Symmetry in Recognition of Supramolecular Synthons–Competition between Hydrogen Bonding and Coordination Bond in Multinuclear Cu<sup>II</sup>–4<i>f</i> Complexes with Bicompartmental Schiff Base Ligand
Classic Cu–O coordination bonds in <b>1</b> or elongated semi-coordination ones in <b>2</b> and <b>3</b> were applied to construct Cu<sup>II</sup>–4<i>f</i> complexes composed of trinuclear subunits linked through <i&...
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MDPI AG
2019-04-01
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| Series: | Symmetry |
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| Online Access: | https://www.mdpi.com/2073-8994/11/4/460 |
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| author | Barbara Miroslaw Dariusz Osypiuk Beata Cristóvão Halina Głuchowska |
| author_facet | Barbara Miroslaw Dariusz Osypiuk Beata Cristóvão Halina Głuchowska |
| author_sort | Barbara Miroslaw |
| collection | DOAJ |
| description | Classic Cu–O coordination bonds in <b>1</b> or elongated semi-coordination ones in <b>2</b> and <b>3</b> were applied to construct Cu<sup>II</sup>–4<i>f</i> complexes composed of trinuclear subunits linked through <i>μ</i>-NO<sub>3</sub><sup>−</sup> ions with formulae given as [Cu<sub>2</sub>Tm(H<sub>2</sub>tehy)<sub>2</sub>]<sub>2</sub>(NO<sub>3</sub>)<sub>6</sub>·H<sub>2</sub>O, (<b>1</b>), {[Cu<sub>2</sub>Ho(H<sub>2</sub>tehy)<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub>][Cu<sub>2</sub>Ho(H<sub>2</sub>tehy)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]}(NO<sub>3</sub>)<sub>4</sub>·2H<sub>2</sub>O, (<b>2</b>), and {[Cu<sub>2</sub>Er(H<sub>2</sub>tehy)<sub>2</sub>(H<sub>2</sub>O)]<sub>2</sub>([Cu<sub>2</sub>Er(H<sub>2</sub>tehy)<sub>2</sub>(NO<sub>3</sub>)]<sub>2</sub>}(NO<sub>3</sub>)<sub>10</sub>·2H<sub>2</sub>O·4CH<sub>3</sub>OH, (<b>3</b>), where <b>H<sub>2</sub>tehy</b> = C<sub>19</sub>H<sub>20</sub>N<sub>2</sub>O<sub>4</sub> is a tetrahydroxy Schiff base ligand. Topological analysis showed that the same characteristic motif of coordination accompanied by hydrogen bonds involving the uncoordinated nitrate oxygen atom and ligand’s phenoxy O atoms is responsible for linking trinuclear subunits into a hexanuclear one as well as for bridging the hexanuclear coordination units in <b>3</b> into a 1D supramolecular polymer, with the Cu–O distance being 3.19(1) Å, much longer than the limit of a semi-coordination bond (3.07 Å). The Cambridge Structural Database was used to discuss issues of crystallographic criteria (distance and angular preferences) for the assessment of the stabilizing or destabilizing effect of hydrogen bonding on coordination. The presented results show that the symmetrically repeated arrangement of molecules may provide a useful tool for identifying higher order non-covalently bonded supramolecular aggregates. The complexes <b>1</b>–<b>3</b> have been characterized by X-ray diffraction, FTIR, and thermal analysis. The magnetic studies indicated the ferromagnetic interaction between Cu<sup>II</sup> and Ho<sup>III</sup> ions. |
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| spelling | doaj.art-bce9ffd30c3c41469e670af21ebdfb7d2022-12-22T02:56:47ZengMDPI AGSymmetry2073-89942019-04-0111446010.3390/sym11040460sym11040460Symmetry in Recognition of Supramolecular Synthons–Competition between Hydrogen Bonding and Coordination Bond in Multinuclear Cu<sup>II</sup>–4<i>f</i> Complexes with Bicompartmental Schiff Base LigandBarbara Miroslaw0Dariusz Osypiuk1Beata Cristóvão2Halina Głuchowska3Department of Crystallography, Faculty of Chemistry, Maria Curie-Sklodowska University, Maria Curie-Sklodowska sq. 3, 20-031 Lublin, PolandDepartment of General and Coordination Chemistry, Faculty of Chemistry, Maria Curie-Sklodowska University, Maria Curie-Sklodowska sq. 2, 20-031 Lublin, PolandDepartment of General and Coordination Chemistry, Faculty of Chemistry, Maria Curie-Sklodowska University, Maria Curie-Sklodowska sq. 2, 20-031 Lublin, PolandDepartment of General and Coordination Chemistry, Faculty of Chemistry, Maria Curie-Sklodowska University, Maria Curie-Sklodowska sq. 2, 20-031 Lublin, PolandClassic Cu–O coordination bonds in <b>1</b> or