A luminescent Zn(II) complex, [Zn(bpy)(aba)(2)] (1) {bpy = 2,2'-bipyridyl and aba = 4-dimethylaminobenzoate} has been synthesized as a white solid. Complex 1 shows unusually high selectivity toward nitrobenzene in the presence of other organic guests in solution, as well as in the vapor phase, resulting in both a dramatic color change and a concomitant quenching of luminescence. When crystallized from nitrobenzene, 1 affords deep red crystals with the composition [Zn(bpy)(aba)(2)]center dot C6H5NO2 (2) as a hydrogen-bonded channel structure via unusual intermolecular C-H center dot center dot center dot C(sp(3)) and H,,, H interactions. Inside the channels, nitrobenzene molecules form infinite polar linear tapes through strong C-H center dot center dot center dot O interactions in a head-to-tail fashion. The desorption and resorption of nitrobenzene can be achieved in a thermally reversible manner that can be monitored by X-ray powder diffraction patterns.