Supramolecular architecture of metal–organic frameworks involving dinuclear copper paddle-wheel complexes

Abstract

The two centrosymmetric dinuclear copper paddle-wheel complexes tetrakis(μ-4-hydroxybenzoato-κ(2)O:O')bis[aquacopper(II)] dimethylformamide disolvate dihydrate, [Cu2(C7H5O3)4(H2O)2]·2C3H7NO·2H2O, (I), and tetrakis(μ-4-methoxybenzoato-κ(2)O:O')bis[(dimethylformamide-κO)copper(II)], [Cu2(C8H7O3)4(C3H7NO)2], (II), crystallize with half of the dinuclear paddle-wheel cage unit in the asymmetric unit and, in addition, complex (I) has one dimethylformamide (DMF) and one water solvent molecule in the asymmetric unit. In both (I) and (II), two Cu(II) ions are bridged by four syn,syn-η(1):η(1):μ carboxylate groups, showing a paddle-wheel cage-type structure with a square-pyramidal coordination geometry. The equatorial positions of (I) and (II) are occupied by the carboxylate groups of 4-hydroxy- and 4-methoxybenzoate ligands, and the axial positions are occupied by aqua and DMF ligands, respectively. The three-dimensional supramolecular metal-organic framework of (I) consists of three different R2(2)(20) and an R4(4)(36) ring motif formed via O-H···O and OW-HW···O hydrogen bonds. Complex (II) simply packs as molecular species.

Supramolecular architectures in CoIIand CuIIcomplexes with thiophene-2-carboxylate and 2-amino-4,6-dimethoxypyrimidine ligands

“…1812.571 6 1013.441 3 26.4918 4et al, 2011). In the dimeric Cu-Cu units, the Cu1Á Á ÁCu1 i separation is 2.7411 (5) Å , which is in good agreement with the value in other copper(II) carboxylate paddle-wheel structures (Gomathi & Muthiah, 2013;Jenniefer & Muthiah, 2013;Blake et al, 2002;Smith et al, 1991;Kuchtanin et al, 2013;Paredes-Garcia et al, 2013;Lu, 2003). Along the coordination polymer chain, the NÁ Á ÁN distance in the ring of the bridging-spacer pyrimidine ligand is 2.416 (2) Å , leading to a CuÁ Á ÁCu separation of 6.4922 (5) Å (Fig.…”

Synthesis, crystal structure and Hirshfeld surface analysis of hexaaquanickel(II) bis(4-hydroxybenzoate) dihydrate

“…It demonstrates a wide spectrum of biological actions including antimicrobial, antifungal, antialgal, and antiviral activity, the regulation of plant growth and other types of bioactivities (Manuja et al, 2013;Cho et al, 1998;Sytar et al, 2012). As a result of the presence of carboxyl and hydroxyl groups, PHBA can easily form metal complexes (Lo et al, 2020;Sekine et al, 2018;Gomathi & Muthiah, 2013;Ibragimov et al, 2017a,b). The biological properties of ligand compounds, e.g.…”

Modulatingp-hydroxycinnamate behavior as a ditopic linker or photoacid in copper(ii) complexes with an auxiliary pyridine ligand

“…In complexes containing this ligand, the phenol group usually participates in the generation of supramolecular networks via H-bonds. 11,12 However, it is less common that this -OH group coordinates with metal sites forming 2D coordination polymers. 13 Recently, our group has shown that, in the [Cu( pOHBz) 2 (dPy) 2 ] (dPy = 4-Phpy, 4-Bzpy, 3-PhPy) family of compounds, small changes in the nature and position of the pyridine substituent govern the different roles of the phenol group of the pOHBz ligand: it can be involved in hydrogenbond interactions that lead to the formation of supramolecular networks, or it can be bonded to the copper cation, yielding 2D coordination polymers.…”