The role of intermolecular interactions in the assemblies of Fe{sup II} and Co{sup II} tetrakis-isothiocyanatometalates with tris(1,10-phenanthroline)-Ru{sup II}: Crystal structures of two dual-metal assemblies featuring octahedral cationic and tetrahedral anionic modules
- Department of Chemical and Biological Engineering, Chalmers University of Technology, SE-412 96 Goeteborg (Sweden)
Two new dual-metal assemblies: 2[Ru(phen){sub 3}]{sup 2+}.[Fe(SCN){sub 4}]{sup 2-}.2SCN{sup -}.4H{sub 2}O 1 and [Ru(phen){sub 3}]{sup 2+}.[Co(SCN){sub 4}]{sup 2-}2, (phen:1,10-phenanthroline), have been prepared and their structures were characterized by X-ray diffraction. In 1, the cationic octahedral enantiomers are arranged with a {lambda}{delta}{lambda}{delta}{lambda} sequence supported by {pi}-{pi} stacking and the anionic inorganic tetrahedral units are oriented between these stacks by interacting with the nearby water molecules through strong O-H...O and O-H...S hydrogen bonds. In 2, homochiral double helices in the b-direction are revealed, with tetrakis-isothiocyanate Co{sup II} anions arranged in the crystal to furnish one-dimensional (1D)-helical chains with S...S intermolecular interactions at 3.512(2) and 3.966(2) A supporting [Ru(phen){sub 3}]{sup 2+}{lambda}- and {delta}-helices with Ru...Ru shortest distance of 8.676(7) A. In both 1 and 2, the supramolecular assembly is maintained by C-H...S hydrogen bonds extending between the phenanthroline aromatic carbons in the cationic nodes and the sulphur atoms of the isothiocyanates anions. Analysis of S...S interactions in isothiocyanate containing compounds using Cambridge structural database (CSD) showed an angle dependence categorizing these interactions into 'type-I' and 'type-II'. - Graphical abstract: Side projection in 2 showing the crankshaft caused by S...S interactions in [Co(NCS){sub 4}]{sup 2-} in-between [Ru{sup II}(phen){sub 3}]{sup 2+} helices. Only isothiocyanates arms of [Co(NCS){sub 4}]{sup 2-} that are part of S...S interactions are shown and [Ru{sup II}(phen){sub 3}]{sup 2+} are presented as polyhedra.
- OSTI ID:
- 21128431
- Journal Information:
- Journal of Solid State Chemistry, Vol. 181, Issue 9; Other Information: DOI: 10.1016/j.jssc.2008.04.039; PII: S0022-4596(08)00219-3; Copyright (c) 2008 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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