By using pyridyl sulfide ligands, two CuII complexes, [{Cu2[CH3(CH)2COO]4(4-dps)}2 ·1.5H2O] ( 1) and [Cu2[CH3(CH)2COO]4(4-dpds)] ( 2) (4-dps = 4,4′-dipyridyl sulfide, 4-dpds = 4,4′-dipyridyl disulfide), were synthesized and structurally characterized. Complex 1 shows a 1D zigzag chain, further, the adjacent chains are interconnected through O-H ···O hydrogen bonds to form 1D nanotubes. Complex 2 consists of alternate linking of a Cu2[CH3(CH)2COO]4 unit and a 4-dpds ligand to construct same zigzag chains. According to the crystal structures, the full geometry optimizations of complexes 1 and 2 were carried out by using hybrid DFT methods at B3LYP/6-31G(d) level. Meantime, the DFT-BS approach was applied to study the magnetic coupling behavior for the two complexes, and the result reveals that the calculated exchange coupling constants J were in good agreement with the experimental θ data. Both 1 and 2 showed antiferromagnetic behavior. [ABSTRACT FROM AUTHOR]