Interplay of π-stacking and inter-stacking interactions in two-component crystals of neutral closed-shell aromatic compounds: periodic DFT study

Меликова, С.М.; Voronin, Alexander P.; Panek, Jarosław J.; Frolov, Nikita E.; Shishkina, Anastasia V.; Rykounov, Alexey A.; Tretyakov, Peter Yu.; Vener, Mikhail V.

doi:10.1039/d0ra04799f

Cited by 26 publications

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“…Note also that the electrostatic contribution is quite significant for the compound 1 , which—at a first glance, due to the symmetry of the molecular skeleton—should be much less polar than the compounds 2 and 3 possessing polar hydroxyl substituents. Our earlier experience with aromatic systems of high symmetry [ 36 ] indicates that quadrupole–quadrupole interactions are significant sources of interaction strength for symmetric molecules of this kind, and this work shows that these interactions in 1 can compete in strength with dipole–dipole forces in 2 and 3 . Interestingly, the dimer 2b is arranged in a head-to-tail manner, which is less optimal (electrostatic energy of −0.96 kcal/mol) for the permanent dipole interactions than the head-to-head arrangement found in 3b (−4.25 kcal/mol electrostatic term).…”

Section: Results and Discussionmentioning

confidence: 62%

Competition of Intra- and Intermolecular Forces in Anthraquinone and Its Selected Derivatives

et al. 2021

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Intra- and intermolecular forces competition was investigated in the 9,10-anthraquinone (1) and its derivatives both in vacuo and in the crystalline phase. The 1,8-dihydroxy-9,10-anthraquinone (2) and 1,8-dinitro-4,5-dihydroxy-anthraquinone (3) contain Resonance-Assisted Hydrogen Bonds (RAHBs). The intramolecular hydrogen bonds properties were studied in the electronic ground and excited states employing Møller-Plesset second-order perturbation theory (MP2), Density Functional Theory (DFT) method in its classical formulation as well as its time-dependent extension (TD-DFT). The proton potential functions were obtained via scanning the OH distance and the dihedral angle related to the OH group rotation. The topological analysis was carried out on the basis of theories of Atoms in Molecules (AIM—molecular topology, properties of critical points, AIM charges) and Electron Localization Function (ELF—2D maps showing bonding patterns, calculation of electron populations in the hydrogen bonds). The Symmetry-Adapted Perturbation Theory (SAPT) was applied for the energy decomposition in the dimers. Finally, Car–Parrinello molecular dynamics (CPMD) simulations were performed to shed light onto bridge protons dynamics upon environmental influence. The vibrational features of the OH stretching were revealed using Fourier transformation of the autocorrelation function of atomic velocity. It was found that the presence of OH and NO2 substituents influenced the geometric and electronic structure of the anthraquinone moiety. The AIM and ELF analyses showed that the quantitative differences between hydrogen bonds properties could be neglected. The bridged protons are localized on the donor side in the electronic ground state, but the Excited-State Intramolecular Proton Transfer (ESIPT) was noticed as a result of the TD-DFT calculations. The hierarchy of interactions determined by SAPT method indicated that weak hydrogen bonds play modifying role in the organization of these crystal structures, but primary ordering factor is dispersion. The CPMD crystalline phase results indicated bridged proton-sharing in the compound 2.

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Section: Results and Discussionmentioning

confidence: 62%

Competition of Intra- and Intermolecular Forces in Anthraquinone and Its Selected Derivatives

et al. 2021

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“…In the theoretical study of crystals, much attention is paid to assessing the energy of intermolecular interactions. In contrast to the gas phase, such a calculation in a solid is a non-trivial problem, which involves the "isolation" of the energy (enthalpy) of a specific intermolecular interaction from the energy of the crystal lattice (enthalpy of sublimation) [128]. In most cases, empirical approaches are used that relate the energy of intermolecular interaction with one or another parameter of the electron density at the bond critical point [129][130][131].…”

Section: The Energies Of Intermolecular Interactions Of H 2 O 2 In Organic Crystals: Calculations By the Kohn-sham Methods With Periodic mentioning

confidence: 99%

“…At the moment, there is one example of a bifurcate H-bond formed by a hydrogen peroxide molecule and a nitro group 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazoisowurtzitane [84] in one of the polymorphs of the crystalline peroxosolvate of this molecule (Figure 15). In organic crystals, nonconventional O•••H-C [128] bonds often arise. In crystalline peroxosolvates, such bonds are rarely formed [165].…”

