Metal arsonate polymers of Cd, Zn, Ag and Pb supported by 4-aminophenylarsonic acid

Abstract

The coordination preferences of 4-aminophenylarsonic acid, 4-NH2C6H4AsO3H2, (p-arsanilic acid) with CdCl2·2.5H2O, ZnCl2, Ag(SO3CF3) and Pb(NO3)2 have been investigated affording five new metal arsonate polymers. The reaction between 4-aminophenylarsonic acid and CdCl2·2.5H2O resulted in a one-dimensional polymer, [{Cd(4-NH3C6H4AsO3H)(Cl)2}(H2O)2]n, 1, in which the polymeric chain is propagated by bridging chlorides. Exchange of CdCl2 for ZnCl2 afforded [{Zn2(4-NH3C6H4AsO3)(Cl)2}(H2O)2(Cl)]n, 2, featuring interlinked 6- and 8-membered [Zn–O–As] ring systems. The reaction of Ag(SO3CF3) with 4-aminophenylarsonic acid, afforded polymeric 3, [Ag(4-NH2C6H4AsO3H)(4-NH2C6H4AsO3H2)]n where coordination of the amino group to the silver center is observed and [{Ag2(4-NH3C6H4AsO3H)(4-NH3C6H4AsO3)(μ2-SO3CF3)2}(SO3CF3)2]n, 4. By comparison, the reaction of p-arsanilic acid with Pb(NO3)2 yielded a polymeric chain [Pb(4-NH3C6H4AsO3H)(NO3)2]n, 5 of similar topology to 1. The structures of 1–5 have been indiscriminately characterized by single crystal X-ray diffraction and their composition supported by relevant spectroscopic techniques. A comparison of the structural features of these polymers is used to determine the coordination preference of the ligand and factors influencing structural motifs, for example, the role of the anion.