Jump to main content
Jump to site search

Issue 4, 2001
Previous Article Next Article

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

Author affiliations

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

Back to tab navigation

Supplementary files

Article information


Submitted
11 Oct 2000
Accepted
21 Nov 2000
First published
31 Jan 2001

J. Chem. Soc., Dalton Trans., 2001, 456-465
Article type
Paper

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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.


Search articles by author

Spotlight

Advertisements