A kinetically controlled trans bifunctionalized organoimido derivative of hexamolybdate, (n-Bu4N)(2){trans-[Mo6O17(NAr)(2)]} (Ar = 2,6-dimethylphenyl) 1, in which the two 2,6-dimethylphenylimido groups are bonded to hexamolybdate at the trans positions, has been successfully synthesized in ca. 60% yield under mild reaction conditions. Its trans structure has been confirmed by a single-crystal X-ray diffraction study. In the crystals, cluster anions of 1 self-assemble into a 3D netlike structure via two different kinds of C-H center dot center dot center dot O hydrogen bondings, in which 1D supramolecular rectangular channels containing tetrabutylammonium cations form along the a axis. Compound 1 has also been characterized by H-1 NMR, IR, and UV-vis spectroscopic studies. UV-vis-near-IR reflectance spectroscopy measurements reveal the compound's nature of semiconductivity with an optical energy gap of 2.55 eV.