Dataset Information

Hydrogen bonding patterns and C-H...π interactions in the structure of the antiparkinsonian drug (R)-rasagiline mesylate determined using laboratory and synchrotron X-ray powder diffraction data.

ABSTRACT: The structure of (R)-rasagiline mesylate [(R)-RasH⁺·Mes^-], an active pharmaceutical ingredient used to treat Parkinson's disease, is presented. The structure was determined from laboratory and synchrotron powder diffraction data, refined using the Rietveld method, and validated and optimized using dispersion-corrected DFT calculations. The unit-cell parameters obtained in both experiments are in good agreement and the refinement with both datasets converged to good agreement factors. The final parameters obtained from laboratory data were a = 5.4905 (8), b = 6.536 (2), c = 38.953 (3) Å, V = 1398.0 (4) Å³ and from synchrotron powder data were a = 5.487530 (10) Å, b = 6.528939 (12) Å, c = 38.94313 (9) Å, V = 1395.245 (5) Å³ with Z = 4 and space group P2₁2₁2₁. Preferred orientation was properly accounted for using the synchrotron radiation data, leading to a March-Dollase parameter of 1.140 (1) instead of the 0.642 (1) value obtained from laboratory data. In the structure, (R)-RasH⁺ moieties form layers parallel to the ab plane connected by mesylate ions through N-H...O and C-H...O hydrogen bonds. These layers stack along the c axis and are further connected by C-H...π interactions. Hirshfeld surface analysis and fingerprint plot calculations indicate that the main interactions are: H...H (50.9%), H...C/C...H (27.1%) and H...O/O...H (21.1%).

SUBMITTER: Dugarte-Dugarte AJ

PROVIDER: S-EPMC10833353 | biostudies-literature | 2023 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Hydrogen bonding patterns and C-H...π interactions in the structure of the antiparkinsonian drug (R)-rasagiline mesylate determined using laboratory and synchrotron X-ray powder diffraction data.

Dugarte-Dugarte Analio J AJ Toro Robert A RA van de Streek Jacco J Henao José Antonio JA Fitch Andrew N AN Dejoie Catherine C Delgado José Miguel JM Díaz de Delgado Graciela G

Acta crystallographica Section B, Structural science, crystal engineering and materials 20231011 Pt 6

The structure of (R)-rasagiline mesylate [(R)-RasH<sup>+</sup>·Mes<sup>-</sup>], an active pharmaceutical ingredient used to treat Parkinson's disease, is presented. The structure was determined from laboratory and synchrotron powder diffraction data, refined using the Rietveld method, and validated and optimized using dispersion-corrected DFT calculations. The unit-cell parameters obtained in both experiments are in good agreement and the refinement with both datasets converged to good agreemen ...[more]

PMID: 37820013

Similar Datasets

Project description:Starting from a synthetic sample with composition Al2(SO4)3·16.6H2O, the high-temperature- and moisture-dependent behavior of alunogen has been unraveled by TGA measurements, in situ powder X-ray diffraction as well as by gravimetric moisture sorption/desorption studies. Heating experiments using the different techniques show that alunogen undergoes a first dehydration process already starting at temperatures slightly above 40 °C. The crystalline product of the temperature-induced dehydration corresponds to the synthetic equivalent of meta-alunogen and has the following chemical composition: Al2(SO4)3·13.8H2O or Al2(SO4)3(H2O)12·1.8H2O. At 90 °C a further reaction can be monitored resulting in the formation of an X-ray amorphous material. The sequence of "amorphous humps" in the patterns persists up to 250 °C, where a re-crystallization process is indicated by a sudden appearance of a larger number of sharp Bragg peaks. Phase analysis confirmed this compound to be anhydrous Al2(SO4)3. Furthermore, meta-alunogen can be also obtained from alunogen at room temperature when stored at relative humidities (RH) lower than 20 %. The transformation is reversible, however, water sorption of meta-alunogen to alunogen and the corresponding desorption reaction show considerable hysteresis. For RH values above 80 %, deliquescence of the material was observed. Structural investigations on meta-alunogen were performed using a sample that has been stored at dry conditions (0 % RH) over phosphorus pentoxide. Powder diffraction data were acquired on an in-house high-resolution diffractometer in transmission mode using a sealed glass capillary as sample holder. Indexing resulted in a triclinic unit cell with the following lattice parameters: a = 14.353(6) Å, b = 12.490(6) Å, c = 6.092(3) Å, α = 92.656(1)°, β = 96.654(1)°, γ = 100.831(1)°, V = 1062.8(8) Å3 and Z = 2. These data correct earlier findings suggesting an orthorhombic cell. Ab-initio structure solution in space group P [Formula: see text], using simulated annealing, provided a chemically meaningful structure model. The asymmetric unit of meta-alunogen contains three symmetry independent SO4-tetrahedra and two Al(H2O)6 octahedra. The polyhedra are isolated, however, linkage between them is provided by Coulomb interactions and hydrogen bonding. In addition to the water molecules which directly belong to the coordination environment of the aluminum cations there are two additional zeolitic water sites (Ow1 and Ow2). If both positions are fully occupied meta-alunogen corresponds to a 14-hydrate. Structural similarities and differences between the previously unknown structure of meta-alunogen and alunogen are discussed in detail. Since hydrous aluminum sulfates have been postulated to occur in Martian soils, our results may help identifying meta-alunogen by X-ray diffraction not only on the surface of the Earth but also using the Curiosity Rover's ChemMin instrument.

