We synthesized a discrete type of organic-inorganic hybrid crystal [Cu(ina)2(NH3)2(H2O)2] (ina = isonicotinate). The monomer units connect to each other with hydrogen bonds and pi-pi interactions, forming a three-dimensional network. Removal of ammonia and water molecules by vacuum heating treatment induced a substantial change from nonporous to porous crystals. The resultant porous crystals can predominantly adsorb supercritical hydrogen rather than nitrogen vapor at 77 K.