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Issue 5, 2009
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Second-sphere hydrogen-bonding in heteroditopic mercaptopyridinium copper(I) frameworks

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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.

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

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Publication details

The article was received on 06 Aug 2008, accepted on 21 Nov 2008 and first published on 15 Jan 2009


Article type: Paper
DOI: 10.1039/B813672F
CrystEngComm, 2009,11, 763-769

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

    S. Bianketti, A. J. Blake, C. Wilson, P. Hubberstey, N. R. Champness and M. Schröder, CrystEngComm, 2009, 11, 763
    DOI: 10.1039/B813672F

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