Synthesis, X-ray Characterization and Density Functional Theory (DFT) Studies of Two Polymorphs of the α,α,α,α, Isomer of Tetra-<i>p</i>-Iodophenyl Tetramethyl Calix[4]pyrrole: On the Importance of Halogen Bonds
This manuscript reports the improved synthesis of the α,α,α,α isomer of tetra-<i>p</i>-iodophenyl tetra-methyl calix[4]pyrrole and the X-ray characterization of two solvate polymorphs. In the solid state, the calix[4]pyrrole receptor adopts the cone co...
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MDPI AG
2020-01-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/2/285 |
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| author | Dragoș Dăbuleanu Antonio Bauzá Joaquín Ortega-Castro Eduardo C. Escudero-Adán Pablo Ballester Antonio Frontera |
| author_facet | Dragoș Dăbuleanu Antonio Bauzá Joaquín Ortega-Castro Eduardo C. Escudero-Adán Pablo Ballester Antonio Frontera |
| author_sort | Dragoș Dăbuleanu |
| collection | DOAJ |
| description | This manuscript reports the improved synthesis of the α,α,α,α isomer of tetra-<i>p</i>-iodophenyl tetra-methyl calix[4]pyrrole and the X-ray characterization of two solvate polymorphs. In the solid state, the calix[4]pyrrole receptor adopts the cone conformation, including one acetonitrile molecule in its aromatic cavity by establishing four convergent hydrogen bonds between its nitrogen atom and the four pyrrole NHs of the former. The inclusion complexes pack into rods, displaying a unidirectional orientation. In turn, the rods form flat 2D-layers by alternating the orientation of their <i>p</i>-iodo substituents. The 2D layers stack on top of another, resulting in a head-to-head and tail-to-tail orientation of the complexes or their exclusive arrangement in a head-to-tail geometry. The dissimilar stacking of the layers yields two solvate polymorphs that are simultaneously present in the structures of the single crystals. The ratio of the two polymorph phases is regulated by the amount of acetonitrile added to the chloroform solutions from which the crystals grow. Halogen bonding interactions are highly relevant in the crystal lattices of the two polymorphs. We analyzed and characterized these interactions by means of density functional theory (DFT) calculations and several computational tools. Remarkably, single crystals of a solvate containing two acetonitrile molecules per calix[4]pyrrole were obtained from pure acetonitrile solution. |
| first_indexed | 2024-12-20T02:09:08Z |
| format | Article |
| id | doaj.art-b219ed9fc60a410295653ae9f427b816 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-20T02:09:08Z |
| publishDate | 2020-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-b219ed9fc60a410295653ae9f427b8162022-12-21T19:57:07ZengMDPI AGMolecules1420-30492020-01-0125228510.3390/molecules25020285molecules25020285Synthesis, X-ray Characterization and Density Functional Theory (DFT) Studies of Two Polymorphs of the α,α,α,α, Isomer of Tetra-<i>p</i>-Iodophenyl Tetramethyl Calix[4]pyrrole: On the Importance of Halogen BondsDragoș Dăbuleanu0Antonio Bauzá1Joaquín Ortega-Castro2Eduardo C. Escudero-Adán3Pablo Ballester4Antonio Frontera5Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Avinguda Països Catalans, 16, 43007 Tarragona, SpainDepartament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, 07122 Palma de Mallorca (Baleares), SpainDepartament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, 07122 Palma de Mallorca (Baleares), SpainInstitute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Avinguda Països Catalans, 16, 43007 Tarragona, SpainInstitute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Avinguda Països Catalans, 16, 43007 Tarragona, SpainDepartament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, 07122 Palma de Mallorca (Baleares), SpainThis manuscript reports the improved synthesis of the α,α,α,α isomer of tetra-<i>p</i>-iodophenyl tetra-methyl calix[4]pyrrole and the X-ray characterization of two solvate polymorphs. In the solid state, the calix[4]pyrrole receptor adopts the cone conformation, including one acetonitrile molecule in its aromatic cavity by establishing four convergent hydrogen bonds between its nitrogen atom and the four pyrrole NHs of the former. The inclusion complexes pack into rods, displaying a unidirectional orientation. In turn, the rods form flat 2D-layers by alternating the orientation of their <i>p</i>-iodo substituents. The 2D layers stack on top of another, resulting in a head-to-head and tail-to-tail orientation of the complexes or their exclusive arrangement in a head-to-tail geometry. The dissimilar stacking of the layers yields two solvate polymorphs that are simultaneously present in the structures of the single crystals. The ratio of the two polymorph phases is regulated by the amount of acetonitrile added to the chloroform solutions from which the crystals grow. Halogen bonding interactions are highly relevant in the crystal lattices of the two polymorphs. We analyzed and characterized these interactions by means of density functional theory (DFT) calculations and several computational tools. Remarkably, single crystals of a solvate containing two acetonitrile molecules per calix[4]pyrrole were obtained from pure acetonitrile solution.https://www.mdpi.com/1420-3049/25/2/285polymorphshalogen bondssupramolecular chemistrylattice energiesdensity functional theory (dft) calculations |
| spellingShingle | Dragoș Dăbuleanu Antonio Bauzá Joaquín Ortega-Castro Eduardo C. Escudero-Adán Pablo Ballester Antonio Frontera Synthesis, X-ray Characterization and Density Functional Theory (DFT) Studies of Two Polymorphs of the α,α,α,α, Isomer of Tetra-<i>p</i>-Iodophenyl Tetramethyl Calix[4]pyrrole: On the Importance of Halogen Bonds Molecules polymorphs halogen bonds supramolecular chemistry lattice energies density functional theory (dft) calculations |
| title | Synthesis, X-ray Characterization and Density Functional Theory (DFT) Studies of Two Polymorphs of the α,α,α,α, Isomer of Tetra-<i>p</i>-Iodophenyl Tetramethyl Calix[4]pyrrole: On the Importance of Halogen Bonds |
| title_full | Synthesis, X-ray Characterization and Density Functional Theory (DFT) Studies of Two Polymorphs of the α,α,α,α, Isomer of Tetra-<i>p</i>-Iodophenyl Tetramethyl Calix[4]pyrrole: On the Importance of Halogen Bonds |
| title_fullStr | Synthesis, X-ray Characterization and Density Functional Theory (DFT) Studies of Two Polymorphs of the α,α,α,α, Isomer of Tetra-<i>p</i>-Iodophenyl Tetramethyl Calix[4]pyrrole: On the Importance of Halogen Bonds |
| title_full_unstemmed | Synthesis, X-ray Characterization and Density Functional Theory (DFT) Studies of Two Polymorphs of the α,α,α,α, Isomer of Tetra-<i>p</i>-Iodophenyl Tetramethyl Calix[4]pyrrole: On the Importance of Halogen Bonds |
| title_short | Synthesis, X-ray Characterization and Density Functional Theory (DFT) Studies of Two Polymorphs of the α,α,α,α, Isomer of Tetra-<i>p</i>-Iodophenyl Tetramethyl Calix[4]pyrrole: On the Importance of Halogen Bonds |
| title_sort | synthesis x ray characterization and density functional theory dft studies of two polymorphs of the α α α α isomer of tetra i p i iodophenyl tetramethyl calix 4 pyrrole on the importance of halogen bonds |
| topic | polymorphs halogen bonds supramolecular chemistry lattice energies density functional theory (dft) calculations |
| url | https://www.mdpi.com/1420-3049/25/2/285 |
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