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Issue 13, 1999
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Controlling copper(I) halide framework formation using N-donor bridging ligand symmetry: use of 1,3,5-triazine to construct architectures with threefold symmetry

Abstract

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 [Cu3X3(tri)] (X = Br or I) are structurally similar, despite crystallising in different space groups. They are composed of (CuX) columns linked by triazine molecules to generate three-dimensional constructions with non-crystallographically imposed threefold symmetry. The (CuX) columnar motif can be described as a series of perpendicularly stacked Cu3X3 chairs, alternately rotated by 60° and linked by Cu–X contacts. The tetrahedral co-ordination geometry of the copper centres is completed by a tridentate triazine bridge which links two copper atoms in separate columns. Thus, each (CuX) column is linked to six adjacent (CuX) columns. The structure of [Cu2Br2(tri)] comprises (CuBr) columns and castellated (CuBr) chains linked by triazine molecules to generate a construction with crystallographically imposed threefold symmetry. The (CuBr) columns are similar to but more regular than those found in [Cu3Br3(tri)]. In this case, however, each column is linked to six adjacent chains. The (CuBr) 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 stoichiometry identical to that of [Cu2Br2(tri)], [Cu2I2(tri)] has a completely different structure. The triazine molecules act as bidentate bridging ligands to link (CuI) layers thereby giving alternating inorganic and organic layers. The tetrahedral co-ordination geometry of the copper centres in the (CuI) layers, which are effectively undulating hexagonal nets, is provided by three iodide anions from the layers and by a bridging triazine molecule.

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Supplementary files


Article type: Paper
DOI: 10.1039/A902290B
J. Chem. Soc., Dalton Trans., 1999, 2103-2110

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

    A. J. Blake, N. R. Brooks, N. R. Champness, P. A. Cooke, A. M. Deveson, D. Fenske, P. Hubberstey, W. Li and M. Schröder, J. Chem. Soc., Dalton Trans., 1999, 2103
    DOI: 10.1039/A902290B

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