Supramolecular Nature of Multicomponent Crystals Formed from 2,2′-Thiodiacetic Acid with 2,6-Diaminopurine or N9-(2-Hydroxyethyl)adenine
The synthesis and characterization of the multicomponent crystals formed by 2,2′-thiodiacetic acid (Htda) and 2,6-diaminopurine (Hdap) or N9-(2-hydroxyethyl)adenine (9heade) are detailed in this report. These crystals exist in a salt rather than a co-crystal form, as confirmed by single crystal X-ra...
| Autores: | , , , , , , |
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| Formato: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2023 |
| País: | España |
| Recursos: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/352754 |
| Acesso em linha: | http://hdl.handle.net/10261/352754 |
| Access Level: | acceso abierto |
| Palavra-chave: | 2,2′-thiodiacetic acid 2,6-diaminopurine N9-(2-hydroxyethyl)adenine Crystal structures Molecular salts Proton transfer prediction |
| Resumo: | The synthesis and characterization of the multicomponent crystals formed by 2,2′-thiodiacetic acid (Htda) and 2,6-diaminopurine (Hdap) or N9-(2-hydroxyethyl)adenine (9heade) are detailed in this report. These crystals exist in a salt rather than a co-crystal form, as confirmed by single crystal X-ray diffractometry, which reflects their ionic nature. This analysis confirmed proton transfer from the 2,2′-thiodiacetic acid to the basic groups of the coformers. The new multicomponent crystals have molecular formulas [(H9heade)(Htda)] 1 and [(Hdap)(tda)]·2HO 2. These were also characterized using FTIR, H and C NMR and mass spectroscopies, elemental analysis, and thermogravimetric/differential scanning calorimetry (TG/DSC) analyses. In the crystal packing the ions interact with each other via O–H⋯N, O–H⋯O, N–H⋯O, and N–H⋯N hydrogen bonds, generating cyclic hydrogen-bonded motifs with graph-set notation of (Formula presented.) (16), (Formula presented.) (10), (Formula presented.) (10), (Formula presented.) (10), (Formula presented.) (9), (Formula presented.) (8), and (Formula presented.) (8), to form different supramolecular homo- and hetero-synthons. In addition, in the crystal packing of 2, pairs of diaminopurinium ions display a strong anti-parallel π,π-stacking interaction, characterized by short inter-centroids and interplanar distances (3.39 and 3.24 Å, respectively) and a fairly tight angle (17.5°). These assemblies were further analyzed energetically using DFT calculations, MEP surface analysis, and QTAIM characterization. |
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