A series of coordination polymers, [M(C
5O
5)(dpe)] (M = Mn
1, Fe
2, Cd
3 and Co
4; dpe = 1,2-bis(4-pyridyl)ethane) with a 2D metal–organic framework (MOF) has been synthesized and characterized by single-crystal X-ray diffraction studies. Structural determination reveals that compounds
1–
4 are isostructural and possess a 2D brick-wall-like layered framework with a rectangle grid as the basic building unit through the connectivity of metal ions with μ
3-, μ
4-croconates and
anti-dpe ligands. Two 2D layers are then cross-linkaged by
gauche-dpe ligands to complete a 2D bi-layered MOF and then extended to a 3D supramolecular architecture through π–π and C–H
O interactions between the croconate and pyridyl rings of dpe, which exhibit high thermo-stability and keep their crystalline forms up to 350 °C. The magnetic exchange coupling between the metal centers for compounds
1,
2 and
4 was analyzed and based on the Curie–Weiss expression and a binuclear magnetic model. The negative values of the Weiss constant and the magnetic exchange coupling constant indicate the antiferromagnetic nature between the metal ions
via the bridges of bis-bidentate adjacent μ
3-croconate ligands.