Structural and Hirshfeld Surface Analysis of Thallium(I) and Indium(III) Complexes of a Soft Scorpionate Ligand
Two complexes containing a soft sulfur-substituted tris(pyrazolyl)hydroborate ligand, namely [Tl<sup>I</sup>(Tm<sup>tBu</sup>)]<sub>2</sub>∙2H<sub>2</sub>O and [In<sup>III</sup>(Tm<sup>tBu</sup>)<sub>2</sub>](InCl<...
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MDPI AG
2023-04-01
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| Online Access: | https://www.mdpi.com/2073-4352/13/5/745 |
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| author | Kiyoshi Fujisawa Ayaka Kuboniwa Sang Loon Tan Edward R. T. Tiekink |
| author_facet | Kiyoshi Fujisawa Ayaka Kuboniwa Sang Loon Tan Edward R. T. Tiekink |
| author_sort | Kiyoshi Fujisawa |
| collection | DOAJ |
| description | Two complexes containing a soft sulfur-substituted tris(pyrazolyl)hydroborate ligand, namely [Tl<sup>I</sup>(Tm<sup>tBu</sup>)]<sub>2</sub>∙2H<sub>2</sub>O and [In<sup>III</sup>(Tm<sup>tBu</sup>)<sub>2</sub>](InCl<sub>4</sub>), where Tm<sup>tBu</sup> is the tris(3-<i>tert</i>-butyl-2-sulfanylidene-1<i>H</i>-imidazol-1-yl)hydroborate anion, have been characterized. The {TlS}<sub>2</sub> core of the former has the shape of a diamond. Each S atom of the Tm<sup>tBu</sup> anion coordinates differently: one S is connected to one Tl atom, one bridges both Tl atoms, while the third S atom connects solely to the second Tl atom. The S<sub>4</sub> donor set defines a seesaw geometry. The independent H<sub>2</sub>O molecule forms O–H···S and localized O–H···π(pyrazolyl) contacts. Flattened octahedral geometries defined by S<sub>6</sub> donor sets are noted for the two independent cations in [In<sup>III</sup>(Tm<sup>tBu</sup>)<sub>2</sub>](InCl<sub>4</sub>). In the crystal of [Tl<sup>I</sup>(Tm<sup>tBu</sup>)]<sub>2</sub>∙2H<sub>2</sub>O, pyrazolyl-C–H···O(water) interactions connect the dimeric units into a linear supramolecular chain, chains pack without directional interactions between them. In the crystal of [In<sup>III</sup>(Tm<sup>tBu</sup>)<sub>2</sub>](InCl<sub>4</sub>), alternating rows of independent cations are interspersed by anions. The primary points of contact within a three-dimensional architecture are of the type In–Cl···π(pyrazolyl) and C–H···Cl. The assessment of the molecular packing was complemented by considering the calculated Hirshfeld surfaces and two-dimensional fingerprint plots (overall and delineated into individual contacts). |
| first_indexed | 2024-03-11T03:49:24Z |
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| id | doaj.art-2321f011abf24d3ca3934d11ce268dd2 |
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| language | English |
| last_indexed | 2024-03-11T03:49:24Z |
| publishDate | 2023-04-01 |
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| spelling | doaj.art-2321f011abf24d3ca3934d11ce268dd22023-11-18T00:59:19ZengMDPI AGCrystals2073-43522023-04-0113574510.3390/cryst13050745Structural and Hirshfeld Surface Analysis of Thallium(I) and Indium(III) Complexes of a Soft Scorpionate LigandKiyoshi Fujisawa0Ayaka Kuboniwa1Sang Loon Tan2Edward R. T. Tiekink3Department of Chemistry, Ibaraki University, Mito 310-8512, Ibaraki, JapanDepartment of Chemistry, Ibaraki University, Mito 310-8512, Ibaraki, JapanResearch Centre for Crystalline Materials, School of Medical and Life Sciences, Sunway University, Bandar Sunway 47500, Selangor Darul Ehsan, MalaysiaResearch Centre for Crystalline Materials, School of Medical and Life Sciences, Sunway University, Bandar Sunway 47500, Selangor Darul Ehsan, MalaysiaTwo complexes containing a soft sulfur-substituted tris(pyrazolyl)hydroborate ligand, namely [Tl<sup>I</sup>(Tm<sup>tBu</sup>)]<sub>2</sub>∙2H<sub>2</sub>O and [In<sup>III</sup>(Tm<sup>tBu</sup>)<sub>2</sub>](InCl<sub>4</sub>), where Tm<sup>tBu</sup> is the tris(3-<i>tert</i>-butyl-2-sulfanylidene-1<i>H</i>-imidazol-1-yl)hydroborate anion, have been characterized. The {TlS}<sub>2</sub> core of the former has the shape of a diamond. Each S atom of the Tm<sup>tBu</sup> anion coordinates differently: one S is connected to one Tl atom, one bridges both Tl atoms, while the third S atom connects solely to the second Tl atom. The S<sub>4</sub> donor set defines a seesaw geometry. The independent H<sub>2</sub>O molecule forms O–H···S and localized O–H···π(pyrazolyl) contacts. Flattened octahedral geometries defined by S<sub>6</sub> donor sets are noted for the two independent cations in [In<sup>III</sup>(Tm<sup>tBu</sup>)<sub>2</sub>](InCl<sub>4</sub>). In the crystal of [Tl<sup>I</sup>(Tm<sup>tBu</sup>)]<sub>2</sub>∙2H<sub>2</sub>O, pyrazolyl-C–H···O(water) interactions connect the dimeric units into a linear supramolecular chain, chains pack without directional interactions between them. In the crystal of [In<sup>III</sup>(Tm<sup>tBu</sup>)<sub>2</sub>](InCl<sub>4</sub>), alternating rows of independent cations are interspersed by anions. The primary points of contact within a three-dimensional architecture are of the type In–Cl···π(pyrazolyl) and C–H···Cl. The assessment of the molecular packing was complemented by considering the calculated Hirshfeld surfaces and two-dimensional fingerprint plots (overall and delineated into individual contacts).https://www.mdpi.com/2073-4352/13/5/745thalliumindiummain group chemistrytripodal ligandthiol ligandcrystal structure |
| spellingShingle | Kiyoshi Fujisawa Ayaka Kuboniwa Sang Loon Tan Edward R. T. Tiekink Structural and Hirshfeld Surface Analysis of Thallium(I) and Indium(III) Complexes of a Soft Scorpionate Ligand Crystals thallium indium main group chemistry tripodal ligand thiol ligand crystal structure |
| title | Structural and Hirshfeld Surface Analysis of Thallium(I) and Indium(III) Complexes of a Soft Scorpionate Ligand |
| title_full | Structural and Hirshfeld Surface Analysis of Thallium(I) and Indium(III) Complexes of a Soft Scorpionate Ligand |
| title_fullStr | Structural and Hirshfeld Surface Analysis of Thallium(I) and Indium(III) Complexes of a Soft Scorpionate Ligand |
| title_full_unstemmed | Structural and Hirshfeld Surface Analysis of Thallium(I) and Indium(III) Complexes of a Soft Scorpionate Ligand |
| title_short | Structural and Hirshfeld Surface Analysis of Thallium(I) and Indium(III) Complexes of a Soft Scorpionate Ligand |
| title_sort | structural and hirshfeld surface analysis of thallium i and indium iii complexes of a soft scorpionate ligand |
| topic | thallium indium main group chemistry tripodal ligand thiol ligand crystal structure |
| url | https://www.mdpi.com/2073-4352/13/5/745 |
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