The aim of the present work was the synthesis of coordination polymers based on hexanuclear manganese pivalate clusters [Mn6O2(O2CCMe3)10L4]. This family of clusters contains the same structural unit [Mn6O2(O2CCMe3)10] and various capped monodentate neutral ligands L which can be replaced by bridging ligands to obtain the coordination polymers. The [Mn6O2(piv)10(Hpiv)4]·(1) and [Mn6O2(piv)10(THF)4]·(2) clusters and exo-polydentate ligands such as 1,3,5-triazine, pyridine3,5-dicarboxylic acid and 4-pyridinecarboxylic acid ethyl ester (PyEt) have been tried as the starting materials for polymer construction. The synthesis has been carried out using different solvents. It was found that only the reaction of cluster 2 with PyEt resulted in formation of 1D-coordination polymer [Mn6O2(O2CCMe3)10(Hpiv)2(PyEt)]n.(3) shown in Fig. 1. Compound 3 crystallizes in the monoclinic space group Cc, a = 24.9206(3) Å, b = 14.3552(2) Å, c = 26.5404(4) Å, β = 115.847(2)º. The PyEt acts as exo-bidentate ligand and is coordinated via the pyridine nitrogen atom in apical position to Mn site of one of clusters and via oxygen atom of ethyl ester group to the neighboring one. The chains run along [101] direction and are packed parallel to each other in the lattice.Fig.1. View of 1D zigzag chains of 3. Hydrogen atoms are omitted for clarity. In other cases, the crystals of discrete hexanuclear clusters solvates with partial or complete substitution of initial terminal ligand by solvent molecules were obtained. Thus, the replacement of one Hpiv molecule is observed in cluster [Mn6O2(piv)10(Hpiv)3EtOH]·Hpiv, while the complete substitution pivalate molecules leads to the formation of [Mn6O2(O2CCMe3)10(EtOH)3MeCN]·MeCN·EtOH. Acknowledgment. This study was supported by the Swiss National Science Foundation (SCOPES IZ73Z0_127925).