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International Union of Crystallography, Acta Crystallographica Section C: Crystal Structure Communications, 11(68), p. m295-m299, 2012

DOI: 10.1107/s0108270112038048

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Cadmium(II) chloride, bromide and iodide complexes with 4,4′-bipyridazine: when are diazine and halide bridges (in)compatible?

This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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Abstract

In poly[di-μ-chlorido-μ-(4,4′-bipyridazine)-κ2N1:N1′-cadmium(II)], [CdCl2(C8H6N4)]n, (I), and its isomorphous bromide analogue, [CdBr2(C8H6N4)]n, (II), the halide atom lies on a mirror plane and the CdIIion resides at the intersection of two perpendicular mirror planes withm2msite symmetry. The pyridazine rings of the ligand lie in a mirror plane and are related to each other by a second mirror plane perpendicular to the first. The compounds adopt the characteristic structure of the [MIIX2(bipy)] type (bipy is bipyridine) based on crosslinking of [Cd(μ-X)2]nchains [Cd—Cl = 2.5955 (9) and 2.6688 (9) Å; Cd—Br = 2.7089 (4) and 2.8041 (3) Å] by bitopic rod-like organic ligands [Cd—N = 2.368 (3)–2.380 (3) Å]. This feature is discussed in terms of supramolecular stabilization, implying that the periodicity of the inorganic chain [Cd...Cd = 3.7802 (4) Å in (I) and 3.9432 (3) Å in (II)] is favourable for extensive parallel π–π stacking of monodentate pyridazine rings, with centroid–centroid distances of 3.7751 (4) Å in (I) and 3.9359 (4) Å in (II). This is not the case for the longer iodide bridges, which cannot stabilize such a pattern. In poly[tetra-μ-iodido-μ4-(4,4′-bipyridazine)-κ4N1:N2:N1′:N2′-dicadmium(II)], [Cd2I4(C8H6N4)]n, (III), the ligands are situated across a centre of inversion; they are tetradentate [Cd—N = 2.488 (2) and 2.516 (2) Å] and link successive [Cd(μ-I)2]nchains [Cd—I = 2.8816 (3)–3.0069 (4) Å] into corrugated layers.