Towards an understanding of crystallization from solution. DFT studies of multi-component serotonin crystals

Rychkov, Denis A.; Hunter, Stuart; Kovalskii, Viktor Yu.; Lomzov, Alexander A.; Pulham, Colin R.; Болдырева, Е. В.

doi:10.1016/j.comptc.2016.04.027

Cited by 6 publications

(4 citation statements)

References 40 publications

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“…Such information will ultimately allow better prediction of solid-form landscapes and polymorphism. [30][31][32][33][34] Tolazamide, N-[(azepan-1-ylamino)carbonyl]-4-methylbenzenesulfonamide ( Fig. 1), is an oral blood glucose lowering drug of the sulfonylurea class.…”

Section: Introductionmentioning

confidence: 99%

Effect of pressure on two polymorphs of tolazamide: why no interconversion?

et al. 2017

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Two polymorphs of tolazamide, N-[(azepan-1-ylamino)carbonyl]-4-methylbenzenesulfonamide, a sulfonylurea anti-diabetic drug, have different densities and molecular packings. Polymorph II converts into polymorph I in the solid state on heating or via recrystallization if solvent-assisted. The effect of pressure on the two forms and the possibility of a transformation to a denser form on compression have been studied.No phase transitions have been observed in either of the forms in a pentane-isopentane mixture (when no recrystallization is possible). Polymorph II recrystallized partly into a denser polymorph I in methanol at 0.1 GPa, but the transformation stopped at an early stage. Solid state DFT calculations of the two forms as well as conformational landscape investigation in the gas phase were used to rationalize this result. The anisotropic pressure-induced strain of the two polymorphs has been compared in relation to changes in the hydrogen bond geometry and the behavior of stacking interactions. † Electronic supplementary information (ESI) available: Information on tolazamide crystallization in methanol, low-temperature experiments, details of computational techniques and other data for tolazamide polymorphs: summary of the structural data at multiple pressures and temperatures; data on H-bonds and stacking interactions under pressure, parameters of the equations of state, and information on the strain ellipsoids; figures presenting the tolazamide molecule conformational landscape, conformational disorder in form II and pressure dependencies of tolazamide polymorphs' enthalpies. CCDC 1495203-1495210 and 1493069-1493078. For ESI and crystallographic data in CIF or other electronic format see

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Section: Introductionmentioning

confidence: 99%

Effect of pressure on two polymorphs of tolazamide: why no interconversion?

et al. 2017

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“…The challenge for theoreticians is therefore to find simulation methods that are sufficiently accurate for relative energy and structure determination purposes within reasonable computational costs. There are two categories of methods to describe the (organic) solid state: (i) the crystalline orbital methods for periodic systems − and (ii) localized orbital/fragment embedding field approaches for both periodic and nonperiodic systems. − Here, the focus is on the first category of methods. Owing to its reliability to describe the structure of gases, liquids, and inorganic crystals, density functional theory (DFT) is a good candidate for optimizing the structure of molecular crystals.…”

Section: Introductionmentioning

confidence: 99%

Assessing Density Functional Theory Approaches for Predicting the Structure and Relative Energy of Salicylideneaniline Molecular Switches in the Solid State

et al. 2017

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The geometrical structures of salicylideneaniline (anil) molecular switches in the solid state have been determined using periodic structure calculations and a variety of density functional theory (DFT) exchange-correlation (XC) functionals, of which several have been tuned for the solid state. The first target was on predicting the unit cell and intramolecular geometrical parameters for three anil derivatives, i.e., the (E)-2-methoxy-6-(pyridine-3-yliminomethyl)phenol (PYV3) and N-(5chloro-2-hydroxybenzylidene)-aniline (HC) crystals, where the enol (E) form is dominant in the crystalline state at low temperature (∼100 K), and the N-(5-chloro-2-hydroxybenzylidene)-hydroxyaniline (POC) crystal, which is mostly composed of the keto (K) form. The best performance for the unit cell parameters, in comparison with single-crystal X-ray diffraction (XRD) data, is achieved with XC functionals developed for the solid state (PBEsol and PBEsol0) as well as with ωB97X. On the other hand, the differences between the functionals are much smaller when considering the bond lengths and the valence angles so that the deviations with respect to XRD data in the bond length alternations of the key O−CC−CN−C (or OC−CC−N− C) π-conjugated segment are smaller than 0.02 Å for PBEsol0 and ωB97X. Similar trends are observed for the two polymorphic cocrystals of PYV3 with fumaric or succinic acid. The second target was the characterization of the variations of energy and structural parameters when switching between the enol and keto forms. All XC functionals predict that PYV3 presents a larger ΔE KE value than HC, and as expected, both are larger than for POC. Still, only hybrid functionals correctly predict which form is the most stable in the crystalline state. Then, the bond length changes in the O−CC−CN−C (or OC−CC−N−C) πconjugated segment that occur upon enol to keto transformation are similarly predicted by all functionals and are consistent with the reversal of the single/double bonds pattern.

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“…The difference in the ability of diOHBAs to form multiple crystal forms could be associated with the differences in propensity to form different intermolecular interactions. One of the tools that could be used for exploring this feature is ESP surfaces [ 66 , 67 ]. ESP surfaces generated for diOHBAs are given in Figure 7 and are arranged from left to right according to the grouping as in Table 1 (the observed tendencies in the propensity to form solid phases in the selected solvents).…”

Section: Resultsmentioning

confidence: 99%

Combined Use of Structure Analysis, Studies of Molecular Association in Solution, and Molecular Modelling to Understand the Different Propensities of Dihydroxybenzoic Acids to Form Solid Phases

Mishnev

Be̅rziņš

2021

Pharmaceutics

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The arrangement of hydroxyl groups in the benzene ring has a significant effect on the propensity of dihydroxybenzoic acids (diOHBAs) to form different solid phases when crystallized from solution. All six diOHBAs were categorized into distinctive groups according to the solid phases obtained when crystallized from selected solvents. A combined study using crystal structure and molecule electrostatic potential surface analysis, as well as an exploration of molecular association in solution using spectroscopic methods and molecular dynamics simulations were used to determine the possible mechanism of how the location of the phenolic hydroxyl groups affect the diversity of solid phases formed by the diOHBAs. The crystal structure analysis showed that classical carboxylic acid homodimers and ring-like hydrogen bond motifs consisting of six diOHBA molecules are prominently present in almost all analyzed crystal structures. Both experimental spectroscopic investigations and molecular dynamics simulations indicated that the extent of intramolecular bonding between carboxyl and hydroxyl groups in solution has the most significant impact on the solid phases formed by the diOHBAs. Additionally, the extent of hydrogen bonding with solvent molecules and the mean lifetime of solute–solvent associates formed by diOHBAs and 2-propanol were also investigated.

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Towards an understanding of crystallization from solution. DFT studies of multi-component serotonin crystals

Cited by 6 publications

References 40 publications

Effect of pressure on two polymorphs of tolazamide: why no interconversion?

Effect of pressure on two polymorphs of tolazamide: why no interconversion?

Assessing Density Functional Theory Approaches for Predicting the Structure and Relative Energy of Salicylideneaniline Molecular Switches in the Solid State

Combined Use of Structure Analysis, Studies of Molecular Association in Solution, and Molecular Modelling to Understand the Different Propensities of Dihydroxybenzoic Acids to Form Solid Phases

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