Coordination networks through the dimensions: From discrete clusters to 1D, 2D, and 3D silver(I) coordination polymers with rigid aliphatic amino ligands

The use of a ligand directed strategy in the assembly of discrete clusters, 1D chains, 2D layers, and 3D networks using aliphatic N-donor ligands has been investigated. The ligands are a family of amines with rigid backbones [cis,cis-1,3,5-triaminocyclohexane (cis-tach), cis,trans-1,3,5-triaminocyclohexane (trans-tach), cis-1,3-diaminocyclohexane (cis-dach), and cis-3,5-diaminopiperidine (cis-dapi)], and their complexation with Ag(l) salts results in a diverse set of architectures with the following compositions: [Ag-3(cis-tach)(2)]F(3)(.)4CH(3)OH(.)0.5H(2)O (1), [Ag-3(cis-tach)(2)]F(3)(.)6H(2)O (2), {[Ag(cis-dach)]ClO4}(n) (3), {[Ag(cis-tach)]NO3}(n) (4), {[Ag(trans-tach)]PF6}(n) (5), and {[Ag(cis-dapi)]CF3SO3}(n) (6). Structural analysis shows that compounds 1 and 2 are discrete M3L2 cage-type clusters with varying solvent molecule content. Short (AgAg)-Ag-... contacts (3.021(8) Angstrom) are observed to dimerize discrete units in compound 2. Compound 3 is a 1D zigzag chain formed by coordination to the two primary amines of cis-dach, whereas the tridentate ligands in compounds 4 and 5 (cis-tach and trans-tach, respectively) are able to form tubular architectures by virtue of their ability to "wrap" round the channel walls. An infinite 2D coordination network is demonstrated by compound 6, in which the three coplanar amino donors of cis-dapi coordinate to the trigonal planar Ag(l) ions to form a layered structure of 6(3) topology. These are compared with a previously reported 3D structure, {[Ag(transtach)]NO3}(n) (7), that belongs to this family of architectures.