Acta Crystallographica Section C

Crystal Structure Communications

Volume 61, Part 1 (January 2005)

metal-organic compounds

bm1594 scheme

Acta Cryst. (2005). C61, m34-m39 [doi:10.1107/S0108270104029051]

The effect of hydrogen-bonding anions on the structure of metal-sulfimide complexes

S. H. Dale, M. R. J. Elsegood, K. E. Holmes and P. F. Kelly

Abstract: Investigations into the effects of the choice of anion on the hydrogen-bonding interactions between anions and metal-sulfimide cationic complexes have led to the study of three novel compounds. Hexakis(S,S-diphenylsulfimide)cobalt(II) diiodide S,S-diphenylsulfimide acetonitrile disolvate, [Co(C₁₂H₁₁NS)₆]I₂·C₁₂H₁₁NS·2C₂H₃N, crystallizes in the centrosymmetric space group P $\overline 1$ with Z = 2. Six diphenylsulfimide ligands coordinate to the cobalt centre through their N atoms. Two iodide counter-ions hydrogen bond to the cation through N-HI interactions, with NI distances in the range 3.7302 (19)-3.8461 (19) Å. One extra molecule of sulfimide is included in the asymmetric unit, regardless of the metal-ligand ratio used in the synthesis, and this sulfimide molecule also hydrogen bonds to one of the iodide counter-ions through one N-HI hydrogen bond. The reaction of FeCl₃·6H₂O with S,S-diphenylsulfimide monohydrate yields hexakis(S,S-diphenylsulfimide)iron(III) trichloride, [Fe(C₁₂H₁₁NS)₆]Cl₃. The complex crystallizes in the centrosymmetric cubic space group $Pa\overline 3$ and the asymmetric unit contains one-sixth of a formula unit. Two of the chloride anions each hydrogen bond to three sulfimide NH groups on opposite sides of the [Fe(Ph₂SNH)₆]³⁺ cation. The third chloride anion does not take part in any strong hydrogen bonding; instead it is surrounded by aromatic groups and is involved in C-HCl hydrogen bonds. The reaction of [Pt(Ph₂SNH)₄]Cl₂ with I₂ facilitates oxidation of the Pt^II metal centre to Pt^IV, producing tetrakis(S,S-diphenylsulfimide)diiodoplatinum(IV) dichloride dichloromethane disolvate, [PtI₂(C₁₂H₁₁NS)₄]Cl₂·2CH₂Cl₂. The crystal structure is centrosymmetric, with the elongated octahedral cationic complex situated on an inversion centre. The chloride anions are hydrogen bonded to the cation through N-HCl hydrogen bonds, with two cis NH groups hydrogen bonded to each anion. Strong hydrogen bonding within these three compounds is limited to N-Hhalide hydrogen bonds between the cation and two anions, with a three-up/three-down arrangement of the NH groups in the first two compounds. The anions also `cap' the NH groups in the third compound. In all three cases, the anions are also involved in weaker hydrogen bonds utilizing the plethora of relatively acidic aryl CH groups in the structures.

Formula: [Co(C₁₂H₁₁NS)₆]I₂·C₁₂H₁₁NS·2C₂H₃N, [Fe(C₁₂H₁₁NS)₆]Cl₃ and [PtI₂(C₁₂H₁₁NS)₄]Cl₂·2CH₂Cl₂


	Structure factor file (CIF format) (957.8 kbytes) Contains datablock I

	Structure factor file (CIF format) (126.7 kbytes) Contains datablock II

	Structure factor file (CIF format) (315.3 kbytes) Contains datablock III

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.

other supplementary material

If the supplementary material that you require is not shown in the list above, it may only be available in our hard-copy archive. However, our policy is to progressively digitize old hard-copy supplementary documents where possible.

Please help us to work towards this goal by completing the form below. This will register your wish to receive a supplementary document, which we shall scan to create a PDF and then make available via the web to you and to other requestors in the future.

Name
E-mail
Address