Silver(I)–phenoxyalkanoates. The crystal and molecular structures of polymeric [(4-chloro-2-methylphenoxy)ethanoato-O,O′]silver(I), [(2,4-dichlorophenoxy)-ethanoato-O,O′]silver(I), and di-µ-[(2-chlorophenoxy)ethanoato-O,O′]-disilver(I)–silver(I) perchlorate (1/1)

Abstract

The crystal structures of three polymeric silver(I) phenoxyalkanoates have been determined by X-ray diffraction. The isomorphous complexes, [(4-chloro-2-methylphenoxy)ethanoato]silver(I)(1) and [(2,4-dichlorophenoxy)ethanoato]silver(I)(2) are chain polymers of the type [{AgL}_n] and involve only two-co-ordinate linear bonds to silver [Ag–O, 2.185(3)–2.217(3)Å; O–Ag–O, 176.8(2), 177.5(2)°]. Complex (1) is monoclinic, space group P2₁/n, Z= 8, in a cell with a= 9.100(2), b= 13.503(6), c= 15.702(5)Å, β= 100.12(2)°, and was refined to R= 0.053 for 2 743 observed reflections. Complex (2) was confirmed as isomorphous and isostructural with (1) using single-crystal and X-ray powder diffractometry. Di-µ-[(2-chlorophenoxy)ethanoato]-disilver(I)–silver(I) perchlorate, [{Ag₂L₂·AgClO₄}_n], (3), forms triclinic crystals, space group P, with Z= 2, in a cell of dimensions a= 10.245(2), b= 10.798(2), c= 11.067(2)Å, α= 75.27(2), β= 68.27(2), γ= 82.70(2)°. The structure was refined to R= 0.052 for 3 661 observed reflections. Complex (3) is a sheet polymer based on bis(carboxylate) bridged Ag₂L₂ units [Ag–O, 2.229(4)–2.299(4)Å]. In the two axial sites of the dimers are a co-ordinated perchlorate group [Ag–O, 2.454(4)Å] and a bridging carboxyl oxygen [Ag–O, 2.373(4)Å], while an angular bridge is also formed between the centrosymmetrically related dimer pairs by the third silver [Ag–O, 2.322(4), 2.296(4)Å; O–Ag–O, 126.4(4)°].