The asymmetric unit of the title three-dimensional metal–organic hybrid compound, [Co2(C6H2O4S)2(C3H7NO)2]n, comprises two cobalt(II) cations, one residing on a twofold axis and the other on a centre of inversion, one thiophene-2,5-dicarboxylate (tdc2−) ligand and one coordinating dimethylformamide (DMF) solvent molecule. Both of the cobalt(II) cations exhibit an octahedral coordination environment from the four carboxyl O atoms of the tdc2− anions in a μ4-κ1:κ1:κ1:κ1 fashion and two O atoms from DMF. A pair of carboxyl O atoms and one DMF molecule connect the adjacent cobalt(II) cations into an infinite chain, leading to a rod-spacer framework with rhombus-window channels, yet no residual solvent-accessible voids are present because the coordinating DMF molecules are oriented into the potential channels.