Section: Crystal (Coformer)mentioning

confidence: 99%

“…Note that in the case of coformers, the size of which significantly exceeds the size of a hydrogen peroxide molecule, H-bonds can arise between the coformers (Figure 10, In organic crystals, nonconventional O•••H-C [128] bonds often arise. In crystalline peroxosolvates, such bonds are rarely formed [165].…”

Section: Crystal (Coformer) the Number Of H-bonds The Proton Donor Groupmentioning

confidence: 99%

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Crystalline Peroxosolvates: Nature of the Coformer, Hydrogen-Bonded Networks and Clusters, Intermolecular Interactions

et al. 2020

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Despite the technological importance of urea perhydrate (percarbamide) and sodium percarbonate, and the growing technological attention to solid forms of peroxide, fewer than 45 peroxosolvates were known by 2000. However, recent advances in X-ray diffractometers more than tripled the number of structurally characterized peroxosolvates over the last 20 years, and even more so, allowed energetic interpretation and gleaning deeper insight into peroxosolvate stability. To date, 134 crystalline peroxosolvates have been structurally resolved providing sufficient insight to justify a first review article on the subject. In the first chapter of the review, a comprehensive analysis of the structural databases is carried out revealing the nature of the co-former in crystalline peroxosolvates. In the majority of cases, the coformers can be classified into three groups: (1) salts of inorganic and carboxylic acids; (2) amino acids, peptides, and related zwitterions; and (3) molecular compounds with a lone electron pair on nitrogen and/or oxygen atoms. The second chapter of the review is devoted to H-bonding in peroxosolvates. The database search and energy statistics revealed the importance of intermolecular hydrogen bonds (H-bonds) which play a structure-directing role in the considered crystals. H2O2 always forms two H-bonds as a proton donor, the energy of which is higher than the energy of analogous H-bonds existing in isostructural crystalline hydrates. This phenomenon is due to the higher acidity of H2O2 compared to water and the conformational mobility of H2O2. The dihedral angle H-O-O-H varies from 20 to 180° in crystalline peroxosolvates. As a result, infinite H-bonded 1D chain clusters are formed, consisting of H2O2 molecules, H2O2 and water molecules, and H2O2 and halogen anions. H2O2 can form up to four H-bonds as a proton acceptor. The third chapter of the review is devoted to energetic computations and in particular density functional theory with periodic boundary conditions. The approaches are considered in detail, allowing one to obtain the H-bond energies in crystals. DFT computations provide deeper insight into the stability of peroxosolvates and explain why percarbamide and sodium percarbonate are stable to H2O2/H2O isomorphic transformations. The review ends with a description of the main modern trends in the synthesis of crystalline peroxosolvates, in particular, the production of peroxosolvates of high-energy compounds and mixed pharmaceutical forms with antiseptic and analgesic effects.

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“…The experimental parameters of such systems cannot be correctly reproduced using the approximation of small molecular clusters. Using the periodic density functional theory is a reasonable compromise that allows the parameters of complex multicomponent pharmaceuticals to be accurately predicted [ 19 ].…”

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confidence: 99%

Editorial to the Special Issue “Gulliver in the Country of Lilliput: An Interplay of Noncovalent Interactions”

Shenderovich

2020

Molecules

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Interplay of π-stacking and inter-stacking interactions in two-component crystals of neutral closed-shell aromatic compounds: periodic DFT study

Abstract: The interplay of π-stacking and inter-stacking interactions in two-component organic crystals without conventional hydrogen bonds.

Cited by 26 publications

References 100 publications

Competition of Intra- and Intermolecular Forces in Anthraquinone and Its Selected Derivatives

Competition of Intra- and Intermolecular Forces in Anthraquinone and Its Selected Derivatives

Crystalline Peroxosolvates: Nature of the Coformer, Hydrogen-Bonded Networks and Clusters, Intermolecular Interactions

Editorial to the Special Issue “Gulliver in the Country of Lilliput: An Interplay of Noncovalent Interactions”

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