(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

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Pages m79-m80

doi:10.1107/S1600536812051227

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(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

(Received 6 December 2012; accepted 18 December 2012; online 9 January 2013)

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≡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
α = 96.876 (4)°
β = 95.619 (3)°
γ = 93.023 (3)°
V = 2073.9 (10) Å³
Z = 2
Mo Kα radiation
μ = 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 > 2σ(I)
R_int = 0.081

Refinement

R[F² > 2σ(F²)] = 0.084
wR(F²) = 0.228
S = 1.25
7496 reflections
596 parameters
H-atom parameters constrained
Δρ_max = 1.75 e Å⁻³
Δρ_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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812051227/sj5287sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812051227/sj5287Isup2.hkl

checkCIF report

Comment top

The compound [Ru^II(tpy)(tpy')](PF₆)₂×2MeCN crystallized in the triclinic space group (P1) from an acetonitrile solution. The crystal structure of its dication [Ru(tpy)(tpy')]²⁺ (I) is reported here for the first time, despite its well demonstrated relevance as a metallo-synthon unit into the construction of alkyne-bridged polyad arrays with optical/electronic applications (for example, see: Benniston et al., 2005; Grosshenny et al., 1996; Ziessel et al., 2004) and, more recently, as interesting precursors to optically/electrochemically active interfacial assemblies via surface click chemistry at the alkynyl group (for example, see: Ruther et al., 2011).

The only other crystallographically characterized compound featuring the {Ru(tpy–C≡C)} fragment is the homoleptic complex [Ru^II(tpy")₂](PF₆)₂ (II; tpy" = S-(4-[2,2':6',2"]terpyridin-4'-ylethynyl-phenyl ester), which was applied in studies of molecular electronics involving charge transport through single molecules (II) in break-junction configurations (Ruben et al., 2008). In this case, the compound also crystallized in the triclinic space group (P1). In II, the two elongated ligands pointed along the long axis of the complex, with only slight distortion across the metal center (N–Ru–N angle: 178.9 (4)°). The mean Ru—N bond distances (1.966 (8) Å for the central nitrogen and 2.066 (10) Å for the outer nitrogen atoms trans to each other) as well as the tpy" bite angles (158.3 (4)°) are very similar to those observed for I.

These distances and angles are also in very good agreement with typical values reported for [Ru(tpy)₂]²⁺ (e.g., Lashgari et al., 1999; Scudder et al., 2005). The bite angle of terpyridines is well known to be far from the ideal 180° due to the unfavorable N,N,N geometric configuration of the mer-terdentate ligand (Hammarström & Johansson, 2010). In I, the two terpyridyl ligands are approximately planar, with only a slight bending towards the outer ring atoms (maximum deviation from planarity: 0.093 (10) Å for atom C13 at tpy and 0.110 (8) Å for atom C30 at tpy'). The acetylenic group (–C31≡C32–H32) lies along the main axis passing through the metal center as well as in the same plane as its adjacent terpyridyl moiety, with a maximum deviation of only 0.071 (11) Å (C32) from coplanarity. The length of the triple bond between C31 and C32 is 1.175 (13) Å.

Related literature top

For the crystal structure of a Ru^II–terpyridine complex containing the {Ru(tpy–C≡C)} fragment, see: Ruben et al. (2008). For a comparative discussion, see the Comment section in the Supplementary materials. For bond distances 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 top

The compound [Ru(tpy)(tpy')](PF₆)₂ was prepared from the precursor [Ru(tpy)(tpy'-TMS)](PF₆)₂ (tpy'-TMS = 4'-trimethylsilylethynyl-(2,2':6',2"-terpy)) as described in the literature (Benniston et al., 2005). Also synthesized according to reported procedures were the starting materials Ru(tpy)Cl₃ (Sullivan et al., 1980) and tpy'-TMS (Grosshenny et al., 1997). The identity of the cation [Ru(tpy)(tpy')]²⁺ (I) in solution was also confirmed by electrochemical and spectroscopic methods. Single crystals suitable for X-ray analysis were grown by slow diffusion of Et₂O into MeCN solutions of [Ru(tpy)(tpy')](PF₆)₂ in a long thin tube.

Structure description top

For the crystal structure of a Ru^II–terpyridine complex containing the {Ru(tpy–C≡C)} fragment, see: Ruben et al. (2008). For a comparative discussion, see the Comment section in the Supplementary materials. For bond distances 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).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); 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).

