Three Ni II -based metal–organic frameworks (MOFs) were synthesized from the nitro-functionalized dicarboxylate ligand 2,2′-dinitro-biphenyl-4,4′-dicarboxylate (H 2 dnpdc) and different N-donor bridging ligands. X-ray analyses revealed that all compounds exhibit 3D architectures. Compound 1, {Ni(dnpdc)(bipy)} n , exhibits 3D framework in which the 2D Ni(dnpdc) sheets are pillared by bipy, with a new (4,6)-connected self-penetrated net topology. In compound 2, {[Ni 3 (dnpdc) 3 (bipy) 3 (H 2 O) 2 ]·(H 2 O) 2 } n , the binuclear Ni 2 (COO) 2 units and mononuclear units are interlinked by the dnpdc and bipy ligands into 3D framework, which displays a rare 3-fold interpenetrated (4,6)-connected net topology. Compound 3, {Ni(dnpdc)(bpee)·H 2 O} n , displays a 6-fold interpenetrated diamond net based on the mononuclear Ni II unit. The magnetic studies of 1 reveal that the double carboxylate bridges in the nonplanar syn-skew conformation mediate ferromagnetic interactions between the Ni II ions.