Search

Background Design of new metal complexes is an interesting field for development of new functional molecular based materials. In this process by the usage of mixed functional ligands one can precisely tune the physical and chemical properties of those metal complexes. However, it is difficult to obtain the desired complex in many cases for factors like different coordination abilities of the ligands and the types of anions have a great influence on the structure. Results A series of five copper(II) complexes [Cu(Bipy) (5-TPC) 2(H2O)] (1), [Cu(Phen) (5-TPC) 2(H2O)] (2), [Cu(NO3) (4,7-Phen) (5-TPC) (H2O)].H2O (3), [Cu(Bipy) 2(5-TPC)]2.(ClO4)2 (4), and [Cu2(Bipy)4(H2PO4)] (5) (where Bipy = 2,2'-bipyridine, Phen = 1,10-phenanthroline, 4,7-Phen = 4,7-hydroxy-1,10-phenanthroline, 5-TPC = 5-chloro-2 thiophene carboxylate) has been synthesized and characterised using single crystal X-ray diffraction studies. In all the compounds, the N,N' ligand coordinates in a bidentate chelating manner and the copper has a square pyramidal geometry. Conclusions Complexes (1,2) are expected to be isostructural due to similarity of the N.N'-chelating ligands used, but due to the difference in supramolecular architectures no similar unit cells were observed. This is important in crystal engineering point of view. Complexes (1-4) possess the neutral mononuclear and complex (5) possesses a dinuclear entity. These entities are connected by intermolecular interactions like X...π, H...X, (X = Cl) generating supramolecular architectures. [ABSTRACT FROM AUTHOR]

Highlights: [•] Two paddle wheel typed two Cu(II) complexes have been synthesized. [•] The complexes have been characterized by IR, EPR and X-ray diffraction studies. [•] It is interesting that complexes (1) and (2) differ in the axial coordinated solvent. [•] Influences of the axial solvents on supramolecular architectures are investigated. [Copyright &y& Elsevier]

Abstract: In the present study 1,2-bis(4-pyridyl)ethane (BPA) crystallizes with 2-chlorobenzoic acid (2CBA), 4-methylbenzoic acid (4MBA), phthalic acid (PA), succinic acid (SA) and adipic acid (AA) to yield co-crystals BPA.2CBA (1), BPA.4MBA (2), BPA.PA (3), BPA.SA (4) and BPA.AA (5) respectively. All the five co-crystals are constituted by the utilization of the (7) synthon, created by the combination of hard N-H⋯O and complementary soft C–H⋯O hydrogen bonds. 1 and 2 illustrate the formation of three component aggregate as in both cases BPA interacts with carboxylic acids to form supramolecular ladder-type assembies. Molecular recognition in co-crystals 3–5 results in the formation of extended infinite tapes and differ further as a consequence of the soft C–H⋯O bonds and stacking interactions. Structure 3 shows the formation of zig-zag tapes while 4 and 5 form linear infinite tapes. Structure 4 shows isostructural behaviour with an analogous structure previously reported (Bowes et al. (2003) ).The isostructurality is because of the structural resemblance between both the entities in the co-crystals – fumaric acid/succinic acid and 1,2-bis(4-pyridyl)ethane/1,2-bis(4-pyridyl)ethene. Compound 5 shows good degree of resemblance with another reported analogous structure-1,2-bis(4-pyridyl)ethene adipic acid. (Zhang et al. (2003) ). Structure 5 and the reported structure form similar supramolecular sheets through intertape interactions differing from each other only in the alignment of neighboring tapes. The linear tapes in both the cases are linked laterally through different C–H⋯O interactions and ventrally through different stacking interactions. This work illustrates the construction of different supramolecular architectures and the role of weak C–H⋯O hydrogen bonds and stacking interactions in the higher level of supramolecular organization. [Copyright &y& Elsevier]