Two new coordination polymers based on hexanuclear metal cluster cores, Zn-6(HCOO)(6)(DBrTPA)(3)(DMF)(6) (1) and Mn-6(HCOO)(6)(BTC)(2)(DMF)(6) (2) have been solvothermally synthesized. It is noteworthy that the formic ligands were in situ generated by the hydrolysis of DMF solvent under the solvothermal conditions and incorporated into these two compounds. The temperature-dependence of magnetic susceptibility for 2 shows antiferromagnetic interactions between metal centers.