(4′-Ethynyl-2,2′:6′,2′′-terpyridine)(2,2′:6′,2′′-terpyridine)­ruthenium(II) bis­(hexa­fluoridophosphate) acetonitrile disolvate

Chen, W.; Rein, F.N.; Scott, B.L.; Rocha, R.C.

doi:10.1107/S1600536812051227

Volume 69
Part 2
Pages m79-m80
February 2013

Received 6 December 2012
Accepted 18 December 2012
Online 9 January 2013

Key indicators
Single-crystal X-ray study
T = 140 K
Mean (C-C) = 0.013 Å
Disorder in solvent or counterion
R = 0.084
wR = 0.228
Data-to-parameter ratio = 12.6
Details

(4'-Ethynyl-2,2':6',2''-terpyridine)(2,2':6',2''-terpyridine)ruthenium(II) bis(hexafluoridophosphate) acetonitrile disolvate

Weizhong Chen,^a Francisca N. Rein,^a Brian L. Scott ^a and Reginaldo C. Rocha ^a ^*

^aLos Alamos National Laboratory, Los Alamos, NM 87545, USA
Correspondence e-mail: rcrocha@lanl.gov

The title heteroleptic bis-terpyridine complex, [Ru(C₁₅H₁₁N₃)(C₁₇H₁₁N₃)](PF₆)₂·2CH₃CN, crystallized from an acetonitrile solution as a salt containing two hexafluoridophosphate counter-ions and two acetonitrile solvent molecules. The Ru^II atom has a distorted octahedral geometry due to the restricted bite angle [157.7 (3)°] of the two mer-arranged N,N',N''-tridendate ligands, viz. 2,2':6',2''-terpyridine (tpy) and 4'-ethynyl-2,2':6',2''-terpyridine (tpy'), which are essentially perpendicular to each other, with a dihedral angle of 87.75 (12)° between their terpyridyl planes. The rod-like acetylene group lies in the same plane as its adjacent terpyridyl moiety, with a maximum deviation of only 0.071 (11) Å from coplanarity with the pyridine rings. The mean Ru-N bond length involving the outer N atoms trans to each other is 2.069 (6) Å at tpy and 2.070 (6) Å at tpy'. The Ru-N bond length involving the central N atom is 1.964 (6) Å at tpy and 1.967 (6) Å at tpy'. Two of the three counter anions were refined as half-occupied.

Related literature

For the crystal structure of a Ru^II-terpyridine complex containing the {Ru(tpy-C [triple bond] C)} fragment, see: Ruben et al. (2008). For a comparative discussion, see the Comment section in the Supplementary materials. For bond lengths and angles in related tpy complexes, see: Lashgari et al. (1999); Scudder et al. (2005). For the preparation of the starting materials, see: Benniston et al. (2005); Grosshenny et al. (1997); Sullivan et al. (1980); Ziessel et al. (2004). For general properties of this complex and related systems, see: Grosshenny et al. (1996); Hammarström & Johansson (2010); Ruther et al. (2011); Ziessel et al. (2004).

Experimental

Crystal data

[Ru(C₁₅H₁₁N₃)(C₁₇H₁₁N₃)](PF₆)₂·2C₂H₃N
M_r = 963.67
Triclinic, $[P \overline 1]$
a = 8.704 (2) Å
b = 8.860 (2) Å
c = 27.277 (7) Å
= 96.876 (4)°
= 95.619 (3)°
= 93.023 (3)°
V = 2073.9 (10) Å³
Z = 2
Mo K radiation
= 0.55 mm^-1
T = 140 K
0.10 × 0.08 × 0.06 mm

Data collection

Bruker D8 with APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007) T_min = 0.947, T_max = 0.968
19870 measured reflections
7496 independent reflections
5137 reflections with I > 2(I)
R_int = 0.081

Refinement

R[F² > 2(F²)] = 0.084
wR(F²) = 0.228
S = 1.25
7496 reflections
596 parameters
H-atom parameters constrained
_max = 1.75 e Å^-3
_min = -0.94 e Å^-3

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ5287 ).

Acknowledgements

Support by the US Department of Energy through the Laboratory Directed Research and Development (LDRD) program at LANL is gratefully acknowledged.

References

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metal-organic compounds