Second-sphere hydrogen-bonding in heteroditopic mercaptopyridinium copper(I) frameworks

Bianketti, S., Blake, A. J., Wilson, C. , Hubberstey, P., Champness, N. R. and Schröder, M. (2009) Second-sphere hydrogen-bonding in heteroditopic mercaptopyridinium copper(I) frameworks. CrystEngComm, 11(5), pp. 763-769. (doi: 10.1039/B813672F)

Abstract

A series of Cu(I) complexes of 4-mercaptopyridine (LH) are reported that form three-dimensional hydrogen-bonded frameworks in the solid-state. The 4-mercaptopyridine ligands co-ordinate to the Cu(I) cations via thiolate donors, leaving a pyridinium hydrogen-bond donor available for interaction with the relevant counter-anions. Four new Cu(I) complexes, [Cu2(LH)6]·2Cl 1, [Cu2(LH)6]·SiF6·2MeOH 2, [Cu4(LH)10]·4NO3·MeOH·H2O 3 and {[Cu6(LH)13]·2BF4·2SiF6·7.5MeOH}∞4 are reported and have been structurally characterised by single crystal X-ray diffraction. In each case hydrogen-bonded arrays are formed via N–H⋯anion hydrogen-bonds or by including hydrogen-bonding to guest solvent molecules. Whereas compound 1 adopts a rutile-like structure with [Cu2(LH)6]2+ and Cl− nodes adopting six- and three-connected arrangements, respectively, compounds 2 and 3 adopt six-connected nets of α-Po (41263) topology. Compound 4 forms a thiolate bridged co-ordination polymer constructed from repeating units of six Cu(I) centres connected by ten bridging and three terminal thiolate-bound LH donors, with complex hydrogen-bonding observed between the polymer cation and counter-anions.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Wilson, Dr Claire
• Authors: Bianketti, S., Blake, A. J., Wilson, C., Hubberstey, P., Champness, N. R., and Schröder, M.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: CrystEngComm
• Publisher: Royal Society of Chemistry
• ISSN: 1466-8033
• Published Online: 15 January 2009