Hydrazones (R1R2C=NNR2R4) represent a class of organic ligands capable to coordinate with diverse metal centers generating varied molecular architectures. The Schiff base with the hydrazone fragment provide a good platform for generating a verity of new ligands their metal complexes with promising chemical, physical, biological properties useful for their practical applications. The interest in Mn(II)-based coordination compounds arise not only from its biomimetic roles or as a cofactor for some enzymes, but also because they are good precursors for magnetic materials, as well as for its intricate structures. The crystals of discrete coordination compounds [Mn(H2L1)2(H2O)2](NO3)2 (1) and [Mn3(H2L1)2(NCS)2Cl4(H2O)2] (2) were obtained by template assembly of components, while 2D coordination polymers {[Mn3(L1)3(H2O)2]·1.5C2H5OH}n (3) and {[MnL2]·dmf}n (4) by the direct reaction between pre-synthesized 2,6-diacetylpyridine bis(isonicotinoylhydrazone) (H2L1) and 2,6-diacetylpyridine bis(nicotinoylhydrazone) (H2L2) ligands and manganese sulfate salt (Figure1). Single-crystal X-ray diffraction analysis shows that Schiff bases behave as neutral (1 and 2) and bideprotonated (3 and 4) ligands and coordinate to the Mn(II) ion through azomethine and central pyridyl nitrogen atoms, as well as through carbohydrazide oxygen atoms, while isonicotinic/nicotinic pyridine rings extend the structure dimensionality up to 2D in 2-4. The thermal analysis has been established the influence of the inorganic anion on the stability of synthesized compounds, thus, compound 1 which contains the nitrate anion begins to decompose at a lower temperature than the H2L1 ligand due to the nitrate ion oxidizing effect. The chloride ion, on the other hand, increases the thermal stability of the coordinating compound. In the absence of the inorganic anions, it was noticed that compounds begin to decompose at a temperature close or slightly higher to the ligand.