thiazole Derivative

“…CrystalExplorer17.5 has been adopted to calculate and visualize the energy frameworks of the molecular system by using B3LYP function under 6–31G (d,p) bases set level. This technique provides us deep information about the type of energies responsible for supramolecular architecture of crystal packing in the molecular system, by analyzing the nature of different types of interactions between the molecular pairs such as dispersion, electrostatic, repulsion, and polarization (see Table 9 in supporting information (SI)) . The molecular environment has been constructed by taking one molecule at its center and around with the maximum distance of 3.8 Å.…”

“…The molecular environment has been constructed by taking one molecule at its center and around with the maximum distance of 3.8 Å. The benchmarked energies used to construct the energy framework in the calculation were scaled according to Mackenzie et al While the scale factors of others energies are 1.057, 0.740, 0.871 and 0.618 for electrostatic, dispersion, polarization, and repulsion interactions, respectively . In Figure the cylinders indicate the relative strengths in energy framework of molecular packing in all directions.…”

Unsubstituted Oxacalix[n]arenes (n=4 and 8): A Conformational Study in Solution and Solid State and Interaction Studies with Aromatic Guests

“…Dominant intermolecular interactions within the crystal structures of the two polymorphs of 1 a were explored by the whole‐molecule approach of energy framework analysis, using the CrystalExplorer software (See SI for details), together with a more detailed look on specific intermolecular contacts. Packing of the macrocycles is mainly directed by off‐center aromatic‐aromatic interactions, known for electron‐rich aromatic systems, and multiple weak C−H⋅⋅⋅O hydrogen bonds.…”