Figures top

Fig. 1. Figure 1. The single-crystal structure of the cation (I) in [Ru^II(tpy)(tpy')](PF₆)₂×2MeCN. Displacement ellipsoids are drawn at the 50% probability level. Except for H32, H atoms are omitted for clarity.

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

Crystal data top

[Ru(C₁₅H₁₁N₃)(C₁₇H₁₁N₃)](PF₆)₂·2C₂H₃N	Z = 2
M_r = 963.67	F(000) = 964
Triclinic, P1	D_x = 1.543 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.704 (2) Å	Cell parameters from 1822 reflections
b = 8.860 (2) Å	θ = 4.7–41.0°
c = 27.277 (7) Å	µ = 0.55 mm⁻¹
α = 96.876 (4)°	T = 140 K
β = 95.619 (3)°	Block, orange
γ = 93.023 (3)°	0.10 × 0.08 × 0.06 mm
V = 2073.9 (10) Å³

Data collection top

Bruker D8 with APEXII CCD diffractometer	7496 independent reflections
Radiation source: fine-focus sealed tube	5137 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.081
ω scans	θ_max = 25.3°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −10→10
T_min = 0.947, T_max = 0.968	k = −10→10
19870 measured reflections	l = −32→32

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.084	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.228	H-atom parameters constrained
S = 1.25	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
7496 reflections	(Δ/σ)_max < 0.001
596 parameters	Δρ_max = 1.75 e Å⁻³
0 restraints	Δρ_min = −0.94 e Å⁻³

Crystal data top

[Ru(C₁₅H₁₁N₃)(C₁₇H₁₁N₃)](PF₆)₂·2C₂H₃N	γ = 93.023 (3)°
M_r = 963.67	V = 2073.9 (10) Å³
Triclinic, P1	Z = 2
a = 8.704 (2) Å	Mo Kα radiation
b = 8.860 (2) Å	µ = 0.55 mm⁻¹
c = 27.277 (7) Å	T = 140 K
α = 96.876 (4)°	0.10 × 0.08 × 0.06 mm
β = 95.619 (3)°

