Abstract: | Two organic–inorganic hybrid compounds have been prepared by the combination of the 4‐(E)‐2‐(pyridin‐1‐ium‐2‐yl)ethenyl]pyridinium cation with perhalometallate anions to give 4‐(E)‐2‐(pyridin‐1‐ium‐2‐yl)ethenyl]pyridinium tetrachloridocobaltate(II), (C12H12N2)CoCl4], (I), and 4‐(E)‐2‐(pyridin‐1‐ium‐2‐yl)ethenyl]pyridinium tetrachloridozincate(II), (C12H12N2)ZnCl4], (II). The compounds have been structurally characterized by single‐crystal X‐ray diffraction analysis, showing the formation of a three‐dimensional network through X—H...ClnM? (X = C, N+; n = 1, 2; M = CoII, ZnII) hydrogen‐bonding interactions and π–π stacking interactions. The title compounds were also characterized by FT–IR spectroscopy and thermogravimetric analysis (TGA). |