Two supramolecular isomers of [Ni(4-bpd)(2)(NCS)(2)] (4-bpd = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene) with 2D 4(4) square-grid and 3D 6(5).8 frameworks are co-crystallized in a one-pot reaction, both of which exhibit interesting luminescence properties and reversible adsorption-desorption with respect to guest solvents.