A deprotonation-protonation method for including in the external sphere of different inorganic anions has been elaborated. On this way two CoII coordination complexes [Co(L+2H)(SO4)(H2O)]SO4·2H2O (1) and [Co(L)(H2O)2](ClO4)2 (2) where L is 2,6-diacetylpyridine-bis-(isonicotinic acid hydrazone) have been obtained. The direct synthesis to obtain crystals suitable for X-ray diffraction from CoSO4 salt was unsuccessful. The CoL carcass is stable to pH variation. As a starting material was used [Co(L)(H2O)2](NCS)2. This compound was treated with NH4OH solution until the green crystalline compound is transformed into an orange precipitate – [Co(L-2H)(H2O)2]. If a suspension of this orange precipitate is treated with acid solution like H2SO4 or HClO4, the high soluble 1 and 2 compounds were obtained in about 24 hours. The structures and compositions have been characterized using elemental analysis, IR and Xray. In the IR spectrum of 1 two bands at 2605-2615 and 2460-2472 cm-1 are observed, which confirm the presence of PyH+ . The peaks at 1627- 1639 cm-1 in 1 and 2 are attributed to coordinated ketone group. The appearance of this peak after acidulation is the fact that the protonation has been successful. The coordinated and uncoordinated 2 SO4 anions have peaks at 1019-1187 cm-1 being in agreement with literature data. The  ClO4 anion also has peaks at 1007-1162 cm-1 . The X-ray single crystal study has shown that the seven-coordinated Co(II) ion has a pentagonalbipyramidal environment formed by the pentadentate bis-Schiff base ligand. The apical coordination positions are occupied by 2 SO4 anion and water molecule for 1 and two water molecules for 2.figureFig.1 Structure of [Co(L+2H)(SO4)(H2O)]SO4·2H2OfigureFig. 2 Structure of [Co(L)(H2O)2](ClO4)2