Controlling copper (I) halide framework formation using N-donor bridging ligand symmetry: use of 1, 3, 5-triazine to construct architectures with threefold symmetry

摘要

The formation of co-ordination polymers between copper (I) halides and 1, 3, 5-triazine (tri), a potentially tridentate N-donor bridging ligand with threefold symmetry, has been studied. Complexes with both 3:1 and 2:1 molar ratios are formed by both CuBr and CuI. The compounds [Cu_3X_3(tri)]_(infinity) (X = Br or I) are structurally similar, despite crystallising in different space groups. They are composed of (CuX)_(infinity) columns linked by triazine molecules to generate three-dimensional constructions with non-crystallographically imposed threefold symmetry. The (CuX)_(infinity) columnar motif can be described as a series of perpendicularly stacked Cu_3X_3 chairs, alternately rotated by 60 deg and linked by Cu-X contacts. The tetrahedral coordination geometry of the copper centres is completed by a tridentate triazine bridge which links two copper atoms in separate columns. Thus, each (CuX)_(infinity) column is linked to six adjacent (CuX)_(infinity) columns. The structure of [Cu_2Br_2(tri)]_(infinity) comprises (CuBr)_(infinity) columns and castellated (CuBr)_(infinity) chains linked by triazine molecules to generate a construction with crystallographically imposed threefold symmetry. The (CuBr)_(infinity) columns are similar to but more regular than those found in [Cu_3Br_3(tri)]_(infinity). In this case, however, each column is linked to six adjacent chains. The (CuBr)_(infinity) castellated chain motif is very unusual. The tetrahedral copper centres are co-ordinated by two adjacent bromide anions and by two triazine molecules each of which links a second chain and a column. Consequently, each chain is linked to four neighbouring chains and two neighbouring columns. Despite a stoichimometry identical to that of [Cu_2Br_2(tri)]_(infinity), [Cu_2I_2(tri)]_(infinity) has a completely different structure. The triazine molecules act as bidentate bridging ligands to link (CuI)_(infinity) layers thereby giving alternating inorganic and organic layers. The tetrahedral co-ordination geometry of the copper centers in the (CuI)_(infinity) layers, which are effectively undulating hexagonal nets, is provided by three iodide anions from the layers and by a bridging triazine molecule.