bis(2-nitroaniline) picrate (BNP) single crystals was grown by slow evaporation growth technique using mixed solvent system with methanol-acetone (1:1, v/v) at a constant temperature, and the structure was interpreted by single crystal X-ray, Power Diffraction (XRD) analysis. Inter- and intramolecular hydrogen bonding interactions were interpreted, and crystal cohesion was architectured by N-H center dot center dot center dot O, O-H center dot center dot center dot O, C-H center dot center dot center dot N, H center dot center dot center dot H, O center dot center dot center dot O, and pi center dot center dot center dot pi staking interactions. All intermolecular interactions occurring in the crystal lattice were calculated using fingerprint analysis. Interaction strengths were graphically illustrated by the Hirshfeld surface analysis. The band gap energy of BNP was estimated by the application of the Kubelka-Munk algorithm. Nonlinear optical behavior was confirmed by the Kurtz-Perry technique. Optimized geometry was derived by the density functional theory calculations. The first-order molecular hyperpolarizability (beta) and excited state energies were estimated by the time-dependent density functional theory analysis.