Two new polyoxovanadoborates based crystalline lattices are being reported: K-5(H3O)(2)(1,3-diapH(2))(2)[V12B18O60H6]center dot 10.80H(2)O (1), and K-2(H3O)(7)(enH(2))[V12B18O60H6]center dot 9H(2)O (2). These structures are characterized by presenting multiple hydrogen bonds between the diprotonated diamines (enH(2) and 1,3-diapH(2)) and hydronium ions, and the oxygen atoms of the [V12B18O60H6] cluster. The crystalline packing and stability of these new polyoxovanadoborates is dominated by the different types of hydrogen interactions present in the lattices ranging from unidirectional to trifurcated ones. The crystallographic data, together with the BVS method, permit to assign a mixed valence ratios for the [V12B18O60H6] anionic cluster for (1) and (2) being 11/1 (V-IV/V-V) ratio.