Intermolecular Interactions in Molecular Organic Crystals upon Relaxation of Lattice Parameters

Stein, Matthias; Heimsaat, Madalen

doi:10.3390/cryst9120665

Cited by 18 publications

(12 citation statements)

References 59 publications

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“…Some approximations give negative values of this coefficient. Note that such a result was already obtained in a number of articles (see Tables 2 and 3 in Reference [57], Table 2 in Reference [58], Figure 4 in Reference [59], and Table S19 in Reference [34]). These results demonstrate that the change in the unit cell volume during the lattice optimization does not always correspond to the experimental data.…”

Section: Effect Of Optimization On Cell Parameterssupporting

confidence: 62%

Combined X-ray Crystallographic, IR/Raman Spectroscopic, and Periodic DFT Investigations of New Multicomponent Crystalline Forms of Anthelmintic Drugs: A Case Study of Carbendazim Maleate

et al. 2020

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Synthesis of multicomponent solid forms is an important method of modifying and fine-tuning the most critical physicochemical properties of drug compounds. The design of new multicomponent pharmaceutical materials requires reliable information about the supramolecular arrangement of molecules and detailed description of the intermolecular interactions in the crystal structure. It implies the use of a combination of different experimental and theoretical investigation methods. Organic salts present new challenges for those who develop theoretical approaches describing the structure, spectral properties, and lattice energy Elatt. These crystals consist of closed-shell organic ions interacting through relatively strong hydrogen bonds, which leads to Elatt > 200 kJ/mol. Some technical problems that a user of periodic (solid-state) density functional theory (DFT) programs encounters when calculating the properties of these crystals still remain unsolved, for example, the influence of cell parameter optimization on the Elatt value, wave numbers, relative intensity of Raman-active vibrations in the low-frequency region, etc. In this work, various properties of a new two-component carbendazim maleate crystal were experimentally investigated, and the applicability of different DFT functionals and empirical Grimme corrections to the description of the obtained structural and spectroscopic properties was tested. Based on this, practical recommendations were developed for further theoretical studies of multicomponent organic pharmaceutical crystals.

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Section: Effect Of Optimization On Cell Parameterssupporting

confidence: 62%

Combined X-ray Crystallographic, IR/Raman Spectroscopic, and Periodic DFT Investigations of New Multicomponent Crystalline Forms of Anthelmintic Drugs: A Case Study of Carbendazim Maleate

et al. 2020

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“…Data are taken from ref . f Calculated with B97-D/def2-TZVP in TURBMOLE . Data are taken from ref . g Calculated with PBE-XDM in Quantum EXPRSSO . Data are taken from ref . h Calculated with B3LYP-D*/TZP in CRYSTAL and LMP2/p-aug-6-31G(d,p) in CRYSCOR .…”

Section: Resultsmentioning

confidence: 99%

XO-PBC: An Accurate and Efficient Method for Molecular Crystals

Chen

2020

J. Chem. Theory Comput.

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In this work, we propose the XO-PBC method, which combines the eXtended ONIOM method (XO) with the periodic boundary condition (PBC) for the description of molecular crystals. XO-PBC tries to embed a finite cluster cut out from the solid into the periodic environment, making it feasible to employ advanced molecular quantum chemistry methods, which are usually prohibitively expensive for direct PBC calculations. In particular, XO-PBC utilizes the results from force calculations to design the scheme to fragment the molecule when crystals are made of large molecules and to select cluster model systems automatically consisting of dimer up to tetramer interactions for embedding. By applying an appropriate theory to each model, a satisfactory accuracy for the system under study is ensured, while a high efficiency is achieved with massively parallel computing by distributing model systems onto different processors. A comparison of the XO-PBC calculations with the conventional direct PBC calculations at the B3LYP level demonstrates its accuracy at substantially low cost for the description of molecular crystals. The usefulness of the XO-PBC method is further exemplified, showing that XO-PBC is able to predict the lattice energies of various types of molecular crystals within chemical accuracy (<4 kJ/mol) when the doubly hybrid density functional XYG3 is used as the target high level and the periodic PBE as the basic low level. The XO-PBC method provides a general protocol that brings the great predictive power of advanced electronic structure methods from molecular systems to the extended solids.

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“…Results are reported in Table S1 in the Supporting Information and show that all Grimme’s correction leads to a preference for the P1B polymorph and the differences between the three methods are small (5.5 kJ·mol –1 ). Moreover, according to the literature, PBE-D3 is accurate enough for modeling molecular crystals , and, indeed, it has been even used to compute reference values for the validation of less computationally demanding approaches . Ionic cores were described with the projector augmented wave (PAW) pseudopotentials. , The valence electrons were represented through a plane-wave basis set with a kinetic energy cutoff of 600 eV.…”

Section: Methodsmentioning

confidence: 99%

Controlling the Formation of Two Concomitant Polymorphs in Hg(II) Coordination Polymers

et al. 2022

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Controlling the formation of the desired product in the appropriate crystalline form is the fundamental breakthrough of crystal engineering. On that basis, the preferential formation between polymorphic forms, which are referred to as different assemblies achieved by changing the disposition or arrangement of the forming units within the crystalline structure, is one of the most challenging topics still to be understood. Herein, we have observed the formation of two concomitant polymorphs with general formula {[Hg(Pip) 2 (4,4′-bipy)]·DMF} n ( P1A, P1B ; Pip = piperonylic acid; 4,4′-bipy = 4,4′-bipyridine). Besides, [Hg(Pip) 2 (4,4′-bipy)] n ( 2 ) has been achieved during the attempts to isolate these polymorphs. The selective synthesis of P1A and P1B has been successfully achieved by changing the synthetic conditions. The formation of each polymorphic form has been ensured by unit cell measurements and decomposition temperature. The elucidation of their crystal structure revealed P1A and P1B as polymorphs, which originates from the Hg(II) cores and intermolecular associations, especially pinpointed by Hg···π and π···π interactions. Density functional theory (DFT) calculations suggest that P1B , which shows Hg(II) geometries that are further from ideality, is more stable than P1A by 13 kJ·mol –1 per [Hg(Pip) 2 (4,4′-bipy)]·DMF formula unit, and this larger stability of P1B arises mainly from metal···π and π···π interactions between chains. As a result, these structural modifications lead to significant variations of their solid-state photoluminescence.

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Intermolecular Interactions in Molecular Organic Crystals upon Relaxation of Lattice Parameters

Cited by 18 publications

References 59 publications

Combined X-ray Crystallographic, IR/Raman Spectroscopic, and Periodic DFT Investigations of New Multicomponent Crystalline Forms of Anthelmintic Drugs: A Case Study of Carbendazim Maleate

Combined X-ray Crystallographic, IR/Raman Spectroscopic, and Periodic DFT Investigations of New Multicomponent Crystalline Forms of Anthelmintic Drugs: A Case Study of Carbendazim Maleate

XO-PBC: An Accurate and Efficient Method for Molecular Crystals

Controlling the Formation of Two Concomitant Polymorphs in Hg(II) Coordination Polymers

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