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Issue 22, 2002
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Bridging mode flexibility of 1,3-dithiacyclohexane in silver(i) co-ordination polymers

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Abstract

Co-ordination polymers with Ag∶1,3-dithiane molar ratios of 1∶1, {[Ag2(1,3-dithiane)2][X][Y]} (X = Y = NO3, 1; X = Y = PF6, 2; X = Y = BF4, 3; X = BF4, Y = Cl, 4; X = Y = NO2, 5, and 2∶1, {[Ag2(1,3-dithiane)(SO4)(H2O)2]·H2O}6, the extended structures of which are 1-D chains and 2-D sheets, respectively, have been synthesised and structurally characterised. The recurrent structural motif is the [Ag2(μ-1,3-dithiane)2]2+ cationic dimer in which two chair-conformation 1,3-dithiane molecules act as two-connecting units to bridge two Ag(I) centres. In 1, 2, and 6, the dimers are linked into near-linear chains by pairs of bridging anions via formation of an Ag2X2 rhomboid dimer. In 3, instead of forming the Ag2X2 (X = F) rhomboid dimer, two [BF4] anions form μ2-F,F′-bridges which support weak Ag–S interactions between cations to give a saw-tooth chain structure. This extra Ag–S contact makes the 1,3-dithiane a three-connecting unit. In 4 and 5, the Ag(I) centres of the cationic dimer are bridged not only by two 1,3-dithiane molecules but also by a Cl or NO2 anion, respectively, to give [Ag2(μ-1,3-dithiane)22-Cl)]+ (4) and [Ag2(μ-1,3-dithiane)22-O,O′-NO2)]+ (5). In 4, the Cl anion acts as a μ4-bridge to link three [Ag2(μ-1,3-dithiane)2]2+ moieties and generate a zig-zag chain. In 5, one oxygen of the bridging NO2 anions acts as a μ2-bridge to link two [Ag2(μ-1,3-dithiane)2]2+ dimers and generate a saw-tooth chain. Although the chains in 1, 2, 3 and 5 are uncharged, that in 4 is cationic and that in 6 is anionic. Charge balance in 4 is maintained by a non-co-ordinated [BF4] anion; that in 5 is maintained by ‘Ag(H2O)2+’, the co-ordination polyhedron of which is completed by sulfur donors from separate 1,3-dithiane molecules, which thus act as four-connecting units, and by two oxygens of separate SO42− anions to give a two-dimensional sheet structure.

Graphical abstract: Bridging mode flexibility of 1,3-dithiacyclohexane in silver(i) co-ordination polymers

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Supplementary files

Article information


Submitted
30 May 2002
Accepted
07 Aug 2002
First published
18 Oct 2002

J. Chem. Soc., Dalton Trans., 2002, 4134-4142
Article type
Paper

Bridging mode flexibility of 1,3-dithiacyclohexane in silver(I) co-ordination polymers

L. Brammer, C. S. Rodger, A. J. Blake, N. R. Brooks, N. R. Champness, J. W. Cunningham, P. Hubberstey, S. J. Teat, C. Wilson and M. Schröder, J. Chem. Soc., Dalton Trans., 2002, 4134
DOI: 10.1039/B205278B

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