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Dinuclear complex [Co2(H2O)4(dmb)2(muc)][muc] (1) (muc = muconate; dmb = 5,5′-dimethyl-2,2′-bipyridine), was obtained by self-assembly solution reaction, under ambient conditions, and it was structurally characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction. The complex 1 crystallizes in the monoclinic system in the C2/c space group. Noticeably, the six-coordinated Co(II) centers display a distorted-trigonal prismatic configuration. This uncommon coordination geometry is attained due to the hydrogen bonding interactions of the crystalline structure of 1, yielding thus a 2D supramolecular array. Magnetic properties measurements reveal that metaprism 1 exhibits weak antiferromagnetic ordering with θ(C-W) = -14.4 K and an E2 = 0.032 cm−1 accordingly to Curie–Weiss model and Rueff phenomenological approach, respectively. Influence of the 2D supramolecular array in the distorted trigonal prismatic geometry of a dinuclear Co(II)-muconate complex exhibiting weak antiferromagnetic exchange. [ABSTRACT FROM AUTHOR]