Synthesis and Structures of Silver Halide Complexes [Ph₃PCH=CH₂]_n[Ag₂Br₃]_n, [Ph₃PCH=CH₂]_n[Ag₅Br₆]_n, and [Ph₃PCH₂CH=CHCH₂PPh₃][Ag₂I₄]

Haloargentate complexes [Ph₃PCH=CH₂]_n[Ag₂Br₃]_n (I), [Ph₃PCH=CH₂]_n[Ag₅Br₆]_n (II), and [Ph₃PCH₂CH=CHCH₂PPh₃][Ag₂I₄] (III) were synthesized by the reaction of silver bromide with (2-bromoethyl)- and vinyltriphenylphosphonium bromides, as well as silver iodide with but-2-ene-1,4-diyl-bis(triphenylphosphonium) diiodide in DMSO. The obtained products were characterized by IR spectroscopy and X-ray diffraction (CCDC nos. 2173339 (I), 2172944 (II), 1985085 (III)). According to X-ray diffraction data, compounds I–III consist of organyltriphenylphosphonium cations with tetrahedrally coordinated phosphorus atoms and the corresponding haloargentate anions of 1D-polymeric (I, II) or non-polymeric (III) structures. Anions [Ag₂Br₃ \(]_{n}^{{n-}}\) , [Ag₅Br₆ \(]_{n}^{{n-}}\) are built of tetrahedral {AgBr₄} fragments, while anion [Ag₂I₄]^2– is built of two trigonal fragments {AgBr₃}. In all the resulting complexes, the Ag centers are additionally bonded to each other by argentophilic contacts with Ag···Ag distances in the range of 2.8162(12)–3.371(2) Å.