Complementarity of halide-mediated hydrogen-bonding and alkyl substitution in the construction of two-dimensional rhombic (4,4) grids using bis(N-alkylamidino-O-alkylurea)copper(ii) halides

Suksangpanya, U., Blake, A. J., Hubberstey, P., Parker, D. J., Teat, S. J. and Wilson, C. (2003) Complementarity of halide-mediated hydrogen-bonding and alkyl substitution in the construction of two-dimensional rhombic (4,4) grids using bis(N-alkylamidino-O-alkylurea)copper(ii) halides. CrystEngComm, 5(3), pp. 10-22. (doi: 10.1039/b210185h)

Abstract

A series of hydrogen-bonded networks based on bis(N-alkylamidino-O-alkylurea)copper(II) cations, [CuL2]2+, bridged by either chloride or bromide have been synthesised, of which six have been structurally characterised by single crystal X-ray diffraction methods. The [CuL2]2+ cation acts as a four-connecting centre and forms 2-D rhombic (4,4) grids for the majority of the compounds studied. However, the grids do not adopt a common intermolecular hydrogen-bonding pattern. Three distinct systems can be differentiated: one mediated solely by halide anions, a second mediated by protic solvent molecules as well as halide anions, and a third with no intermolecular interactions. There is evidence for complementarity in (4,4) rhombic grids mediated solely by halide anions, as grid formation only occurs when there is a match between the size of the cavity formed within the grid and the space required by the pendant alkyl groups of the N-alkylamidino-O-alkylurea ligands. Such complementarity occurs for [Cu(Lmm)2]·2Cl (Lmm = N-methylamidino-O-methylurea) and [Cu(Lme)2]·2Br (Lme = N-methylamidino-O-ethylurea). Chloride bridges generate a cavity which can accommodate four juxtaposed methyl groups while bromide bridges generate a cavity large enough to accommodate two methyl and two ethyl groups. Rhombic (4,4) grid formation based on simple halide bridges does not take place for [Cu(Lmm)2]·2Br·2MeOH, [Cu(Lee)2]·2Cl·H2O (Lee = N-ethylamidino-O-ethylurea), [Cu(Lee)2]·2Br·MeOH or [Cu(L2m)2]·2Cl·2MeOH (L2m = N-benzylamidino-O-methylurea). The cavity generated by bromide bridges is too large for the four methyl groups of [Cu(Lmm)2]2+ cations. To overcome this problem and still form a (4,4) grid, the hydrogen-bonding assembly in [Cu(Lmm)2]·2Br·2MeOH incorporates a methanol molecule. The spatial requirements of the four ethyl groups of the [Cu(Lee)2]2+ cations are greater than can be provided by either of the grids generated by chloride or bromide bridges. Consequently, 1-D chains rather than 2-D rhombic (4,4) grids are formed. The cavity required to accommodate two benzyl groups and two methyl groups of the [Cu(L2m)2]2+ cations is far larger than can be provided by chloride bridges. Hence, although the disposition of copper(II) centres in [Cu(L2m)2]·2Cl·2MeOH is similar to those in [Cu(Lmm)2]·2Cl and [Cu(Lme)2]·2Br, the molecular units are not linked by hydrogen-bonding interactions. A common feature of the halide bridges is a hydrogen-bonded supramolecular synthon in which the anion acts as acceptor to two pairs of N–H donors thus forming two R12(6) motifs with a common halide anion.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Wilson, Dr Claire
• Authors: Suksangpanya, U., Blake, A. J., Hubberstey, P., Parker, D. J., Teat, S. J., and Wilson, C.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: CrystEngComm
• Publisher: Royal Society of Chemistry
• ISSN: 1466-8033
• ISSN (Online): 1466-8033
• Published Online: 15 January 2003