Bis(2,2′-bipyridine)(5-isothio­cyanato-1,10-phenanthroline)ruthenium(II) bis­(hexa­fluoridophosphate) acetonitrile solvate

Nag, S.; Pal, A.K.; Hanan, G.S.

doi:10.1107/S1600536809035302

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page m1184

doi:10.1107/S1600536809035302

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Bis(2,2′-bipyridine)(5-isothiocyanato-1,10-phenanthroline)ruthenium(II) bis(hexafluoridophosphate) acetonitrile solvate

Samik Nag,^a Amlan K. Pal ^a ^* and Garry S. Hanan ^a

^aDépartement de Chimie, Université de Montréal, CP 6128, Succ. Centre-ville, Montréal, Québec, Canada H3C 3J7
^*Correspondence e-mail: amlan.kumar.pal@umontreal.ca

(Received 21 August 2009; accepted 1 September 2009; online 9 September 2009)

The title compound, [Ru(C₁₀H₈N₂)₂(C₁₃H₇N₃S)](PF₆)₂·CH₃CN, was synthesized by the reaction of thiophosgene and bis(2,2′-bipyridine)(1,10-phenanthrolin-5-amine)ruthenium(II) bis(hexafluoridophosphate). The Ru^II atom adopts a slightly distorted octahedral RuN₆ coordinaton formed by four N atoms of two bipyridine ligands and by two N atoms of the 1,10-phenantroline ligand. The isothiocyanate group is almost linear, with an N—C—S angle of 174.4 (6)°. Two of the three hexafluoridophosphate counter-anions are located on inversion centres.

Related literature

The title compound was previously synthesized by two other groups (Ryan et al., 1992 ; Khimich et al., 2007 ). However, the crystal structure was not reported at that time. For the crystal structures of related compounds, see: Ye et al. (1999 ); Huang & Ogawa (2006 ); Batey et al. (2007 ). For the importance and applications of Ru^II complexes with bipyridine ligands, see: Bertini et al. (1994 ); Medlycott & Hanan (2005 , 2006 ).

Experimental

Crystal data

[Ru(C₁₀H₈N₂)₂(C₁₃H₇N₃S)](PF₆)₂·C₂H₃N
M_r = 981.71
Triclinic, $[P \overline 1]$
a = 9.129 (3) Å
b = 12.397 (4) Å
c = 17.084 (5) Å
α = 88.618 (4)°
β = 89.704 (5)°
γ = 72.870 (4)°
V = 1847.1 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.67 mm⁻¹
T = 150 K
0.24 × 0.13 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.83, T_max = 0.95
178384 measured reflections
6687 independent reflections
6155 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.152
S = 1.18
6687 reflections
536 parameters
H-atom parameters constrained
Δρ_max = 1.45 e Å⁻³
Δρ_min = −0.86 e Å⁻³

Table 1
Selected bond lengths (Å)

Ru—N1	2.056 (4)
Ru—N3	2.059 (4)
Ru—N2	2.059 (4)
Ru—N4	2.064 (4)
Ru—N6	2.065 (4)
Ru—N5	2.072 (4)

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; 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: UdMX (Maris, 2004 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809035302/wm2252sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035302/wm2252Isup2.hkl

checkCIF report

Comment top

Ru^II polypyridyl complexes, mainly [Ru(bpy)₃]²⁺ (bpy = 2,2'-bipyridine) and its derivatives have been studied extensively during the past three decades for their excellent photophysical properties characterized by long excited state lifetimes which makes them suitable choice for chromophores in light-harvesting devices (Medlycott & Hanan, 2005, 2006). Such good emissive properties of this class of compounds also make them useful in labelling biomolecules (Bertini et al., 1994). The title compound can be used to label biomolecules through a thiourea linkage by reaction of the isothiocyanate group on it with an amino group of the protein (Ryan et al., 1992; Khimich et al., 2007).

