5 ]$5H 2 O} n (4), in the presence of ancillary ligands (4,4 0 -bpy ¼ 4,4 0 -bipyridine, 1,4-bib ¼ 1,4-bis(1-imidazolyl)benzene). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by IR spectra, elemental analyses, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Complex 1 exhibits a 3D framework with one-dimensional channels along the [111] direction, which can be defined as a (4,10)-connected deh1 net with the point Schläfli symbol of {3$4 5 } 2 {3 4 $4 12 $5 10 $6 14 $7 3 $8 2 }. Compound 2 contains two interpenetrated 3D networks, each of which can be viewed as a (4,4)-connected mog moganite network with the point Schläfli symbol of {4$6 4 $8} 2 {4 2 $6 2 $8 2 }. In Complex 3, both the Hbptc 3À and the 1,4-bib show m 2 coordination mode, the former of which links two Co2 cations to form a 1D anionic chain and the latter of which links two Co1 cations to generate a 1D cationic chain. Interestingly, the 1D anionic chains are assembled through abundant strong hydrogen bonds to generate a 3D supermolecular structure with large one-dimensional channels occupied by the 1D cationic chains along the c axis. Complex 4 consists of two interpenetrated 3D networks, each of which can be simplified as a novel (3,4,4)-connected framework with the point Schlafi symbol of {4$6$8}{4$6 3 $8 2 }{6 4 $8$10}. In addition, the magnetic properties for 1, 2 and the photoluminescent properties for 3, 4 were investigated. The magnetic results show that there exist antiferromagnetic interactions between Cu(II) ions in 1 and 2.