Crystal Structure, Hirshfeld Analysis, and DFT Calculations of Three Trinuclear Cu(II) Polymorphs
The crystal structure of the ferromagnetically-coupled Cu<sup>II</sup><sub>3</sub>−pyrazolato complex, (Bu<sub>4</sub>N)<sub>2</sub>[Cu<sub>3</sub>(μ<sub>3</sub>-Cl)<sub>2</sub>(μ-4-NO<sub>2</sub>-pz)<...
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MDPI AG
2022-11-01
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| author | Kelly L. Rue Logesh Mathivathanan Gellert Mezei Alexander M. Mebel Raphael G. Raptis |
| author_facet | Kelly L. Rue Logesh Mathivathanan Gellert Mezei Alexander M. Mebel Raphael G. Raptis |
| author_sort | Kelly L. Rue |
| collection | DOAJ |
| description | The crystal structure of the ferromagnetically-coupled Cu<sup>II</sup><sub>3</sub>−pyrazolato complex, (Bu<sub>4</sub>N)<sub>2</sub>[Cu<sub>3</sub>(μ<sub>3</sub>-Cl)<sub>2</sub>(μ-4-NO<sub>2</sub>-pz)<sub>3</sub>Cl<sub>3</sub>] (<b>1a</b>, pz = pyrazolato anion), was originally determined in the triclinic <i>P</i>-1 space group. By varying the recrystallization solvent and temperature, two additional true polymorphs were crystallized in the monoclinic <i>P</i>2<sub>1</sub>/<i>n</i> (<b>1b</b>) and orthorhombic <i>Pbca</i> (<b>1c</b>) space groups. Comparison of the metric parameters of the three polymorphs revealed only minor variations in their bond lengths and angles but clearly distinguishable packing patterns. The DFT calculations showed that, in vacuum, <b>1a</b> had the lowest energetic minimum (also the densest of three polymorphs), whereas <b>1b</b> and <b>1c</b> lay at 6.9 kcal/mol and 7.8 kcal/mol higher energies. The existence of isolable <b>1b</b> and <b>1c</b> is, therefore, attributed to the intermolecular interactions analyzed by the Hirshfeld methods. |
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| last_indexed | 2024-03-09T18:24:32Z |
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| series | Crystals |
| spelling | doaj.art-7aacc1e93625421c85256952a5dde37e2023-11-24T08:01:50ZengMDPI AGCrystals2073-43522022-11-011211161110.3390/cryst12111611Crystal Structure, Hirshfeld Analysis, and DFT Calculations of Three Trinuclear Cu(II) PolymorphsKelly L. Rue0Logesh Mathivathanan1Gellert Mezei2Alexander M. Mebel3Raphael G. Raptis4Department of Chemistry and Biochemistry, Florida International University, Miami, FL 33199, USADepartment of Chemistry and Biochemistry, Florida International University, Miami, FL 33199, USADepartment of Chemistry, Western Michigan University, Kalamazoo, MI 49008, USADepartment of Chemistry and Biochemistry, Florida International University, Miami, FL 33199, USADepartment of Chemistry and Biochemistry, Florida International University, Miami, FL 33199, USAThe crystal structure of the ferromagnetically-coupled Cu<sup>II</sup><sub>3</sub>−pyrazolato complex, (Bu<sub>4</sub>N)<sub>2</sub>[Cu<sub>3</sub>(μ<sub>3</sub>-Cl)<sub>2</sub>(μ-4-NO<sub>2</sub>-pz)<sub>3</sub>Cl<sub>3</sub>] (<b>1a</b>, pz = pyrazolato anion), was originally determined in the triclinic <i>P</i>-1 space group. By varying the recrystallization solvent and temperature, two additional true polymorphs were crystallized in the monoclinic <i>P</i>2<sub>1</sub>/<i>n</i> (<b>1b</b>) and orthorhombic <i>Pbca</i> (<b>1c</b>) space groups. Comparison of the metric parameters of the three polymorphs revealed only minor variations in their bond lengths and angles but clearly distinguishable packing patterns. The DFT calculations showed that, in vacuum, <b>1a</b> had the lowest energetic minimum (also the densest of three polymorphs), whereas <b>1b</b> and <b>1c</b> lay at 6.9 kcal/mol and 7.8 kcal/mol higher energies. The existence of isolable <b>1b</b> and <b>1c</b> is, therefore, attributed to the intermolecular interactions analyzed by the Hirshfeld methods.https://www.mdpi.com/2073-4352/12/11/1611polymorphismHirshfeld analysisDFT calculationstrinuclear copperpyrazolato ligands |
| spellingShingle | Kelly L. Rue Logesh Mathivathanan Gellert Mezei Alexander M. Mebel Raphael G. Raptis Crystal Structure, Hirshfeld Analysis, and DFT Calculations of Three Trinuclear Cu(II) Polymorphs Crystals polymorphism Hirshfeld analysis DFT calculations trinuclear copper pyrazolato ligands |
| title | Crystal Structure, Hirshfeld Analysis, and DFT Calculations of Three Trinuclear Cu(II) Polymorphs |
| title_full | Crystal Structure, Hirshfeld Analysis, and DFT Calculations of Three Trinuclear Cu(II) Polymorphs |
| title_fullStr | Crystal Structure, Hirshfeld Analysis, and DFT Calculations of Three Trinuclear Cu(II) Polymorphs |
| title_full_unstemmed | Crystal Structure, Hirshfeld Analysis, and DFT Calculations of Three Trinuclear Cu(II) Polymorphs |
| title_short | Crystal Structure, Hirshfeld Analysis, and DFT Calculations of Three Trinuclear Cu(II) Polymorphs |
| title_sort | crystal structure hirshfeld analysis and dft calculations of three trinuclear cu ii polymorphs |
| topic | polymorphism Hirshfeld analysis DFT calculations trinuclear copper pyrazolato ligands |
| url | https://www.mdpi.com/2073-4352/12/11/1611 |
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