Energy/enthalpy of intermolecular hydrogen bonds (H-bonds) in crystals have been calcu-lated in many papers. Most of the theoretical works used non-periodic models. Their applicability for describing intermolecular H-bonds in solids is not obvious since the crystal environment can strongly change H-bond geometry and energy in comparison with non-periodic models. Periodic DFT computations provide a reasonable description of a number of relevant properties of molecular crystals. However, these methods are quite cumbersome and time-consuming compared to non-periodic calculations. Here, we present a fast quantum approach for estimating the energy/enthalpy of intermolecular H-bonds in crystals. It has been tested on a family of crystalline peroxosolvates in which the H···O bond set fills evenly (i.e., without significant gaps) the range of H···O distances from ~1.5 to ~2.1 Å typical for strong, moderate, and weak H-bonds. Four of these two-component crystals (peroxosolvates of macrocyclic ethers and creatine) were obtained and structurally characterized for the first time. A critical comparison of the approaches for estimating the energy of intermolecular H-bonds in organic crystals is carried out, and various sources of errors are clarified.
Bibliographical noteFunding Information:
Funding: The authors thank Russian Foundation for Basic Research for financial support (grant 20-03-00449).
Acknowledgments: The single-crystal X-ray diffraction studies were performed at the Centre of Shared Equipment of IGIC RAS within the State Assignment on Fundamental Research of the Kurnakov Institute of General and Inorganic Chemistry. O.L. acknowledges the financial support of the Israel Science Foundation (grant no. 1215/19). M.V.V. thanks G. L. Perlovich for the possibility of conducting computations using Crystal17.
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- B3LYP vs. PBE-D3
- amino acid
- bifurcated H-bonds
- macrocyclic ether
- multicomponent crystals
- periodic DFT computations