elongated semi-coordination ones in <b>2</b> and <b>3</b> were applied to construct Cu<sup>II</sup>–4<i>f</i> complexes composed of trinuclear subunits linked through <i>μ</i>-NO<sub>3</sub><sup>−</sup> ions with formulae given as [Cu<sub>2</sub>Tm(H<sub>2</sub>tehy)<sub>2</sub>]<sub>2</sub>(NO<sub>3</sub>)<sub>6</sub>·H<sub>2</sub>O, (<b>1</b>), {[Cu<sub>2</sub>Ho(H<sub>2</sub>tehy)<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub>][Cu<sub>2</sub>Ho(H<sub>2</sub>tehy)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]}(NO<sub>3</sub>)<sub>4</sub>·2H<sub>2</sub>O, (<b>2</b>), and {[Cu<sub>2</sub>Er(H<sub>2</sub>tehy)<sub>2</sub>(H<sub>2</sub>O)]<sub>2</sub>([Cu<sub>2</sub>Er(H<sub>2</sub>tehy)<sub>2</sub>(NO<sub>3</sub>)]<sub>2</sub>}(NO<sub>3</sub>)<sub>10</sub>·2H<sub>2</sub>O·4CH<sub>3</sub>OH, (<b>3</b>), where <b>H<sub>2</sub>tehy</b> = C<sub>19</sub>H<sub>20</sub>N<sub>2</sub>O<sub>4</sub> is a tetrahydroxy Schiff base ligand. Topological analysis showed that the same characteristic motif of coordination accompanied by hydrogen bonds involving the uncoordinated nitrate oxygen atom and ligand’s phenoxy O atoms is responsible for linking trinuclear subunits into a hexanuclear one as well as for bridging the hexanuclear coordination units in <b>3</b> into a 1D supramolecular polymer, with the Cu–O distance being 3.19(1) Å, much longer than the limit of a semi-coordination bond (3.07 Å). The Cambridge Structural Database was used to discuss issues of crystallographic criteria (distance and angular preferences) for the assessment of the stabilizing or destabilizing effect of hydrogen bonding on coordination. The presented results show that the symmetrically repeated arrangement of molecules may provide a useful tool for identifying higher order non-covalently bonded supramolecular aggregates. The complexes <b>1</b>–<b>3</b> have been characterized by X-ray diffraction, FTIR, and thermal analysis. The magnetic studies indicated the ferromagnetic interaction between Cu<sup>II</sup> and Ho<sup>III</sup> ions.https://www.mdpi.com/2073-8994/11/4/460semi-coordination bondSchiff base3<i>d</i>–4<i>f</i> complexJahn-Teller distortionhydrogen bond assisted coordination bond |
| spellingShingle | Barbara Miroslaw Dariusz Osypiuk Beata Cristóvão Halina Głuchowska Symmetry in Recognition of Supramolecular Synthons–Competition between Hydrogen Bonding and Coordination Bond in Multinuclear Cu<sup>II</sup>–4<i>f</i> Complexes with Bicompartmental Schiff Base Ligand Symmetry semi-coordination bond Schiff base 3<i>d</i>–4<i>f</i> complex Jahn-Teller distortion hydrogen bond assisted coordination bond |
| title | Symmetry in Recognition of Supramolecular Synthons–Competition between Hydrogen Bonding and Coordination Bond in Multinuclear Cu<sup>II</sup>–4<i>f</i> Complexes with Bicompartmental Schiff Base Ligand |
| title_full | Symmetry in Recognition of Supramolecular Synthons–Competition between Hydrogen Bonding and Coordination Bond in Multinuclear Cu<sup>II</sup>–4<i>f</i> Complexes with Bicompartmental Schiff Base Ligand |
| title_fullStr | Symmetry in Recognition of Supramolecular Synthons–Competition between Hydrogen Bonding and Coordination Bond in Multinuclear Cu<sup>II</sup>–4<i>f</i> Complexes with Bicompartmental Schiff Base Ligand |
| title_full_unstemmed | Symmetry in Recognition of Supramolecular Synthons–Competition between Hydrogen Bonding and Coordination Bond in Multinuclear Cu<sup>II</sup>–4<i>f</i> Complexes with Bicompartmental Schiff Base Ligand |
| title_short | Symmetry in Recognition of Supramolecular Synthons–Competition between Hydrogen Bonding and Coordination Bond in Multinuclear Cu<sup>II</sup>–4<i>f</i> Complexes with Bicompartmental Schiff Base Ligand |
| title_sort | symmetry in recognition of supramolecular synthons competition between hydrogen bonding and coordination bond in multinuclear cu sup ii sup 4 i f i complexes with bicompartmental schiff base ligand |
| topic | semi-coordination bond Schiff base 3<i>d</i>–4<i>f</i> complex Jahn-Teller distortion hydrogen bond assisted coordination bond |
| url | https://www.mdpi.com/2073-8994/11/4/460 |
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