A rigid imidazolate/sulfonate functionalized ligand, 6-(4sulfonatopheny)imidazo[4,5-f]isoindole-5,7-dione (SPID) was designed and used for assembling reactions with Mn 2+ and Cu 2+ ions. 1006 acetamide) were obtained. Single crystal X-ray analyses show that 1 has a 2D (4,4)-net based on 4-connected Mn 2+ nodes and μ 2 -coordinated H -1 SPID spacers, whereas compound 2 has a 2D (6,3)-net built of 3-connected Cu 2+ nodes and μ 3 -coordinated H -2 SPID spacers. Additionally, the thermal behavior of 1 and 2 is presented.