Crown ethers as ancillary ligands in the assembly of silver(i) aggregates containing embedded acetylenediide

Five silver(I) double salts containing embedded acetylenediide, Ag(12]crown-4)(2)]Ag(10)(C(2))(CF(3)CO(2))(9)(12]crown-4)(2)(H(2)O)(3)] x H(2)O (2), Ag(2)C(2) x 5 AgCF(3)CO(2) x (benzo15]crown-5) x 2 H(2)O] x 0.5 H(2)O (3), Ag(4)(18]crown-6)(4)(H(2)O)(3)]Ag(18)(C(2))(3)(CF(3)CO(2))(16)(H(2)O)(2.5)] x 2.5 H(2)O (4), Ag(2)C(2) x 6 AgC(2)F(5)CO(2) x 2(15]crown-5)](2) (5), and (Ag(2)C(2))(2) x (AgC(2)F(5)CO(2))(9) x (18]crown-6)(2) x (H(2)O)(3.5)] x H(2)O (6), have been isolated by varying the types of crown ethers and anions employed. Single-crystal X-ray analysis has shown that complex 2 is composed of winding anionic chains with sandwiched Ag(12]crown-4)(2)](+) ions accommodated in the concave cavities between them. In 3, silver(I) double cages each sandwiched by a couple of benzo15]crown-5 ligands are linked by Ag(2)(CF(3)CO(2))(2)] bridges to form a one-dimensional structure. For 4, an anionic silver column is generated through fusion of two kinds of silver polyhedra (triangulated dodecahedron and bicapped trigonal antiprism), and the charge balance is provided by aqua-ligated Ag(18]crown-6)](+) ions. Complex 5 is a centrosymmetric hexadecanuclear supermolecule composed of two (eta(5)-15]crown-5)(2)(C(2)@Ag(7))(mu-C(2)F(5)CO(2))(5)] moieties connected through a Ag(2)(C(2)F(5)CO(2))(2)] bridge. Compound 6 is a discrete supermolecule containing an asymmetric (C(2))(2)@Ag(13) cluster core capped by two 18]crown-6 ligands in mu(3)-eta(5) and mu(4)-eta(6) ligation modes.