An achiral nonlinear optical chromophore with a "remote functionality" that can act as a ligand is developed on the basis of 4-nitroaniline derivatized with pyridine. The molecules are assembled through complexation with simple achiral zinc(II) salts and the H-bond network mediated by the counterions, to generate noncentrosymmetric materials exhibiting optical second harmonic generation (SHG). The crystal structures of the new complexes are determined; the counterion strongly influences the ligand orientations and lattice structure. SHG of the microcrystalline materials is investigated. Correlation between the structure and SHG is rationalized using semiempirical quantum chemical estimation of the hyperpolarizabilities of molecules and molecular clusters. The metal complexation plays a significant role in molecular assembly but affects the SHG very little, enabling simplified analysis of the bulk property in terms of molecular responses. Organization of remote functionalized molecules by metal ion complexation thus offers a convenient approach to the rational design of quadratic NLO materials.