The crystal structure of the title compound reveals that the ruthenium atom has a slightly distorted octahedral coordinaton sphere and the isothiocyanate group is almost linear with a N—C—S angle of 174.4 (6)°. The six Ru—N bond distances falls in a short range of 2.056 (4) to 2.072 (4) Å, with the two longer ones being that with the phenanthroline moiety. The bite angles for the 2,2'-bipyridine lingands are 79.03 (16)° and 78.91 (15)°, while that for the phenanthroline is 78.91 (15)°.

For crystal structures of related Ru^II complexes with bidentate polypyridyl ligands, see: Ye et al. (1999); Huang & Ogawa (2006); Batey et al. (2007).

Related literature top

The title compound was previously synthesized by two other groups (Ryan et al., 1992; Khimich et al., 2007). However, the crystal structure was not reported at that time. For the crystal structures of related compounds, see: Ye et al. (1999); Huang & Ogawa (2006); Batey et al. (2007). For the importance and applications of Ru^II complexes with bipyridine ligands, see: Bertini et al. (1994); Medlycott & Hanan (2005, 2006).

Experimental top

Bis(2,2'-bipyridine)(1,10-phenanthroline-5-amine)ruthenium(II) bis(hexafluoridophosphate) (450 mg, 0.5 mmol) was dissolved in acetone (100 ml). To this dark red solution was added Na₂CO₃ (212 mg, 2.0 mmol). After addition of CSCl₂ (0.5 ml) to the reaction mixture under N₂ atmosphere, it was stirred for 7 h. Then the solvent was evaporated under reduced pressure and the residue dissolved in dichloromethane and filtered. The filtrate was dried over anhydrous Na₂SO₄. After removal of the solvent under reduced pressure, a red crystalline compound was obtained. Yield: 446 mg (95%). Red crystals suitable for X-ray crystallography were grown by slow diffusion of isopropyl ether into a dilute acetonitrile solution of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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: UdMX (Maris, 2004).

Figures top

Fig. 1. View of the cation in the title compound. Thermal ellipsoids are shown at the 50% probability level. H atoms, hexafluoridophosphate anions and the acetonitrile solvent molecule have been omitted for clarity.

Bis(2,2'-bipyridine)(5-isothiocyanato-1,10-phenanthroline)ruthenium(II) bis(hexafluoridophosphate) acetonitrile solvate top

Crystal data top

[Ru(C₁₀H₈N₂)₂(C₁₃H₇N₃S)](PF₆)₂·C₂H₃N	Z = 2
M_r = 981.71	F(000) = 980
Triclinic, P1	D_x = 1.765 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.129 (3) Å	Cell parameters from 32297 reflections
b = 12.397 (4) Å	θ = 2.3–24.9°
c = 17.084 (5) Å	µ = 0.67 mm⁻¹
α = 88.618 (4)°	T = 150 K
β = 89.704 (5)°	Block, red
γ = 72.870 (4)°	0.24 × 0.13 × 0.10 mm
V = 1847.1 (10) Å³

Data collection top

Bruker APEXII CCD diffractometer	6687 independent reflections
Radiation source: X-ray sealed tube	6155 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
Detector resolution: 8.3 pixels mm^-1	θ_max = 25.3°, θ_min = 1.2°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −14→14
T_min = 0.83, T_max = 0.95	l = −20→20
178384 measured reflections

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.152	H-atom parameters constrained
S = 1.18	w = 1/[σ²(F_o²) + (0.0708P)² + 4.8035P] where P = (F_o² + 2F_c²)/3
6687 reflections	(Δ/σ)_max = 0.001
536 parameters	Δρ_max = 1.45 e Å⁻³
0 restraints	Δρ_min = −0.86 e Å⁻³

