Derivatives of highly nonlinear optical ionic salt organic crystal HMQ-T (2-(4-hydroxy-3-methoxystyryl)-1-methylquinolinium 4-methylbenzenesulfonate) with 2-(4-hydroxy-3-methoxystyryl)-1-methylquinolinium 4-vinylbenzenesulfonate (HMQ-VBS) replacing the 4-methylbenzenesulfonate of HMQ-T have been synthesized and characterized. In addition we synthesized and characterized derivatives of another highly nonlinear optical ionic salt organic crystal OHQ-T (2-(4-hydroxystyryl)-1-methylquinolinium 4-methylbenzenesulfonate) with 2-(4-hydroxystyryl)-1-methylquinolinium 4-vinylbenzenesulfonate (OHQ-VBS) replacing same counteranion. OHQ-VBS crystal exhibits a highly macroscopic nonlinear optical properties with highly second harmonic generation (SHG) efficiency. The cations of OHQ-VBS constitutes strong head-to-tail hydrogen bonds, and they exhibits acentric crystal structure of cations and counteranion layers. Therefore HMQ-VBS crystal exhibits a centrosymmetric crystal structure. X-ray crystallographic analysis revealed that the crystal structure of OHQ-VBS is monoclinic Pn, which is similar to that of OHQ-T, however HMQ-VBS exhibits a centrosymmetric P21/c structure compare to other three molecules.