In this research work, a new extended π-conjugated chromophore of 4-[4-(4-dimethylamino-phenyl) buta-1,3-dienyl]-1-methyl pyridinium p-styrenesulfonate (DCSSS) is synthesized. The present work demonstrates that 4-[4-(4-dimethylamino-phenyl) buta-1,3-dienyl]-1-methyl pyridiniump-styrene sulfonate hydrate (DCSSS·H2O) crystallizes with centrosymmetric space group (P1¯). The asymmetric structure comprises of 4-((1E,3E)-4-(4-(dimethylamino)phenyl)buta-1,3-dien-1-yl)-1-methylpyridinium cation (C18H21N2 +), 4-vinylbenzenesulfonate (C8H7O3S−) anion and a water molecule. The crystal structure is stabilized by C–H⋯O, O–H⋯O, O–H⋯S types of H-bonding interactions along with π–π stacking interaction and C–H···π interactions. In DCSSS, the anion, cation and water molecule are connected by four Owater–H···Owater and Ccation–H···Osulfonate hydrogen bonds, generating R6 6 (18) graph-set notation. This ring motif is sandwiched between two another R4 4 (12) ring motif, which are generated by four O–H⋯O bonds between anion, cation and water molecules, forming laddar lying parallel to the ab plane. The material was characterized by single crystal XRD method, CHN, NMR, FTIR, FT-Raman, TG-DSC and UV-Vis and luminescence studies. To the best of author's knowledge, all these characterizations were made for the first time. We have also emphasized the role of hydrogen bonding on molecular packing to obtain perfectly aligned cations. Third harmonic generation efficiency of the compound is measured by Z-scan technique with continuous wave semiconductor laser of wavelength 532 nm to realize the nonlinear optical properties DCSSS molecule. © 2019 Elsevier B.V.