Keggin-type molecular clusters formed from the partial hydrolysis of aluminum in aqueous solutions have the capacity to adsorb a variety of inorganic and organic contaminants. The adsorptive capability of Keggin-type polyaluminum species, such as Al-13 and Al-30, lead to their wide usage as precursors for heterogeneous catalysts and clarifying agents for water purification applications, but a molecular-level understanding of adsorption process is lacking. Two model Al-30 clusters, whose surface has been modified with chelated metals (Al3+ and Zn2+) have been synthesized and structurally characterized by single-crystal X-ray diffraction. Al(32)IDA [(Al(IDA)H2O)(2)(Al30O8(OH)(60)(H2O)(22))]-(2,6-NDS)(4)(SO4)(2)Cl-4(H2O)(40), IDA = iminodiacetic acid, 2,6-NDS = 2,6 napthalene disulfonate) crystallize in the triclinic space group, P (1) over bar with a = 13.952(2) angstrom, b = 16.319(3) angstrom, c = 23.056(4) angstrom, alpha = 93.31(1)degrees, beta = 105.27(1)degrees, and gamma = 105.52(1)degrees. Zn2Al32 [(Zn(NTA)H2O)(2)(Al(NTA)(OH)(2))(2). (Al-30(OH)(60)(O)(8)(H2O)(20)](2,6-NDS)(5)(H2O)(64), (NTA = nitrilotriacetic acid), also crystallizes in P (1) over bar with unit cell parameter refined as a = 16.733(7) angstrom, b = 18.034(10) angstrom, c = 21.925(11) angstrom, alpha = 82.82(2)degrees, beta = 70.96(2)degrees, and gamma = 65.36(2)degrees. The chelated metal centers adsorb to the surface of the Al-30 clusters through hydroxyl bridges located at the central belt region of the molecule. The observed binding sites for the metal centers mirror the reactivity predicted by previously reported molecular dynamic simulations and can be identified by the acidity and hydration factor of the water group that participates in the adsorption process.