The design of innovative metallo-supramolecular assemblies based on the non-covalent interactions such as π–π stacking and hydrogen bonding may adjust the dimensionality and lead to new topologies with desired functions [1]. It is known that the introduction of polycyclic aromatic chelating ligands containing N-donors, like 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen) into the metal-acetylacetonato systems prevent the formation of higher dimensional coordination networks and may provide supramolecular recognition sites for π–π, C–H–π stacking and C–H···O hydrogen bonding to form supramolecular structures [1d, 2]. Herein, we report three supramolecular systems constructed by combining two or three organizing forces: metal-coordination, hydrogen bonds and π–π stacking interactions, [Cr(acac)2(bipy)]NO3·2H2O (1), [Cr(acac)2(phen)]NO3·2H2O (2) and [Cr(acac)2(phen)]ClO4·0.25H2O (3), Hacac = acetylacetone. Compound 1 crystallizes in the monoclinic centrosymmetric P2/c (No 13) space group and the crystal structure consists of the mononuclear [Cr(acac)2(bipy)]+ cation, NO3- anion and two crystallization water molecules. Compounds 2 and 3 were obtained similarly and crystallize in the monoclinic centrosymmetric P2/c (No 13) (2) and P21/c (No 14) (3) space groups. Compounds 1 and 2 are isomorphous with consequential increase of unit cell volume in 2 (V=2388.04(15) Å) against 1 (V=2295.5(3) Å). The crystal structures of 2 and 3 contain the similar mononuclear [Cr(acac)2(phen)]+ cation and nitrate anion and two solvated water molecules in 2 and perchlorate ion and solvated water molecule in 3 refined with 0.25 occupancy. Each chromium(III) ion displays a distorted octahedral coordination involving two N atoms of the chelating bipy/phen group and four O atoms from two bidentate chelating acac ligands. In the crystal structure of 1 the chelate bipy ligands are stacked by the π–π interactions along the crystallographic b axis, giving supramolecular polymer. In the crystal structures of 2 and 3 π–π stacking interactions are noted between neighboring hydrophobic phen molecules of mononuclear cations, yielding 1D supramolecular zipper-like chains along the b direction in 2 similar to 1 and a direction in 3. Crystal packings in 1 and 2 reveal that the hydrophilic outer sphere groups (NO3- and H2O) are interconnected through the hydrogen bonds generated a tetrameric water cluster, that are further organized in a 1D chain with NO3- anions via hydrogen bond interactions. The disordered ClO4- anions and H2O molecules in crystal packing of 3 are accumulated in the interchain space, held there by the electrostatic and van der Waals forces. Compounds 1-3 show ligand-based luminescent properties.