A supramolecular compound Na-3(HABOB)(H(2)ABOB)[MnMo9O32]center dot 5.5H(2)O (ABOB = moroxydine) has been synthesized and characterized by elemental analyses, IR spectrum, diffuse reflectance spectrum, room temperature magnetic moment, single crystal X-ray diffraction, and TG analysis. It exhibits a two-dimensional, layered inorganic framework constructed from Waugh-type polyanions [MnMo9O32](6-) and Na+ ions linkers. Protonated ABOB molecules are hydrogen-bonded to the left- and right- handed [MnMo9O32](6-) enantiomorphs to construct two kinds of infinite organic-inorganic hybrid chains.