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Symmetry in Recognition of Supramolecular Synthons–Competition between Hydrogen Bonding and Coordination Bond in Multinuclear CuII–4f Complexes with Bicompartmental Schiff Base Ligand

1
Department of Crystallography, Faculty of Chemistry, Maria Curie-Sklodowska University, Maria Curie-Sklodowska sq. 3, 20-031 Lublin, Poland
2
Department of General and Coordination Chemistry, Faculty of Chemistry, Maria Curie-Sklodowska University, Maria Curie-Sklodowska sq. 2, 20-031 Lublin, Poland
*
Author to whom correspondence should be addressed.
Symmetry 2019, 11(4), 460; https://doi.org/10.3390/sym11040460
Received: 9 March 2019 / Revised: 27 March 2019 / Accepted: 27 March 2019 / Published: 2 April 2019
Classic Cu–O coordination bonds in 1 or elongated semi-coordination ones in 2 and 3 were applied to construct CuII–4f complexes composed of trinuclear subunits linked through μ-NO3 ions with formulae given as [Cu2Tm(H2tehy)2]2(NO3)6·H2O, (1), {[Cu2Ho(H2tehy)2(NO3)2][Cu2Ho(H2tehy)2(H2O)2]}(NO3)4·2H2O, (2), and {[Cu2Er(H2tehy)2(H2O)]2([Cu2Er(H2tehy)2(NO3)]2}(NO3)10·2H2O·4CH3OH, (3), where H2tehy = C19H20N2O4 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 3 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 13 have been characterized by X-ray diffraction, FTIR, and thermal analysis. The magnetic studies indicated the ferromagnetic interaction between CuII and HoIII ions. View Full-Text
Keywords: semi-coordination bond; Schiff base; 3d–4f complex; Jahn-Teller distortion; hydrogen bond assisted coordination bond semi-coordination bond; Schiff base; 3d–4f complex; Jahn-Teller distortion; hydrogen bond assisted coordination bond
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MDPI and ACS Style

Miroslaw, B.; Osypiuk, D.; Cristóvão, B.; Głuchowska, H. Symmetry in Recognition of Supramolecular Synthons–Competition between Hydrogen Bonding and Coordination Bond in Multinuclear CuII–4f Complexes with Bicompartmental Schiff Base Ligand. Symmetry 2019, 11, 460.

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