Acta Crystallographica Section B

Structural Science

Volume 64, Part 3 (June 2008)

research papers

Acta Cryst. (2008). B64, 318-329 [ doi:10.1107/S0108768108004151 ]

Five-coordinate copper(II) complexes: crystal structures, spectroscopic properties and new extended structural pathways of [Cu(chelate)₂X]Y, where chelate = dpyam, phen and bipy; X = pseudohalide ligands

S. Youngme, P. Phuengphai, C. Pakawatchai, P. Kongsaeree and N. Chaichit

Abstract: The crystal structures of four distortion isomers of the [Cu(chelate)₂X]⁺ cation, where chelate = 2,2-bipyridine (bipy), 1,10-phenanthroline (phen) and di-2-pyridylamine (dpyam), X = a pseudohalide ligand (NCO, NCS, N₃ and C₂N₃), have been compared by scatterplot analysis with 25 [Cu(chelate)₂X]Y complexes of known crystal structure. The four new complexes [Cu(phen)₂NCO]Br (1), [Cu(phen)₂N₃]BPh₄·H₂O (2), [Cu(dpyam)₂(N₃)]NO₃·H₂O (3) and [Cu(dpyam)₂(N₃)]ClO₄ (4) involve a near regular square-based pyramidal stereochemistry (RSBP). The structures of complexes (1) and (2) are of the rare cases found for the phen analogue. Scatterplots of the 29 cation distortion isomers of the [Cu(chelate)₂X]Y series of complexes suggest that most of the 29 complexes lie on a common structural pathway, involving a mixture of the symmetric, C₂, and the asymmetric, non-C₂, in-plane modes of vibration of the CuN₄N' chromophore. Some datapoints are found to lie on extended routes The resulting structural pathways are consistent with the direct observation of the effect of the modes of vibration on the stereochemistries of the complexes. A comparison of the trends in the 29 datasets suggests a size effect of the phen, bipy and dpyam ligands.

Keywords: copper(II) complex; five-coordinate complex; structural pathway.


	Structure factor file (CIF format) (245.8 kbytes) [ doi:10.1107/S0108768108004151/bp50081sup2.fcf ] Contains datablock 1

	Structure factor file (CIF format) (351.2 kbytes) [ doi:10.1107/S0108768108004151/bp50082sup3.fcf ] Contains datablock 2

	Structure factor file (CIF format) (252.5 kbytes) [ doi:10.1107/S0108768108004151/bp50083sup4.fcf ] Contains datablock 3

	Structure factor file (CIF format) (207.8 kbytes) [ doi:10.1107/S0108768108004151/bp50084sup5.fcf ] Contains datablock 4

Notes:

To open or display or play some files, you may need to set your browser up to use the appropriate software. See the full list of file types for an explanation of the different file types and their related mime types and, where available links to sites from where the appropriate software may be obtained.

The download button will force most browsers to prompt for a file name to store the data on your hard disk.

Where possible, images are represented by thumbnails.