Data collection top

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

Refinement top

R[F² > 2σ(F²)] = 0.084	0 restraints
wR(F²) = 0.228	H-atom parameters constrained
S = 1.25	Δρ_max = 1.75 e Å⁻³
7496 reflections	Δρ_min = −0.94 e Å⁻³
596 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Note: Two of the hexafluorophosphate anions had very large temperature factors when compared to the third. Other characterization by nuclear magnetic resonance, electronic absorption spectroscopy, and electrochemical techniques clearly support the oxidation state +2 for the Ru center. As a result, the two hexafluorophosphate anions were refined at one-half occupancy.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ru1	0.60446 (7)	0.66280 (7)	0.71976 (2)	0.0229 (2)
P1	0.5105 (3)	0.2494 (3)	0.86893 (9)	0.0406 (6)
P2	0.0665 (4)	0.3760 (5)	0.58567 (15)	0.0223 (9)	0.50
P3	0.3376 (7)	0.9331 (5)	0.52521 (18)	0.0460 (13)	0.50
F1	0.4111 (7)	0.3779 (7)	0.8487 (2)	0.0662 (17)
F2	0.3720 (7)	0.1889 (8)	0.8960 (2)	0.083 (2)
F3	0.6136 (8)	0.1235 (7)	0.8895 (3)	0.087 (2)
F4	0.6488 (6)	0.3082 (6)	0.8399 (2)	0.0627 (16)
F5	0.5731 (8)	0.3658 (7)	0.9169 (2)	0.080 (2)
F6	0.4524 (7)	0.1353 (6)	0.8207 (2)	0.0699 (18)
F7	0.2344 (13)	0.4242 (15)	0.5732 (4)	0.071 (4)	0.50
F8	0.0213 (12)	0.3542 (11)	0.5289 (3)	0.048 (3)	0.50
F9	−0.0984 (14)	0.3277 (16)	0.5993 (4)	0.074 (4)	0.50
F10	0.1149 (13)	0.3953 (11)	0.6387 (3)	0.048 (3)	0.50
F11	0.0255 (16)	0.5450 (15)	0.5929 (5)	0.086 (4)	0.50
F12	0.1067 (14)	0.2015 (14)	0.5798 (5)	0.078 (4)	0.50
F13	0.2819 (11)	0.7699 (11)	0.5355 (4)	0.052 (3)	0.50
F14	0.4594 (13)	0.9411 (12)	0.5740 (4)	0.055 (3)	0.50
F15	0.2102 (13)	0.9903 (13)	0.5575 (4)	0.061 (3)	0.50
F16	0.3906 (14)	1.1053 (11)	0.5201 (4)	0.051 (3)	0.50
F17	0.2281 (13)	0.9269 (11)	0.4820 (5)	0.066 (4)	0.50
F18	0.4732 (18)	0.8751 (13)	0.4927 (5)	0.080 (4)	0.50
N1	0.6951 (6)	0.8758 (7)	0.7100 (2)	0.0218 (14)
N2	0.6314 (7)	0.6327 (6)	0.6487 (2)	0.0223 (14)
N3	0.5163 (7)	0.4394 (7)	0.7002 (3)	0.0306 (16)
N4	0.8136 (7)	0.5925 (6)	0.7502 (2)	0.0212 (14)
N5	0.5824 (7)	0.6975 (6)	0.7912 (2)	0.0241 (14)
N6	0.3870 (7)	0.7435 (7)	0.7184 (3)	0.0273 (15)
N7	0.9608 (12)	−0.0287 (12)	0.8456 (4)	0.082 (3)
N8	0.0331 (14)	0.6614 (13)	0.9563 (4)	0.088 (3)
C1	0.7199 (8)	1.0006 (9)	0.7444 (3)	0.0273 (18)
