Abstract: | Different salts of the 2‐phenyl‐1,10‐phenanthrolin‐1‐ium cation, (pnpH)+, are obtained by reacting 2‐phenyl‐1,10‐phenanthroline (pnp), C18H12N2, (I), with a variety of anions, such as hexafluoridophosphate, C18H13N2+·PF6?, (II), trifluoromethanesulfonate, C18H13N2+·CF3SO3?, (III), tetrachloridoaurate, (C18H13N2)AuCl4], (IV), and bromide (as the dihydrate), C18H13N2+·Br?·2H2O, (V). Compound (I) crystallizes with Z′ = 2, with both independent molecules adopting a coplanar conformation. In (II)–(IV), a hydrogen bond exists between the cation and anion, while one of the lattice water molecules serves as a hydrogen‐bonded bridge between the cation and anion in (V). Reaction of (I) with HAuCl4 gives the salt complex (IV); however, reaction with KAuCl4 produces the monodentate complex trichlorido(2‐phenyl‐1,10‐phenanthroline‐κN10)gold(III), AuCl3(C18H12N2)], (VI). Dichlorido(2‐phenyl‐1,10‐phenanthroline‐κ2N,N′)copper(II), CuCl2(C18H12N2)], (VII), results from the reaction of CuCl2·2H2O and (I), in which the CuII center adopts a tetrahedrally distorted square‐planar geometry. The pendent phenyl ring twists to a bisecting position relative to the phenanthroline plane. The square‐planar PdII complex, bromido2‐(phenanthrolin‐2‐yl)phenyl‐κ3C1,N,N′]palladium(II), PdBr(C18H11N2)], (VIII), is obtained from the reaction of (I) with PdCl2(cycloocta‐1,5‐diene)], followed by addition of bromine. A coplanar geometry for the pendent ring is adopted as a result of the tridentate bonding motif. |