Crystal data top

[Ru(C₁₀H₈N₂)₂(C₁₃H₇N₃S)](PF₆)₂·C₂H₃N	γ = 72.870 (4)°
M_r = 981.71	V = 1847.1 (10) Å³
Triclinic, P1	Z = 2
a = 9.129 (3) Å	Mo Kα radiation
b = 12.397 (4) Å	µ = 0.67 mm⁻¹
c = 17.084 (5) Å	T = 150 K
α = 88.618 (4)°	0.24 × 0.13 × 0.10 mm
β = 89.704 (5)°

Data collection top

Bruker APEXII CCD diffractometer	6687 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	6155 reflections with I > 2σ(I)
T_min = 0.83, T_max = 0.95	R_int = 0.061
178384 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.152	H-atom parameters constrained
S = 1.18	Δρ_max = 1.45 e Å⁻³
6687 reflections	Δρ_min = −0.86 e Å⁻³
536 parameters

Special details top

Experimental. X-ray crystallographic data for I were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker smart diffractometer equiped with an APEX II CCD Detector, a graphite monochromator. The crystal-to-detector distance was 5.0 cm, and the data collection was carried out in 512 x 512 pixel mode. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 10.0 degree scan in 33 frames over four different parts of the reciprocal space (132 frames total).

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.