H1	0.6942	0.9936	0.7764	0.033*
C2	0.7826 (9)	1.1392 (9)	0.7334 (3)	0.032 (2)
H2	0.7969	1.2236	0.7575	0.039*
C3	0.8230 (9)	1.1495 (8)	0.6865 (3)	0.032 (2)
H3	0.8692	1.2396	0.6788	0.039*
C4	0.7941 (9)	1.0242 (9)	0.6506 (3)	0.0291 (19)
H4	0.8165	1.0314	0.6183	0.035*
C5	0.7316 (8)	0.8874 (8)	0.6628 (3)	0.0234 (17)
C6	0.6973 (9)	0.7496 (9)	0.6277 (3)	0.0251 (17)
C7	0.7184 (11)	0.7255 (10)	0.5781 (3)	0.042 (2)
H7	0.7616	0.8050	0.5635	0.050*
C8	0.6785 (13)	0.5893 (11)	0.5496 (3)	0.056 (3)
H8	0.6959	0.5754	0.5163	0.067*
C9	0.6102 (12)	0.4699 (10)	0.5717 (3)	0.048 (3)
H9	0.5808	0.3758	0.5533	0.058*
C10	0.5881 (9)	0.4966 (8)	0.6215 (3)	0.0294 (19)
C11	0.5205 (9)	0.3899 (9)	0.6516 (3)	0.034 (2)
C12	0.4598 (11)	0.2427 (9)	0.6311 (4)	0.051 (3)
H12	0.4632	0.2099	0.5976	0.061*
C13	0.3950 (11)	0.1473 (10)	0.6612 (4)	0.061 (3)
H13	0.3528	0.0503	0.6484	0.073*
C14	0.3951 (10)	0.2002 (10)	0.7107 (4)	0.050 (3)
H14	0.3551	0.1369	0.7319	0.059*
C15	0.4541 (9)	0.3471 (9)	0.7297 (4)	0.038 (2)
H15	0.4505	0.3815	0.7631	0.046*
C16	0.9277 (8)	0.5350 (8)	0.7264 (3)	0.0251 (17)
H16	0.9201	0.5297	0.6920	0.030*
C17	1.0570 (9)	0.4828 (9)	0.7508 (3)	0.0312 (19)
H17	1.1334	0.4413	0.7328	0.037*
C18	1.0729 (9)	0.4920 (9)	0.8014 (3)	0.036 (2)
H18	1.1600	0.4586	0.8184	0.043*
C19	0.9558 (9)	0.5523 (9)	0.8265 (3)	0.033 (2)
H19	0.9635	0.5599	0.8610	0.040*
C20	0.8264 (8)	0.6019 (8)	0.8006 (3)	0.0252 (18)
C21	0.6948 (10)	0.6671 (9)	0.8251 (3)	0.0304 (19)
C22	0.6838 (11)	0.6954 (9)	0.8747 (3)	0.038 (2)
H22	0.7631	0.6723	0.8975	0.045*
C23	0.5526 (12)	0.7590 (9)	0.8908 (3)	0.041 (2)
C24	0.4340 (11)	0.7933 (9)	0.8559 (3)	0.041 (2)
H24	0.3463	0.8378	0.8662	0.049*
C25	0.4506 (9)	0.7593 (9)	0.8058 (3)	0.033 (2)
C26	0.3421 (9)	0.7893 (9)	0.7645 (3)	0.032 (2)
C27	0.2062 (9)	0.8608 (9)	0.7703 (4)	0.042 (2)
H27	0.1808	0.8962	0.8018	0.051*
C28	0.1083 (10)	0.8787 (10)	0.7282 (4)	0.053 (3)
H28	0.0161	0.9257	0.7312	0.063*
C29	0.1501 (9)	0.8255 (9)	0.6820 (4)	0.041 (2)
H29	0.0854	0.8357	0.6536	0.049*
C30	0.2887 (9)	0.7569 (9)	0.6782 (4)	0.035 (2)
H30	0.3144	0.7191	0.6470	0.042*
C31	0.5415 (13)	0.7943 (11)	0.9431 (4)	0.058 (3)
C32	0.5330 (16)	0.8213 (12)	0.9860 (4)	0.072 (4)
H32	0.5263	0.8427	1.0199	0.087*
C33	0.9607 (15)	0.0376 (19)	0.8804 (5)	0.104 (6)
C34	0.958 (2)	0.113 (4)	0.9314 (8)	0.36 (3)
H34A	0.8897	0.0544	0.9486	0.541*