Project description:In this paper, we report the results of the first study focused on the thermal stability and dehydration dynamics of the natural zeolite mineral ferrierite. A sample from Monastir, Sardinia [(Na0.56K1.19Mg2.02Ca0.52Sr0.14) (Al6.89Si29.04)O72·17.86H2O; a = 19.2241(3) Å; b = 14.1563(2) Å; c = 7.5106(1) Å, V = 2043.95(7) Å3] was investigated by thermogravimetric analysis and in-situ synchrotron X-ray powder diffraction. Thermogravimetric data show that H2O release begins already in the range 50-100 °C and is complete at ~600 °C. The results of the structure refinements performed in Immm space group by Rietveld analysis with data collected up to 670 °C show that ferrierite belongs to the group of zeolites that do not undergo phase transitions. Upon heating to 670 °C, ferrierite behaves as a non-collapsible structure displaying only a slight contraction of the unit-cell volume (ΔV = -3%). The unit-cell parameter reductions are anisotropic, more pronounced for a than for b and c (Δa = -1.6%; Δb = -0.76%; Δc = -0.70%). This anisotropic response to a temperature increase is interpreted as due to the presence in the ferrierite framework of five-membered ring chains of SiO4 tetrahedra, which impart a higher structural rigidity along b and c. Upon dehydration we observe: (1) the gradual H2O loss, beginning with the molecules hosted in the 10MR channel, is almost complete at 670 °C, in good agreement with the TG data; (2) as a consequence of the decreased H2O content, Mg and K migrate from their original positions, moving from the center of the 10MR channel toward the walls to coordinate the framework oxygen atoms. The observation of transmission electron microscopy selected-area electron diffraction patterns revealed defective crystals with an occasional and moderate structural disorder. Beyond providing information on the thermal stability and behavior of natural ferrierite, the results of this work have significant implications for possible technological applications. These data allow for comparison with the dehydration kinetics/mechanisms of the corresponding synthetic phases, clarifying the role played by framework and extra-framework species on the high-temperature behavior of porous materials with ferrierite topology. Moreover, the information on the thermal behavior of natural ferrierite can be used to predict the energetic performances of analogous synthetic Si-pure counterparts, namely "zeosil-electrolyte" systems, under non-ambient conditions. Specifically, the very high thermal stability of ferrierite determined in this study, coupled with the baric behavior determined in other investigations, suggests that the "Si-FER-electrolyte" system may be an excellent candidate for use as an energy reservoir. Indeed, ferrierite exhibits the so-called "spring behavior," i.e., upon compression in water or in an electrolyte solution, it converts the mechanical energy into interfacial energy, and-when pressure is released-it can completely restore the supplied mechanical energy accumulated during the compression step.

Dataset Information

Hydrogen bonding patterns and C-H...π interactions in the structure of the antiparkinsonian drug (R)-rasagiline mesylate determined using laboratory and synchrotron X-ray powder diffraction data.

Publications

Hydrogen bonding patterns and C-H...π interactions in the structure of the antiparkinsonian drug (R)-rasagiline mesylate determined using laboratory and synchrotron X-ray powder diffraction data.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets