Two new hybrid solids viz. {Hpz}2[H7CrMo6O24]·6H2O (1) and [Co(2-Hampz)2Cl4] (2) have been crystallized via solvent evaporation technique using pyrazole (pz) and 2-aminopyrazine (2-ampz) respectively. The solids were characterized using single crystal X-ray diffraction, fourier transform infrared spectroscopy, elemental analysis, scanning electron microscopy and thermal analysis. The solid 1 crystallized in orthorhombic system with space group Pbca, a = 23.1796(8), b = 11.1281(4), c = 25.1499(9) Å, Z = 8. The solid 2 crystallized in triclinic system with space group P-1, a = 7.1986(5), b = 7.3917(5), c = 7.8896(6) Å, α = 115.758(3), β = 110.450(3), γ = 96.904(3)°, Z = 1. While, solid 1 is a new Anderson–Evans cluster based solid, 2 is a new pseudopolymorph of cobalt complex [Co(2-ampz)4Cl2]. Crystal structure analysis suggested that supramolecular interactions facilitate the crystal packing in solids 1 and 2. In addition, the role of synthetic parameters in dictating the nature of self-assembly of solids 1 and 2 in aqueous medium has also been analyzed.Graphical AbstractAn Anderson–Evans cluster based solid, {Hpz}2[H7CrMo6O24]·6H2O (1) and a new pseudopolymorph of cobalt complex [Co(2-ampz)4Cl2] viz. [Co(2-Hampz)2Cl4] (2) have been synthesized using pyrazole (pz) and 2-aminopyrazine (2-ampz) respectively.