H34B	0.9217	0.2132	0.9303	0.541*
H34C	1.0603	0.1207	0.9485	0.541*
C35	0.1365 (14)	0.5885 (14)	0.9648 (4)	0.063 (3)
C36	0.2593 (15)	0.4921 (15)	0.9767 (5)	0.084 (4)
H36A	0.3438	0.5523	0.9962	0.126*
H36B	0.2941	0.4450	0.9465	0.126*
H36C	0.2220	0.4148	0.9952	0.126*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.0183 (3)	0.0179 (3)	0.0337 (4)	−0.0009 (2)	0.0022 (3)	0.0091 (3)
P1	0.0455 (14)	0.0296 (13)	0.0456 (15)	0.0006 (11)	−0.0040 (11)	0.0080 (11)
P2	0.0167 (19)	0.025 (2)	0.027 (2)	0.0045 (16)	0.0036 (16)	0.0105 (17)
P3	0.072 (4)	0.029 (3)	0.035 (3)	−0.003 (2)	0.010 (3)	−0.005 (2)
F1	0.055 (4)	0.064 (4)	0.086 (4)	0.028 (3)	0.006 (3)	0.025 (3)
F2	0.067 (4)	0.104 (6)	0.080 (5)	−0.027 (4)	0.019 (3)	0.029 (4)
F3	0.072 (5)	0.057 (4)	0.134 (6)	0.011 (3)	−0.018 (4)	0.044 (4)
F4	0.054 (4)	0.055 (4)	0.083 (4)	−0.006 (3)	0.013 (3)	0.021 (3)
F5	0.111 (6)	0.068 (4)	0.052 (4)	−0.030 (4)	−0.008 (4)	0.002 (3)
F6	0.092 (5)	0.045 (4)	0.065 (4)	−0.021 (3)	0.003 (3)	−0.007 (3)
F7	0.055 (8)	0.095 (10)	0.067 (8)	−0.012 (7)	−0.004 (6)	0.038 (7)
F8	0.076 (8)	0.055 (7)	0.009 (5)	−0.040 (6)	0.004 (4)	0.008 (4)
F9	0.062 (8)	0.101 (10)	0.077 (9)	0.020 (7)	0.026 (7)	0.056 (8)
F10	0.083 (8)	0.033 (6)	0.036 (6)	0.015 (5)	0.047 (5)	0.001 (4)
F11	0.085 (10)	0.062 (9)	0.099 (10)	0.021 (7)	−0.043 (8)	0.001 (7)
F12	0.067 (8)	0.060 (8)	0.098 (10)	0.021 (7)	−0.024 (7)	−0.008 (7)
F13	0.035 (6)	0.041 (6)	0.072 (8)	−0.027 (5)	0.016 (5)	−0.023 (5)
F14	0.073 (8)	0.049 (7)	0.047 (7)	0.030 (6)	0.006 (6)	0.006 (5)
F15	0.049 (7)	0.059 (8)	0.073 (8)	0.004 (6)	−0.006 (6)	0.013 (6)
F16	0.080 (9)	0.035 (6)	0.035 (6)	−0.021 (6)	−0.003 (6)	0.002 (5)
F17	0.060 (7)	0.020 (5)	0.109 (10)	−0.015 (5)	−0.032 (7)	0.019 (6)
F18	0.113 (12)	0.050 (8)	0.070 (9)	−0.029 (8)	0.033 (8)	−0.021 (6)
N1	0.014 (3)	0.018 (3)	0.034 (4)	0.006 (2)	−0.001 (3)	0.003 (3)
N2	0.017 (3)	0.013 (3)	0.036 (4)	−0.001 (2)	−0.008 (3)	0.008 (3)
N3	0.023 (4)	0.025 (4)	0.043 (4)	−0.009 (3)	−0.007 (3)	0.015 (3)
N4	0.019 (3)	0.011 (3)	0.032 (4)	−0.001 (2)	−0.002 (3)	0.001 (3)
N5	0.026 (3)	0.011 (3)	0.037 (4)	0.004 (3)	0.009 (3)	0.007 (3)
N6	0.015 (3)	0.020 (3)	0.048 (4)	−0.004 (3)	−0.001 (3)	0.012 (3)
N7	0.078 (7)	0.084 (8)	0.079 (8)	−0.020 (6)	0.031 (6)	−0.024 (6)
N8	0.096 (9)	0.098 (9)	0.065 (7)	0.019 (7)	−0.022 (6)	0.009 (6)
