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Issue 38, 2012
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Structural, theoretical and spectroscopic studies of the dichloride hexahydrate cube [Cl2(H2O)6]2−

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Abstract

The structure of the dichloride hexahydrate cube, [Cl2(H2O)6]2−, as a salt with the tris(diisopropylamino)cyclopropenium cation, [C3(NiPr2)3]+, has been determined by low-temperature X-ray and neutron-diffraction studies. H atoms not involved in O–H⋯Cl bonding are disordered over two 0.5 occupancy sites around the O6 ring. Calculations of the dianionic cube in the gas phase show remarkably good agreement with the solid-state structures with the exception of short O–H bond distances around the O6 ring that suggests the involvement of a dynamic process. The cluster was also characterised by single-crystal infrared spectroscopy, and vibrational wavenumbers were found to be in good agreement with hydrogen bonding distances. Dibromide and difluoride hexahydrates were also studied theoretically, and O⋯O distances were found to decrease in the order difluoride > dichloride > dibromide > (H2O)6 and as O⋯O⋯O angles increased towards an almost planar ring in (H2O)6. NMR spectra of a chloroform solution of the hydrated salt at −25 °C is consistent with cluster formation.

Graphical abstract: Structural, theoretical and spectroscopic studies of the dichloride hexahydrate cube [Cl2(H2O)6]2−

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Publication details

The article was received on 05 Jun 2012, accepted on 31 Jul 2012 and first published on 17 Aug 2012


Article type: Paper
DOI: 10.1039/C2DT31212C
Citation: Dalton Trans., 2012,41, 11765-11775
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    Structural, theoretical and spectroscopic studies of the dichloride hexahydrate cube [Cl2(H2O)6]2−

    J. R. Butchard, O. J. Curnow, D. J. Garrett, R. G. A. R. Maclagan, E. Libowitzky, P. M. B. Piccoli and A. J. Schultz, Dalton Trans., 2012, 41, 11765
    DOI: 10.1039/C2DT31212C

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