Acta Crystallographica Section C

Structural Chemistry

Volume 70, Part 3 (March 2014)


research papers



fa3324 scheme

Acta Cryst. (2014). C70, 250-255    [ doi:10.1107/S2053229614003234 ]

A tale of hydrogen abstraction, initially detected via X-ray diffraction

A. K. Hui, C.-H. Chen, A. M. Terwilliger, R. L. Lord and K. G. Caulton

Abstract: Reaction of a bis-tetra­zinyl pyridine pincer ligand, btzp, with a vanadium(III) reagent gives not a simple adduct but di­chlorido­{3-methyl-6-[6-(6-methyl-1,2,4,5-tetrazin-3-yl-[kappa]N2)pyridin-2-yl-[kappa]N]-1,4-di­hydro-1,2,4,5-tetra­zin-1-yl-[kappa]N1}oxidovanadium(IV) acetonitrile 2.5-solvate, [V(C11H10N9)Cl2O]·2.5CH3CN, a species which X-ray diffraction reveals to have one H atom added to one of the two tetra­zinyl rings. This H atom was first revealed by a short inter­molecular N...Cl contact in the unit cell and subsequently established, from difference maps, to be associated with a hydrogen bond. One chloride ligand has also been replaced by an oxide ligand in this synthetic reaction. This formula for the complex, [V(Hbtzp)Cl2O], leaves open the question of both ligand oxidation state and spin state. A computational study of all isomeric locations of the H atom shows the similarity of their energies, which is subject to perturbation by inter­molecular hydrogen bonding found in X-ray work on the solid state. These density functional calculations reveal that the isomer with the H atom located as found in the solid state contains a neutral radical Hbtzp ligand and tetra­valent d1 V center, but that these two unpaired electrons are more stable as an open-shell singlet and hence anti­ferromagnetically coupled.

CCDC reference: 986586

Formula: [V(C11H10N9)Cl2O]·2.5C2H3N

Keywords: crystal structure; vanadium; hydrogen bonding; non-innocent; tetra­zine; hydrogen abstraction; redox.


pdfdisplay filedownload file

Portable Document Format (PDF) file
[ doi:10.1107/S2053229614003234/fa3324sup3.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