C1	0.022 (4)	0.022 (4)	0.036 (5)	0.003 (3)	0.002 (3)	0.000 (4)
C2	0.035 (5)	0.024 (5)	0.037 (5)	0.013 (4)	−0.002 (4)	0.001 (4)
C3	0.029 (4)	0.010 (4)	0.055 (6)	−0.004 (3)	−0.007 (4)	0.007 (4)
C4	0.025 (4)	0.028 (5)	0.036 (5)	−0.001 (3)	0.000 (4)	0.016 (4)
C5	0.020 (4)	0.021 (4)	0.030 (4)	0.003 (3)	0.004 (3)	0.004 (3)
C6	0.026 (4)	0.023 (4)	0.026 (4)	0.002 (3)	0.000 (3)	0.005 (3)
C7	0.063 (6)	0.024 (5)	0.039 (5)	−0.005 (4)	0.004 (5)	0.016 (4)
C8	0.100 (9)	0.043 (6)	0.022 (5)	0.004 (6)	−0.002 (5)	0.000 (4)
C9	0.080 (7)	0.021 (5)	0.037 (6)	−0.003 (5)	−0.023 (5)	0.003 (4)
C10	0.035 (5)	0.014 (4)	0.037 (5)	−0.003 (3)	−0.013 (4)	0.006 (3)
C11	0.030 (5)	0.014 (4)	0.057 (6)	−0.012 (3)	−0.015 (4)	0.018 (4)
C12	0.059 (6)	0.018 (5)	0.070 (7)	−0.007 (4)	−0.031 (5)	0.012 (4)
C13	0.056 (6)	0.024 (5)	0.096 (9)	−0.025 (5)	−0.045 (6)	0.035 (5)
C14	0.041 (6)	0.027 (5)	0.079 (8)	−0.015 (4)	−0.021 (5)	0.031 (5)
C15	0.017 (4)	0.033 (5)	0.066 (6)	−0.011 (4)	−0.010 (4)	0.027 (4)
C16	0.023 (4)	0.011 (4)	0.041 (5)	−0.005 (3)	0.006 (4)	0.003 (3)
C17	0.017 (4)	0.020 (4)	0.056 (6)	0.002 (3)	0.004 (4)	0.004 (4)
C18	0.018 (4)	0.029 (5)	0.059 (6)	0.005 (3)	−0.007 (4)	0.003 (4)
C19	0.037 (5)	0.028 (5)	0.033 (5)	0.005 (4)	−0.003 (4)	0.000 (4)
C20	0.021 (4)	0.013 (4)	0.043 (5)	0.000 (3)	−0.001 (4)	0.009 (3)
C21	0.038 (5)	0.024 (4)	0.028 (5)	−0.006 (4)	0.000 (4)	0.006 (3)
C22	0.052 (6)	0.027 (5)	0.035 (5)	−0.002 (4)	0.002 (4)	0.011 (4)
C23	0.071 (7)	0.020 (4)	0.036 (5)	0.000 (4)	0.019 (5)	0.006 (4)
C24	0.049 (6)	0.027 (5)	0.053 (6)	0.004 (4)	0.028 (5)	0.012 (4)
C25	0.028 (4)	0.021 (4)	0.053 (6)	0.001 (3)	0.015 (4)	0.010 (4)
C26	0.030 (4)	0.020 (4)	0.049 (5)	−0.004 (3)	0.015 (4)	0.013 (4)
C27	0.026 (5)	0.024 (5)	0.081 (7)	0.000 (4)	0.015 (5)	0.015 (5)
C28	0.024 (5)	0.030 (5)	0.111 (9)	0.003 (4)	0.017 (6)	0.025 (6)
C29	0.019 (4)	0.021 (5)	0.085 (7)	−0.008 (3)	−0.008 (5)	0.033 (5)
C30	0.026 (4)	0.015 (4)	0.066 (6)	−0.003 (3)	0.000 (4)	0.017 (4)
C31	0.083 (8)	0.039 (6)	0.058 (7)	0.019 (6)	0.028 (6)	0.011 (5)
C32	0.134 (12)	0.046 (7)	0.047 (7)	0.035 (7)	0.036 (7)	0.013 (5)
C33	0.055 (8)	0.147 (15)	0.089 (11)	0.011 (9)	−0.007 (7)	−0.058 (10)
C34	0.15 (2)	0.60 (6)	0.23 (3)	0.16 (3)	−0.099 (19)	−0.33 (3)
C35	0.072 (8)	0.077 (8)	0.036 (6)	0.026 (7)	−0.009 (5)	−0.003 (5)
C36	0.082 (10)	0.085 (10)	0.085 (9)	0.004 (8)	0.004 (7)	0.013 (7)

