Solvothermal/hydrothermal reactions of 4, 4′-biphenyldicarboxylic acid (H2bpdc) and cobalt (II) salt with pyridine derivative ligands such as 3-methylpyridine (3-pic), 4-methylpyridine (4-pic), as well as a longer terminal ligand 4-benzylpyridine (4-bzpy) generated four new extended structures: 1D zigzag polymer chain 1 crystallized in C2/c with a formula [Co(bpdc)(3-pic)2]·(3-pic); 1D helical chain compound 2 crystallized in P41
with a formula [Co(bpdc)(4-pic)2], 2D non-interpenetrating network 3 crystallized in P2221
with a formula [Co(bpdc)(4-pic)2]·(4-pic)0.5·H2O, and 2D non-interpenetrating network 4 crystallized in P2/c, formulated as [Co(bpdc)(bzpy)2]. Our studies show that terminal ligands play an important role in affecting the dimensionality and topology of the structures formed. Magnetic susceptibility and isothermal magnetization results revealed an antiferromagnetic ground state for 3 with a transition temperature T = 4.7 K, and paramagnetic behavior at high temperature range for 1 and 2.