The new organic-inorganic hybrids of tetrakis(azepanium) hexachlorostannate(IV) dichloride (1) and tetrakis(azepanium) hexabromostannate(IV) dibromide (2) crystals have been grown after slow evaporation of the solvent and characterized through single-crystal X-ray diffraction analysis. The characteristic functional groups present in the compounds are confirmed by FT-IR analysis. The direct band gap values for the compounds are estimated by the application of Kubelka-Munk function. Photoluminescence studies exhibit fluorescent emission of both the compounds in the solid-state at room temperature. TG/DTA analysis reveals the thermal pattern of the compounds. Bond valence sum (BVS) calculation confirmed the formal oxidation state of tin to be +4. Z-scan studies very much reveal that both the compounds exhibit significant third-order nonlinear optical response. Investigation of the intermolecular interactions and crystal packing using Hirshfeld surface analysis, derived by single-crystal XRD data, reveals the close contacts associated with strong interactions. © 2020 Elsevier B.V.