μ-2,3,5,6-Tetrakis(pyridin-2-yl)pyrazine-bis[(2,2':6',2''-terpyridine)ruthenium(II)] tetrakis(hexafluoridophosphate) acetonitrile tetrasolvate

Jude, Hershel; Scott, Brian L.; Rocha, Reginaldo C.

doi:10.1107/S1600536812051215

Title: μ-2,3,5,6-Tetrakis(pyridin-2-yl)pyrazine-bis[(2,2':6',2''-terpyridine)ruthenium(II)] tetrakis(hexafluoridophosphate) acetonitrile tetrasolvate

Abstract

In the title compound [Ru₂(C₁₅H₁₁N₃)₂(C₂₄H₁₆N₆)](PF₆)₄·4CH₃CN, two of the counter-ions and one of the solvent molecules are disordered with occupancies for the major components between 0.57 (2) and 0.64 (1). The structure of the dinuclear tetracation exhibits significant distortion from planarity in the bridging 2,3,5,6-tetrakis(pyridin-2-yl)pyrazine (tppz) ligand, which has a saddle-like geometry with an average dihedral angle of 42.96 (18)° between adjacent pyridine rings. The metal–ligand coordination environment is nearly equivalent for the two Ru^IIatoms, which have a distorted octahedral geometry due to the restricted bite angle [157.57 (13)–159.28 (12)°] of their two mer-arranged tridendate ligands [2,2':6',2''-terpyridine (tpy) and tppz] orthogonal to each other. At the peripheral tpy ligands, the average Ru—N bond distance is 2.072 (4) Å for the outer N atoms trans to each other (N_outer) and 1.984 (1) Å for the central N atoms (N_central). At the bridging tppz ligand, the average metal–ligand distances are significantly shorter [2.058 (4) Å for Ru—N_outerand 1.965 (1) Å for Ru—N_central] as a result of both the geometric constraints and the stronger π-acceptor ability of the pyrazine-centered bridge. The dihedral angle between the two tpy planes is 27.11 (6)°. The intramolecular linear distance between the two Ru atoms is 6.6102 (7) Å.

Authors:

Jude, Hershel ^[1]; Scott, Brian L. ^[1]; Rocha, Reginaldo C. ^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Publication Date:: Wed Jan 09 00:00:00 EST 2013

Research Org.:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Laboratory Directed Research and Development (LDRD) Program

OSTI Identifier:: 1629089

Resource Type:: Accepted Manuscript

Journal Name:: Acta Crystallographica. Section E

Additional Journal Information:: Journal Volume: 69; Journal Issue: 2; Journal ID: ISSN 1600-5368

Publisher:: International Union of Crystallography

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; single-crystal X-ray study

Citation Formats


                    Jude, Hershel, Scott, Brian L., and Rocha, Reginaldo C. μ-2,3,5,6-Tetrakis(pyridin-2-yl)pyrazine-bis[(2,2':6',2''-terpyridine)ruthenium(II)] tetrakis(hexafluoridophosphate) acetonitrile tetrasolvate.  United States: N. p., 2013. 
Web.  doi:10.1107/S1600536812051215.

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                    Jude, Hershel, Scott, Brian L., & Rocha, Reginaldo C. μ-2,3,5,6-Tetrakis(pyridin-2-yl)pyrazine-bis[(2,2':6',2''-terpyridine)ruthenium(II)] tetrakis(hexafluoridophosphate) acetonitrile tetrasolvate.  United States.  https://doi.org/10.1107/S1600536812051215

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                    Jude, Hershel, Scott, Brian L., and Rocha, Reginaldo C. Wed .  
"μ-2,3,5,6-Tetrakis(pyridin-2-yl)pyrazine-bis[(2,2':6',2''-terpyridine)ruthenium(II)] tetrakis(hexafluoridophosphate) acetonitrile tetrasolvate".  United States.  https://doi.org/10.1107/S1600536812051215.  https://www.osti.gov/servlets/purl/1629089.

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@article{osti_1629089,

  title        = {μ-2,3,5,6-Tetrakis(pyridin-2-yl)pyrazine-bis[(2,2':6',2''-terpyridine)ruthenium(II)] tetrakis(hexafluoridophosphate) acetonitrile tetrasolvate},

  author       = {Jude, Hershel and Scott, Brian L. and Rocha, Reginaldo C.},

  abstractNote = {In the title compound [Ru2(C15H11N3)2(C24H16N6)](PF6)4·4CH3CN, two of the counter-ions and one of the solvent molecules are disordered with occupancies for the major components between 0.57 (2) and 0.64 (1). The structure of the dinuclear tetracation exhibits significant distortion from planarity in the bridging 2,3,5,6-tetrakis(pyridin-2-yl)pyrazine (tppz) ligand, which has a saddle-like geometry with an average dihedral angle of 42.96 (18)° between adjacent pyridine rings. The metal–ligand coordination environment is nearly equivalent for the two RuIIatoms, which have a distorted octahedral geometry due to the restricted bite angle [157.57 (13)–159.28 (12)°] of their two mer-arranged tridendate ligands [2,2':6',2''-terpyridine (tpy) and tppz] orthogonal to each other. At the peripheral tpy ligands, the average Ru—N bond distance is 2.072 (4) Å for the outer N atoms trans to each other (Nouter) and 1.984 (1) Å for the central N atoms (Ncentral). At the bridging tppz ligand, the average metal–ligand distances are significantly shorter [2.058 (4) Å for Ru—Nouterand 1.965 (1) Å for Ru—Ncentral] as a result of both the geometric constraints and the stronger π-acceptor ability of the pyrazine-centered bridge. The dihedral angle between the two tpy planes is 27.11 (6)°. The intramolecular linear distance between the two Ru atoms is 6.6102 (7) Å.},

  doi          = {10.1107/S1600536812051215},

  journal      = {Acta Crystallographica. Section E},

  number       = 2,

  volume       = 69,

  place        = {United States},

  year         = {Wed Jan 09 00:00:00 EST 2013},

  month        = {Wed Jan 09 00:00:00 EST 2013}

}

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Crystal structure of a mononuclear Ru ^II complex with a back-to-back terpyridine ligand: [RuCl(bpy)(tpy–tpy)] ⁺
journal, August 2015

Rein, Francisca N.; Chen, Weizhong; Scott, Brian L.
Acta Crystallographica Section E Crystallographic Communications, Vol. 71, Issue 9
DOI: 10.1107/s2056989015014632

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Title: μ-2,3,5,6-Tetrakis(pyridin-2-yl)pyrazine-bis[(2,2':6',2''-terpyridine)ruthenium(II)] tetrakis(hexafluoridophosphate) acetonitrile tetrasolvate

Abstract

Citation Formats

Crystal structure of a mononuclear Ru II complex with a back-to-back terpyridine ligand: [RuCl(bpy)(tpy–tpy)] + journal, August 2015

Crystal structure of a mononuclear Ru ^II complex with a back-to-back terpyridine ligand: [RuCl(bpy)(tpy–tpy)] ⁺
journal, August 2015