Acta Crystallographica Section C

Crystal Structure Communications

Volume 69, Part 12 (December 2013)


interplay of crystallography, spectroscopy and theoretical methods for solving chemical problems



Acta Cryst. (2013). C69, 1421-1426    [ doi:10.1107/S0108270113024505 ]

RuII-hydride-trop complexes: X-ray single-crystal determination and quantum-chemical calculations

G. Santiso-Quinones, R. Rodriguez-Lugo, V. Sacchetti and H. Grützmacher

Abstract: As part of our search for catalytically active RuII-hydride complexes, we have synthesized and crystallographically characterized three different ruthenium species, namely dihydrido[(SR)-(10,11-[eta])-N-(pyridin-2-ylmethyl-[kappa]N)-5H-di­benzo[a,d]cyclo­hepten-5-amine](tri­phenyl­phosphane-[kappa]P)ruthenium(II) tetra­hydro­furan monosolvate, [RuH2(C21H18N2)(C18H15P)]·C4H8O or (SR)-[RuII(H)2{N-(pyridin-2-yl­meth­yl)tropNH}(PPh3)]·THF, (1), chlorido­{(1SR,2RS)-N,N'-bis­[(10,11-[eta])-5H-dibenzo[a,d]cyclo­hepten-5-amine]­ethane-1,2-di­amine-[kappa]2N,N'}hydridoruthenium(II) di­meth­oxy­ethane hemisolvate, [RuClH(C32H28N2)]·0.5C4H10O2 or (1SR,2RS)-[RuII(H)(Cl){tropNH(CH2)2HNtrop}]·DME, (2), and chlo­rido­{(1SR,2RS)-N,N'-bis­[(10,11-[eta])-5H-dibenzo[a,d]cyclo­hep­ten-5-amine]­propane-1,3-di­amine-[kappa]2N,N'}hydridoruthenium(II), [RuClH(C33H30N2)] or (1SR,2RS)-[RuII(H)(Cl){tropNH(CH2)3HNtrop}], (3), where trop is 5H-dibenzo[a,d]cyclo­hep­tene. In all three complexes, the RuII center resides in an octa­hedral coordination environment. For (1)-(3), the hydride atoms were located in a difference Fourier map and were refined freely. In solution, the 1H NMR spectra of all species show the presence of the hydride resonance. Comparison with quantum-chemical calculations reveals that the crystallographic data sets are plausible. In every case, the prediction is in very good agreement with the observed X-ray data. Not only the observed geometry is predicted well but also the Ru-H(hydride) bond lengths are reproduced remarkably well. Complexes (1) and (2) crystallized in the triclinic P\overline{1} space group, while (3) crystallized in the tetra­gonal space group I41/a. For (3), there is disorder of the axial ligands producing two isomers (in a 98.7:1.3 ratio). Details of the synthesis, characterization, X-ray analysis, and theoretical calculations for complexes (1)-(3) are presented.

Formula: [RuH2(C21H18N2)(C18H15P)]·C4H8O and two analogues

Keywords: crystal structure; quantum-chemical calculations; RuII-hydride-tropamine complexes.


pdfdisplay filedownload file

Portable Document Format (PDF) file
[ doi:10.1107/S0108270113024505/fa3321sup5.pdf ]
Supplementary material


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.

 bibliographic record in  format

  Find reference:   Volume   Page   
  Search:     From   to      Advanced search

Copyright © International Union of Crystallography
IUCr Webmaster