Geometric parameters (Å, º) top

Ru1—N2	1.964 (6)	C8—C9	1.411 (13)
Ru1—N5	1.967 (6)	C9—C10	1.385 (12)
Ru1—N6	2.057 (6)	C10—C11	1.461 (11)
Ru1—N1	2.064 (6)	C11—C12	1.410 (11)
Ru1—N3	2.073 (6)	C12—C13	1.384 (13)
Ru1—N4	2.083 (6)	C13—C14	1.374 (14)
P1—F2	1.577 (6)	C14—C15	1.394 (12)
P1—F6	1.583 (6)	C16—C17	1.381 (10)
P1—F1	1.585 (6)	C17—C18	1.364 (11)
P1—F3	1.588 (6)	C18—C19	1.378 (11)
P1—F5	1.596 (6)	C19—C20	1.389 (11)
P1—F4	1.602 (6)	C20—C21	1.489 (11)
P2—F10	1.453 (11)	C21—C22	1.360 (11)
P2—F8	1.547 (9)	C22—C23	1.386 (12)
P2—F11	1.551 (13)	C23—C24	1.404 (13)
P2—F9	1.568 (12)	C23—C31	1.438 (13)
P2—F7	1.581 (12)	C24—C25	1.388 (11)
P2—F12	1.597 (12)	C25—C26	1.457 (12)
P3—F17	1.435 (12)	C26—C27	1.385 (11)
P3—F15	1.551 (13)	C27—C28	1.390 (13)
P3—F13	1.567 (11)	C28—C29	1.381 (13)
P3—F16	1.597 (11)	C29—C30	1.387 (11)
P3—F14	1.610 (12)	C31—C32	1.175 (13)
P3—F18	1.613 (15)	C33—C34	1.47 (2)
F16—F18ⁱ	1.278 (16)	C35—C36	1.439 (16)
F18—F16ⁱ	1.278 (16)	C1—H1	0.93
N1—C1	1.355 (9)	C2—H2	0.93
N1—C5	1.370 (9)	C3—H3	0.93
N2—C10	1.353 (9)	C4—H4	0.93
N2—C6	1.368 (9)	C7—H7	0.93
N3—C15	1.344 (10)	C8—H8	0.93
N3—C11	1.350 (10)	C9—H9	0.93
N4—C16	1.330 (9)	C12—H12	0.93
N4—C20	1.361 (9)	C13—H13	0.93
N5—C21	1.338 (10)	C14—H14	0.93
N5—C25	1.370 (10)	C15—H15	0.93
N6—C30	1.344 (10)	C16—H16	0.93
N6—C26	1.373 (10)	C17—H17	0.93
N7—C33	1.054 (13)	C18—H18	0.93
N8—C35	1.157 (14)	C19—H19	0.93
C1—C2	1.395 (11)	C22—H22	0.93
C2—C3	1.371 (11)	C24—H24	0.93
C3—C4	1.383 (11)	C27—H27	0.93
C4—C5	1.392 (10)	C28—H28	0.93
C5—C6	1.456 (10)	C29—H29	0.93
C6—C7	1.376 (11)	C30—H30	0.93
C7—C8	1.363 (12)	C32—H32	0.93

