A bitopic ligand, 4-(3,5-dimethylpyrazol-4-yl)-1,2,4-triazole (Hpz-tr) (1), containing two different heterocyclic moieties was employed for the design of copper(II) molybdate solids under hydrothermal conditions. In the multicomponent Cu-II/Hpz-tr/Mo-VI system, a diverse set of coordination hybrids, [Cu(Hpz-tr)(2)SO4]center dot 3H(2)O (2), [Cu(Hpz-tr)Mo3O10)] (3), [Cu-4(OH)(4)(Hpz-tr)(4)Mo8O26]center dot 6H(2)O (4), [Cu(Hpz-tr)(2)Mo4O13] (5), and [Mo2O6(Hpz-tr)]center dot H2O (6), was prepared and characterized. A systematic investigation of these systems in the form of a ternary crystallization diagram approach was utilized to show the influence of the molar ratios of starting reagents, the metal (Cu-II and Mo-VI) sources, the temperature, etc., on the reaction products outcome. Complexes 2-4 dominate throughout a wide crystallization range of the composition triangle, while the other two compounds 5 and 6 crystallize as minor phases in a narrow concentration range. In the crystal structures of 2-6, the organic ligand behaves as a short [N-N]-triazole linker between metal centers Cu-Cu in 2-4, Cu center dot center dot center dot Mo in 5, and Mo center dot center dot center dot Mo in 6, while the pyrazolyl function remains uncoordinated. This is the reason for the exceptional formation of low-dimensional coordination motifs: 1D for 2, 4, and 6 and 2D for 3 and 5. In all cases, the pyrazolyl group is involved in H bonding (H-donor/H-acceptor) and is responsible for pi-pi stacking, thus connecting the chain and layer structures in more complicated H-bonding architectures. These compounds possess moderate thermal stability up to 250-300 degrees C. The magnetic measurements were performed for 2-4, revealing in all three cases antiferromagnetic exchange interactions between neighboring Cu-II centers and long-range order with a net moment below T-c of 13 K for compound 4.