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Issue 4, 2001
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Discrete molecular and extended polymeric copper(I) halide complexes of tetradentate thioether macrocycles

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Abstract

A series of complexes of copper(I) halides with either [12]aneS4 (1,4,7,10-tetrathiacyclododecane) or [16]aneS4 (1,5,9,13-tetrathiacyclohexadecane) have been synthesized, characterised and their crystal structures determined. Discrete molecular entities of formula [CuX([12]aneS4)] (X = Cl, Br or I) were isolated from solutions containing a 1  1 metal  ligand stoichiometry. In [CuX([12]aneS4)] (X = Br or I) the copper(I) centres adopt a rare square pyramidal geometry. Located on fourfold axes of symmetry, the copper(I) centres are co-ordinated by one halide ion [Cu–Br 2.4209(11) or Cu–I 2.573(5) Å] and four sulfur atoms [2.5386(12) (X = Br) and 2.521(5) Å (X = I)]. In contrast, the copper(I) centres in [CuCl([12]aneS4)] adopt the more common tetrahedral co-ordination geometry, which is provided by one chloride ion [Cu–Cl 2.2666(13) Å] and three sulfur donors [Cu–S 2.3331(13), 2.3326(13), 2.4720(11) Å]. Polymeric materials, [Cu4Br4([12]aneS4)2], [Cu4I4([12]aneS4)] and [Cu2I2([16]aneS4)], were obtained from reactions in which metal  ligand stoichiometries of 2  1 and 4  1 were used. [Cu4Br4([12]aneS4)2] contains a previously uncharacterised copper(I) halide motif of formula Cu4X4 which is derived from the common Cu4X4 cubane tetramer and the Cu4X4 step-cubane tetramer. These Cu4X4 clusters are linked by [12]aneS4 molecules to generate a two-dimensional framework [Cu–Br 2.410(2)–2.539(2); Cu–S 2.318(3)–2.385(3) Å]. In [Cu4I4([12]aneS4)], Cu4I4 cubane tetramers are linked by tetradentate [12]aneS4 molecules to give a two-dimensional sheet structure [Cu–I 2.602(1)–3.021(1); Cu–S 2.285(1)]. In [Cu2I2([16]aneS4)] an infinite three-dimensional co-ordination polymer comprising Cu2I2 rhomboid dimers linked by tetradentate [16]aneS4 molecules is formed [Cu–I 2.5972(9)–2.6702(9); Cu–S 2.292(2)–2.357(2) Å]. The Cu2I2 moiety acts as a pseudo-square planar linker while the bridging [16]aneS4 units afford tetrahedral building blocks to give overall a PtS type structure for the polymer.

Graphical abstract: Discrete molecular and extended polymeric copper(I) halide complexes of tetradentate thioether macrocycles

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Publication details

The article was received on 11 Oct 2000, accepted on 21 Nov 2000 and first published on 31 Jan 2001


Article type: Paper
DOI: 10.1039/B008202N
J. Chem. Soc., Dalton Trans., 2001, 456-465

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    Discrete molecular and extended polymeric copper(I) halide complexes of tetradentate thioether macrocycles

    N. R. Brooks, A. J. Blake, N. R. Champness, P. A. Cooke, P. Hubberstey, D. M. Proserpio, C. Wilson and M. Schröder, J. Chem. Soc., Dalton Trans., 2001, 456
    DOI: 10.1039/B008202N

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