Structural and spectroscopic studies of some adducts of silver(I) salts with ethylenethiourea

Syntheses, single crystal X-ray structural and spectroscopic characterizations are described for a variety of adducts of silver salts with ethylenethiourea (etu). Ag(2)SO(4)/etu (1: 6) is isomorphous with its previously studied copper(I) counterpart, the [Ag(S-etu)3](+) species disposed with their silver atoms on crystallographic 3-axes, one of the two independent cations being slightly perturbed by a distant O-sulfate approach along that axis. In AgCl/etu (1:3), the silver atom is in a four-coordinate ClAgS(3) environment, while AgNO(3)/etu (1: 3) takes the form [(etu) 2Ag(mu-Setu) (2)Ag(etu)(2)](NO(3))(2). AgBr/etu (1:2) is binuclear [(etu)(2)Ag(mu-Br)(2)Ag(etu)(2))], unlike its previously studied copper counterpart, which is [(etu)BrCu(mu-S-etu)(2)CuBr(etu)]. AgCl/etu (4: 6) is an interesting ionic polymer [ClAg(4)(etu)(6)]((infinity vertical bar infinity)) Cl(3), containing a novel one-dimensional polymeric cation. Bands in the far IR spectra of these compounds are assigned to nu(AgS) and nu(AgX) (X = halogen) modes, and a correlation between nu(AgS) and the Ag-S bond length d(AgS) is established for silver complexes involving the etu ligand.