A series of zinc dipicolinate (2,6-pyridinedicarboxylate; pdc) complexes [H2tmbpy][Zn(pdc)2]•5H2O (1) {H2tmbpy = 1,3-bis(4-pyridinium)propane(2+)}, [H2bpy][Zn(pdc)2]•6H2O (2) {H2bpy = 4,4'-bipyridinium(2+)}, [H2bpy][Zn(pdc)2]•3.5(4np)•2H2O (3) {4np = 4-nitrophenol}, [H2tmbpy][Zn(pdc)2]•4(2,7dhn)•3H2O (4) {2,7dhn = 2,7-dihydroxynapthalene}, [H2bpy][Zn(pdc)2]•2(2,7dhn)•5H2O (5), [H2bpy][Zn(pdc)2]•2(pyrogl)•6H2O (6) {pyrogl = pyrogallol}, and [H2tmbpy][Zn(pdc)2]•2(2,6dhn)•8H2O (7) {2,6dhn = 2,6-dihydroxynapthalene} were synthesized and characterised. Different packing patterns in these complexes arise from differences in the ability of cations to π-stack with zinc dipicolinate units. In 2, the planar [H2bpy]2+ moieties are π-stacked with adjacent 4,4'-bipyridinium cations and [Zn(pdc)2]2– anions, whereas in 1 π-stacks are formed exclusively between [Zn(pdc)2]2– moieties. 4-nitrophenol can selectively replace the [H2bpy]2+ cations to form an adduct 3, thus representing a novel host-guest system for molecular recognition of 4-nitrophenol. This recognition does not occur upon treatment of 4-nitrophenol with 1 that bears a nonplanar [H2tmbpy]2+ cation. Host-guest interactions of pyrogallol, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynapthalene with the parent complexes 1 and 2 were studied, resulting in the crystallization of 4–7. Crystal structures of 5–7 show that guest organic molecules are accommodated in the layers of zinc dipicolinate anions. The formation of different water clusters is also discussed. Besides, the topological analysis and classification of H-bonded patterns driven by strong hydrogen bonds between the [H2bpy]2+ or [H2tmbpy]2+ cations and [Zn(pdc)2]2– anions, and organic guest molecules was carried out. This analysis revealed: (i) the discrete 0D dimeric (in 1 and 2) or tetrameric (in 7) motifs with the 1M2-1 or 1,3M4-1 topology, respectively, (ii) the infinite 1D zigzag chains with the 2C1 topology in 5, and (iii) the infinite 2D layers with the SP 2-periodic net (4,4)Ia and hcb [Shubnikov hexagonal plane net/(6,3)] topology in 6, respectively.