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

	x	y	z	U_iso*/U_eq
Ru	0.38640 (4)	0.62025 (3)	0.24834 (2)	0.03144 (14)
S	−0.09857 (19)	0.94046 (14)	0.70014 (10)	0.0591 (4)
N1	0.4231 (4)	0.7694 (3)	0.2119 (2)	0.0367 (8)
N2	0.3529 (5)	0.6162 (4)	0.1294 (2)	0.0388 (9)
N3	0.6085 (4)	0.5205 (3)	0.2332 (2)	0.0357 (8)
N4	0.3658 (5)	0.4625 (3)	0.2763 (2)	0.0341 (8)
N5	0.4022 (5)	0.6486 (3)	0.3666 (2)	0.0369 (9)
N6	0.1613 (5)	0.7088 (3)	0.2710 (2)	0.0360 (9)
N7	0.0887 (6)	0.8460 (4)	0.5781 (3)	0.0602 (13)
C1	0.4583 (6)	0.8450 (4)	0.2582 (3)	0.0431 (11)
H1	0.4678	0.8303	0.3130	0.052*
C2	0.4806 (6)	0.9433 (4)	0.2279 (4)	0.0519 (14)
H2	0.5066	0.9947	0.2615	0.062*
C3	0.4652 (6)	0.9660 (5)	0.1489 (4)	0.0565 (15)
H3	0.4791	1.0338	0.1275	0.068*
C4	0.4294 (6)	0.8901 (5)	0.1012 (4)	0.0510 (13)
H4	0.4183	0.9048	0.0464	0.061*
C5	0.4095 (5)	0.7919 (4)	0.1334 (3)	0.0410 (11)
C6	0.3705 (5)	0.7049 (4)	0.0877 (3)	0.0409 (11)
C7	0.3534 (6)	0.7108 (5)	0.0063 (3)	0.0536 (14)
H7	0.3704	0.7722	−0.0229	0.064*
C8	0.3122 (7)	0.6279 (6)	−0.0310 (3)	0.0581 (15)
H8	0.2978	0.6322	−0.0861	0.070*
C9	0.2917 (7)	0.5380 (5)	0.0119 (3)	0.0524 (13)
H9	0.2623	0.4800	−0.0132	0.063*
C10	0.3144 (6)	0.5336 (4)	0.0915 (3)	0.0430 (11)
H10	0.3027	0.4706	0.1209	0.052*
C11	0.7259 (6)	0.5555 (4)	0.2073 (3)	0.0433 (11)
H11	0.7092	0.6338	0.1968	0.052*
C12	0.8704 (6)	0.4822 (5)	0.1952 (3)	0.0463 (12)
H12	0.9506	0.5099	0.1760	0.056*
C13	0.8972 (6)	0.3692 (5)	0.2112 (3)	0.0459 (12)
H13	0.9962	0.3177	0.2042	0.055*
C14	0.7764 (6)	0.3316 (4)	0.2379 (3)	0.0410 (11)
H14	0.7922	0.2537	0.2498	0.049*
C15	0.6340 (6)	0.4075 (4)	0.2469 (3)	0.0371 (10)
C16	0.4958 (6)	0.3749 (4)	0.2704 (3)	0.0359 (10)
C17	0.4963 (7)	0.2647 (4)	0.2856 (3)	0.0447 (12)
H17	0.5869	0.2040	0.2786	0.054*
C18	0.3620 (7)	0.2441 (4)	0.3113 (3)	0.0464 (12)
H18	0.3604	0.1693	0.3234	0.056*
C19	0.2330 (6)	0.3325 (4)	0.3189 (3)	0.0442 (12)
H19	0.1402	0.3198	0.3361	0.053*
C20	0.2374 (6)	0.4408 (4)	0.3015 (3)	0.0386 (10)
H20	0.1469	0.5020	0.3075	0.046*
C21	0.5229 (6)	0.6167 (4)	0.4138 (3)	0.0440 (11)
H21	0.6173	0.5708	0.3936	0.053*
C22	0.5166 (7)	0.6483 (5)	0.4923 (3)	0.0534 (14)
H22	0.6053	0.6249	0.5246	0.064*
C23	0.3801 (7)	0.7136 (5)	0.5214 (3)	0.0505 (13)
H23	0.3741	0.7355	0.5746	0.061*
C24	0.2514 (6)	0.7481 (4)	0.4746 (3)	0.0436 (12)
C25	0.1014 (7)	0.8152 (4)	0.5000 (3)	0.0453 (12)
C26	−0.0220 (7)	0.8445 (5)	0.4516 (4)	0.0527 (14)
H26	−0.1182	0.8893	0.4705	0.063*
C27	−0.0085 (6)	0.8087 (4)	0.3729 (3)	0.0450 (12)
C28	−0.1299 (6)	0.8342 (5)	0.3191 (4)	0.0505 (13)
H28	−0.2295	0.8775	0.3348	0.061*
C29	−0.1060 (6)	0.7975 (5)	0.2446 (3)	0.0495 (13)
H29	−0.1884	0.8139	0.2082	0.059*
C30	0.0415 (6)	0.7351 (4)	0.2220 (3)	0.0437 (11)
H30	0.0572	0.7103	0.1696	0.052*
C31	0.1371 (6)	0.7452 (4)	0.3460 (3)	0.0400 (11)
