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Structural Properties and Topological Diversity of Polymeric Ag(I)-hexamethylenetetramine Complexes: Self-Assembly of Three Novel Two-Dimensional Coordination Networks and Their Supramolecular Interactions

2000; Elsevier BV; Volume: 152; Issue: 1 Linguagem: Inglês

10.1006/jssc.2000.8684

1095-726X

Lucia Carlucci, Gíanfranco Ciani, Davide Μ. Proserpio, Silvia Rizzato,

Crystal structures of chemical compounds

The self-assembly of polymeric open networks from different Ag(I) salts and the potentially tetradentate ligand hexamethylenetetramine (hmt) has revealed a variety of possible structural motifs, depending on the reagent ratios and the counterions, that are discussed in comparison. Three new Ag(I) coordination polymers are here described, namely [Ag2(μ4-hmt)(Tos)2] (Tos=p-toluenesulfonate) (1), [Ag2(μ3-hmt)2(CF3SO3)(H2O)](CF3SO3)·H2O (2), and [Ag3(μ3-hmt)2(H2O)4](PF6)3 (3), that contain two-dimensional infinite layers of different types. Crystal data: 1 C20H26Ag2N4O6S2, monoclinic, C2/c, Z=4, a=9.482(3) Å, b=8.539(3) Å, c=28.461(10) Å, β=91.75(2)°, V=2303.3(13) Å3, R=0.043 (I>2σ(I)); 2 C14H28Ag2F6NO8S2, monoclinic, P21/c, Z=4, a=6.429(2) Å, b=25.247(3) Å, c=16.162(2) Å, β=91.54(2)°, V=2622.4(9) Å3, R=0.050 (I>2σ(I)); 3 C12H32Ag3F18N8O4P3, monoclinic, C2/c, Z=4, a=16.675(4) Å, b=11.102(5) Å, c=18.455(3) Å, β=111.48(2)°, V=3179.2(17) Å3, R=0.040 (I>2σ(I)). Compound 1 is composed of layers of square grids, with the silver ions acting as spacers and interacting with the anions through Ag–O contacts and also via π bonds with the aromatic rings. Compound 2 consists of layers of hexagons, with alternate triconnected Ag(I) ions and tridentate hmt ligands, while compound 3 contains layers of larger hexagonal meshes, with six hmt ligands at the vertices and six biconnected silver atoms as spacers. The latter two species give rise, via hydrogen-bond bridges involving coordinated water molecules, to three-dimensional arrays of new topologies.