A straightforward approach to heterometallic Mn-Fe cluster-based coordination polymers is presented. By employing a mixed-valent mu(3)-oxo trinuclear manganese(II/III) pivalate cluster, isolated as [(MnMn2O)-Mn-II-O-III(O2CCMe3)(6)(hmta)(3)]center dot(solvent) (hmta = hexamethylenetetramine; solvent = n-propanol (1), toluene (2)) in the reaction with a mu(3)-oxo trinuclear iron(III) pivalate cluster compound, [Fe3O(O2CCMe3)(6)(H2O)(3)]O2CCMe3 center dot 2Me(3)CCO(2)H, three new heterometallic {(MnFe2III)-Fe-II} cluster-based coordination polymers were obtained: the one-dimensional polymer, chain compounds {[MnFe2O(O2CCMe3)(6)(hmta)(2)]center dot 0.5MeCN}(n) (3) and {[MnFe2O(O2CCMe3)(6)(hmta)(2)]center dot Me3CCO2H center dot(n-hexane)}(n) (4) and the two-dimensional layer compound {[MnFe2O(O2CCMe3)(6)(hmta)(1.5)]center dot(toluene)}(n) (5). Single-crystal X-ray diffraction analysis reveals a mu(3)-oxo trinuclear pivalate cluster building block as the main constituent in all polymer compounds. Different M:hmta ratios in 1-5 are related to the different structural functions of the N-containing ligand. In clusters 1 and 2, three hmta ligands are monodentate, whereas in chains 3 and 4 two hmta ligands act as bridging ligands and one is a monodentate ligand; in 5, all hmta molecules act as bidentate bridges. Magnetic studies indicate dominant antiferromagnetic interactions between the metal centers in both homometallic {Mn-3}-type clusters 1 and 2 and heterometallic {MnFe2}-type coordination polymers 3-5. Modeling of the magnetic susceptibility data to a isotropic model Hamiltonian yields least-squares fits for the following parameters: J(1)(Mn-II-Mn-III) = -6.6 cm(-1) and J(2)(Mn-III-Mn-III) = -5.4 cm(-1) for 1; J(1) = -5.5 cm(-1) and J(2)(Mn-III-Mn-III) = -3.9 cm(-1) for 2; J(1)(Mn-II-Fe-III) = -17.1 cm(-1) and J(2)(Fe-III-Fe-III) = -43.7 cm(-1) for 3; J(1) = -23.8 cm(-1) and J(2) = -53.4 cm(-1) for 4; J(1) = -13.3 cm(-1) and J(2) = -35.4 cm(-1) for 5. Intercluster coupling plays a significant role in all compounds 1-5.