Synthesis and Characterization of Three Diverse Coordination Frameworks under Co‐ligand Intervention

The chelating organic ligands of 2,2′‐bipyridine (2,2′‐bipy), di(pyrid‐2‐yl)amine (dpa) and 2,6‐di(pyrid‐2‐ylamino)pyridine (dpap) were respectively applied to react with H 2 fum (fumaric acid) and copper salts, affording three different complexes [Cu 2 (fum)(2,2′‐bipy) 4 ]·2ClO 4 ( 1 ), [Cu 2 (µ‐OH) 2 (fum)(dpa) 2 ]·2H 2 O ( 2 ) and [Cu(SO 4 )(H 2 O)(dpap)]·H 2 O ( 3 ). These complexes were determined by single‐crystal X‐ray diffraction. Each penta‐coordinated Cu(II) ion exhibits a distorted trigonal bipyramidal geometry in 1 . The fum ligand links copper ions to form a dinuclear copper unit. While in 2 , the fum ligands connect [Cu 2 (µ‐OH) 2 (dpa) 2 ] unit to construct a 1D zigzag chain. Unexpectedly, when dpap instead of dpa was used under the same conditions, only one mononuclear complex 3 was formed. Crystal packings show that 1 – 3 form 3D supramolecular architectures through non‐covalent interactions (multiple hydrogen bonds and C–H··· π/π‐π interactions). In addition, the study of the magnetic property reveals dominating ferromagnetic interactions between Cu(II) atoms in 1 .