N2—Ru1—N5	178.3 (3)	N2—C6—C7	118.3 (7)
N2—Ru1—N6	101.3 (3)	N2—C6—C5	112.5 (6)
N5—Ru1—N6	79.4 (3)	C7—C6—C5	129.1 (7)
N2—Ru1—N1	79.0 (2)	C8—C7—C6	122.4 (8)
N5—Ru1—N1	99.5 (2)	C7—C8—C9	118.6 (9)
N6—Ru1—N1	89.9 (2)	C10—C9—C8	118.2 (8)
N2—Ru1—N3	78.8 (3)	N2—C10—C9	121.4 (7)
N5—Ru1—N3	102.6 (3)	N2—C10—C11	111.3 (7)
N6—Ru1—N3	92.4 (2)	C9—C10—C11	127.3 (7)
N1—Ru1—N3	157.7 (3)	N3—C11—C12	121.0 (8)
N2—Ru1—N4	100.9 (2)	N3—C11—C10	117.0 (7)
N5—Ru1—N4	78.3 (2)	C12—C11—C10	122.1 (9)
N6—Ru1—N4	157.7 (3)	C13—C12—C11	119.6 (10)
N1—Ru1—N4	94.5 (2)	C14—C13—C12	118.0 (9)
N3—Ru1—N4	91.7 (2)	C13—C14—C15	121.1 (9)
F2—P1—F6	90.3 (4)	N3—C15—C14	120.6 (9)
F2—P1—F1	91.5 (4)	N4—C16—C17	122.4 (8)
F6—P1—F1	90.6 (4)	C18—C17—C16	120.1 (8)
F2—P1—F3	89.5 (4)	C17—C18—C19	118.0 (8)
F6—P1—F3	90.3 (4)	C18—C19—C20	120.4 (8)
F1—P1—F3	178.7 (4)	N4—C20—C19	120.6 (7)
F2—P1—F5	91.2 (4)	N4—C20—C21	115.9 (6)
F6—P1—F5	178.4 (4)	C19—C20—C21	123.5 (7)
F1—P1—F5	89.4 (4)	N5—C21—C22	122.1 (8)
F3—P1—F5	89.7 (4)	N5—C21—C20	110.8 (7)
F2—P1—F4	178.3 (4)	C22—C21—C20	127.0 (8)
F6—P1—F4	88.0 (3)	C21—C22—C23	119.0 (8)
F1—P1—F4	88.2 (3)	C22—C23—C24	119.8 (8)
F3—P1—F4	90.8 (4)	C22—C23—C31	119.7 (9)
F5—P1—F4	90.4 (4)	C24—C23—C31	120.5 (9)
F10—P2—F8	177.8 (6)	C25—C24—C23	118.6 (8)
F10—P2—F11	86.5 (6)	N5—C25—C24	120.0 (8)
F8—P2—F11	94.6 (7)	N5—C25—C26	113.5 (7)
F10—P2—F9	86.5 (6)	C24—C25—C26	126.4 (8)
F8—P2—F9	95.4 (6)	N6—C26—C27	121.9 (8)
F11—P2—F9	89.2 (8)	N6—C26—C25	114.4 (7)
F10—P2—F7	92.1 (6)	C27—C26—C25	123.7 (8)
F8—P2—F7	85.9 (6)	C26—C27—C28	118.8 (9)
F11—P2—F7	91.1 (8)	C29—C28—C27	119.0 (8)
F9—P2—F7	178.6 (6)	C28—C29—C30	119.9 (9)
F10—P2—F12	92.2 (6)	N6—C30—C29	121.8 (9)
F8—P2—F12	86.8 (6)	C32—C31—C23	179.1 (11)
F11—P2—F12	178.3 (8)	N7—C33—C34	173 (2)
F9—P2—F12	89.6 (7)	N8—C35—C36	176.8 (15)
F7—P2—F12	90.1 (7)	N1—C1—H1	119
F17—P3—F15	88.9 (8)	C2—C1—H1	119
F17—P3—F13	92.5 (6)	C1—C2—H2	121
F15—P3—F13	85.6 (6)	C3—C2—H2	120
F17—P3—F16	90.7 (6)	C2—C3—H3	121
F15—P3—F16	89.8 (7)	C4—C3—H3	120
F13—P3—F16	174.3 (6)	C3—C4—H4	120
F17—P3—F14	179.5 (8)	C5—C4—H4	120
F15—P3—F14	90.6 (6)	C6—C7—H7	119
F13—P3—F14	87.7 (6)	C8—C7—H7	119
F16—P3—F14	89.1 (6)	C7—C8—H8	121
F17—P3—F18	92.4 (8)	C9—C8—H8	121
F15—P3—F18	178.6 (8)	C8—C9—H9	121
F13—P3—F18	94.8 (6)	C10—C9—H9	121
F16—P3—F18	89.8 (6)	C11—C12—H12	120
F14—P3—F18	88.1 (7)	C13—C12—H12	120
F18ⁱ—F16—P3	115.0 (10)	C12—C13—H13	121
F16ⁱ—F18—P3	149.8 (10)	C14—C13—H13	121
C1—N1—C5	118.6 (6)	C13—C14—H14	120
C1—N1—Ru1	127.3 (5)	C15—C14—H14	119
C5—N1—Ru1	114.1 (5)	N3—C15—H15	120
C10—N2—C6	121.0 (7)	C14—C15—H15	120
C10—N2—Ru1	119.9 (5)	N4—C16—H16	119
C6—N2—Ru1	119.1 (5)	C17—C16—H16	119
C15—N3—C11	119.8 (7)	C16—C17—H17	120
C15—N3—Ru1	127.2 (6)	C18—C17—H17	120
C11—N3—Ru1	113.0 (5)	C17—C18—H18	121
C16—N4—C20	118.5 (6)	C19—C18—H18	121
C16—N4—Ru1	127.9 (5)	C18—C19—H19	120
C20—N4—Ru1	113.5 (5)	C20—C19—H19	120
C21—N5—C25	120.5 (7)	C21—C22—H22	121
C21—N5—Ru1	121.4 (5)	C23—C22—H22	120
C25—N5—Ru1	118.1 (5)	C23—C24—H24	121
C30—N6—C26	118.4 (7)	C25—C24—H24	121
C30—N6—Ru1	127.3 (6)	C26—C27—H27	121
C26—N6—Ru1	114.4 (5)	C28—C27—H27	121
N1—C1—C2	122.2 (7)	C27—C28—H28	120
C3—C2—C1	119.2 (7)	C29—C28—H28	121
C2—C3—C4	119.2 (7)	C28—C29—H29	120
C3—C4—C5	120.3 (7)	C30—C29—H29	120
N1—C5—C4	120.6 (7)	N6—C30—H30	119
N1—C5—C6	115.2 (6)	C29—C30—H30	119
C4—C5—C6	124.2 (7)	C31—C32—H32	180

Symmetry code: (i) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	[Ru(C₁₅H₁₁N₃)(C₁₇H₁₁N₃)](PF₆)₂·2C₂H₃N
M_r	963.67
Crystal system, space group	Triclinic, P1
Temperature (K)	140
a, b, c (Å)	8.704 (2), 8.860 (2), 27.277 (7)
α, β, γ (°)	96.876 (4), 95.619 (3), 93.023 (3)
V (Å³)	2073.9 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.55
Crystal size (mm)	0.10 × 0.08 × 0.06

Data collection
Diffractometer	Bruker D8 with APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.947, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	19870, 7496, 5137
R_int	0.081
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.084, 0.228, 1.25
No. of reflections	7496
No. of parameters	596
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.75, −0.94

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

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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