Fast Quantum Approach for Evaluating the Energy of Non-Covalent Interactions in Molecular Crystals: The Case Study of Intermolecular H-Bonds in Crystalline Peroxosolvates
Medvedev, AG (Medvedev, Alexander G.); Churakov, AV (Churakov, Andrei, V); Navasardyan, MA (Navasardyan, Mger A.); Prikhodchenko, PV (Prikhodchenko, Petr, V); Lev, O (Lev, Ovadia); Vener, MV (Vener, Mikhail V.)
Molecules, 2022, Volume 27, 4082.
Energy/enthalpy of intermolecular hydrogen bonds (H-bonds) in crystals have been calculated 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 center dot center dot center dot O bond set fills evenly (i.e., without significant gaps) the range of H center dot center dot center dot O distances from -1.5 to -2.1 A 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.
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