Keene, T.D., Hursthouse, M.B. and Price, D.J. (2012) Recurrent H-bond graph motifs between metal tris-ethylenediamine cations and uncoordinated oxalate anions: fitting a three pin plug into a two pin socket. CrystEngComm, 14(1), pp. 116-123. (doi: 10.1039/C1CE05837A)
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Abstract
The structures of four new compositionally related compounds are described; [Cu(en)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>][ox] (1), [Cu(en)<sub>3</sub>][ox] (2), [Co(en)<sub>3</sub>]<sub>2</sub>[ox]<sub>3</sub>(H<sub>2</sub>O)<sub>3.61</sub> (3), and [Co(en)<sub>3</sub>]<sub>2</sub>[ox]<sub>3</sub>(H<sub>2</sub>O)<sub>7</sub> (4) [en = 1,2-ethylenediamine, ox = oxalate]. These materials all inhabit the broader structural landscape for compounds with a generic M<sub>p</sub>(ox)<sub>q</sub>(en)<sub>r</sub>(H<sub>2</sub>O)<sub>s</sub> composition. Here the competing nature of the ligands; ethylenediamine, oxalate and water, results in complex solution chemistry. In addition the very different structure directing effects of each type of ligand yield a range of crystal architectures. In the present cases ethylenediamine displaces the oxalate dianion, which is non-coordinated in each of these compounds. Compound 3 has disordered water of crystallisation, and is a non-stiochoimetric hydrate, while compound 4 shows a correlated disorder in both ligand conformation and water site occupancies. The H-bond motifs linking pseudo 3-fold symmetric M(en)<sub>3</sub><sup>n+</sup> cations to pseudo 2-fold symmetric ox<sup>2-</sup> anions shows frequent occurrence of particular motifs; notably the R<sup>2</sup><sub>2</sub>(8) and R<sup>2</sup><sub>2</sub>(9) graphs and a tendency to form bifurcated hydrogen bonds. The oxalate geometric parameters of twist and C–C bond length in our compounds are correlated with data from related structures in the CSD.
| Item Type: | Articles |
|---|---|
| Keywords: | Hydrogen bond, conflicted symmetry, oxalate |
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Price, Dr Daniel |
| Authors: | Keene, T.D., Hursthouse, M.B., and Price, D.J. |
| Subjects: | Q Science > QD Chemistry |
| College/School: | College of Science and Engineering > School of Chemistry |
| Journal Name: | CrystEngComm |
| Publisher: | Royal Society of Chemistry |
| ISSN: | 1466-8033 |
| Published Online: | 13 October 2011 |
| Copyright Holders: | Copyright © 2012 Royal Society of Chemistry |
| First Published: | First published in CrystEngComm 14(1):116-123 |
| Publisher Policy: | Reproduced in accordance with the copyright policy of the publisher |
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