Two new phenyl-bridged pseudopeptidic ligands have been prepared and structurally characterised. The nature of the ligands' substituents play an important role in the nature of the solid state structure yielding either hydrogen bonded linked sheets of molecules or infinite hydrogen bonded networks. Both these ligands were reacted with a range of zinc(II) salts with the aim of synthesising coordination polymers and networks and exploring the role that anions could play in determining the final structure. The crystal structures of four of these systems (with ZnSO4 and ZnBr2) were determined; in one case, a 3D coordination network was obtained where zinc–ligand coordination bonds generated the 3D arrangements. Three other 3D networks were obtained by anion-mediated hydrogen bonding of coordination 1D chains or 2D sheets. These four very different structures highlight the important role played by the ligands' substituents and the counteranions present in the system.