C32	0.2664 (6)	0.7137 (4)	0.3967 (3)	0.0405 (11)
C33	0.0016 (7)	0.8891 (4)	0.6287 (3)	0.0510 (13)
P1	1.0000	0.5000	0.5000	0.0572 (6)
F11	0.9341 (5)	0.5008 (5)	0.4141 (3)	0.0975 (15)
F12	0.8596 (5)	0.4634 (3)	0.5351 (3)	0.0808 (13)
F13	0.9038 (5)	0.6276 (3)	0.5092 (3)	0.0901 (15)
P2	0.5000	1.0000	0.5000	0.0427 (4)
F21	0.4009 (6)	0.9596 (4)	0.5648 (3)	0.0951 (15)
F22	0.6131 (6)	0.8810 (4)	0.5037 (5)	0.145 (3)
F23	0.4083 (11)	0.9609 (7)	0.4380 (4)	0.177 (4)
P3	0.17933 (17)	0.24155 (12)	0.02025 (9)	0.0502 (4)
F31	0.1520 (7)	0.1887 (4)	0.1024 (3)	0.113 (2)
F32	0.0179 (5)	0.2320 (4)	−0.0039 (5)	0.129 (2)
F33	0.2061 (9)	0.2892 (4)	−0.0615 (3)	0.129 (2)
F34	0.3376 (6)	0.2461 (4)	0.0479 (4)	0.1127 (19)
F35	0.1002 (5)	0.3654 (3)	0.0503 (3)	0.0762 (11)
F36	0.2583 (5)	0.1159 (3)	−0.0085 (2)	0.0712 (10)
C40	0.8638 (9)	0.0429 (5)	0.1327 (4)	0.0609 (16)
C41	1.0145 (9)	−0.0209 (6)	0.1065 (5)	0.0735 (19)
H41A	1.0621	0.0296	0.0780	0.110*
H41B	1.0056	−0.0805	0.0718	0.110*
H41C	1.0779	−0.0550	0.1519	0.110*
N8	0.7473 (8)	0.0933 (5)	0.1538 (4)	0.0753 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru	0.0366 (2)	0.0291 (2)	0.0311 (2)	−0.01360 (15)	0.00462 (14)	−0.00054 (14)
S	0.0651 (9)	0.0567 (9)	0.0595 (9)	−0.0231 (7)	0.0200 (7)	−0.0170 (7)
N1	0.038 (2)	0.0318 (19)	0.042 (2)	−0.0128 (16)	0.0057 (17)	−0.0009 (16)
N2	0.039 (2)	0.045 (2)	0.032 (2)	−0.0127 (18)	0.0064 (16)	−0.0004 (17)
N3	0.038 (2)	0.036 (2)	0.036 (2)	−0.0148 (17)	0.0040 (16)	−0.0035 (16)
N4	0.044 (2)	0.0305 (19)	0.0313 (19)	−0.0155 (17)	0.0008 (16)	−0.0018 (15)
N5	0.046 (2)	0.0314 (19)	0.039 (2)	−0.0206 (17)	0.0010 (18)	0.0002 (16)
N6	0.041 (2)	0.0303 (19)	0.039 (2)	−0.0144 (16)	0.0103 (17)	0.0019 (16)
N7	0.076 (3)	0.056 (3)	0.053 (3)	−0.025 (3)	0.022 (3)	−0.016 (2)
C1	0.044 (3)	0.033 (2)	0.053 (3)	−0.012 (2)	0.009 (2)	−0.002 (2)
C2	0.044 (3)	0.032 (3)	0.081 (4)	−0.013 (2)	0.013 (3)	−0.004 (3)
C3	0.048 (3)	0.039 (3)	0.083 (4)	−0.015 (2)	0.011 (3)	0.018 (3)
C4	0.047 (3)	0.048 (3)	0.061 (3)	−0.020 (2)	0.007 (3)	0.016 (3)
C5	0.035 (2)	0.040 (3)	0.047 (3)	−0.011 (2)	0.008 (2)	0.007 (2)
C6	0.034 (2)	0.049 (3)	0.041 (3)	−0.015 (2)	0.002 (2)	0.005 (2)
C7	0.050 (3)	0.073 (4)	0.041 (3)	−0.026 (3)	0.002 (2)	0.017 (3)
C8	0.055 (3)	0.092 (5)	0.035 (3)	−0.034 (3)	−0.004 (2)	0.003 (3)
C9	0.052 (3)	0.071 (4)	0.041 (3)	−0.028 (3)	0.002 (2)	−0.009 (3)
C10	0.046 (3)	0.046 (3)	0.041 (3)	−0.020 (2)	0.002 (2)	−0.005 (2)
C11	0.045 (3)	0.039 (3)	0.049 (3)	−0.016 (2)	0.004 (2)	−0.006 (2)
C12	0.038 (3)	0.055 (3)	0.050 (3)	−0.018 (2)	0.004 (2)	−0.010 (2)
C13	0.042 (3)	0.048 (3)	0.044 (3)	−0.007 (2)	0.000 (2)	−0.013 (2)
C14	0.046 (3)	0.037 (3)	0.039 (3)	−0.010 (2)	−0.001 (2)	−0.005 (2)
C15	0.045 (3)	0.038 (2)	0.030 (2)	−0.014 (2)	0.0004 (19)	−0.0069 (18)
C16	0.046 (3)	0.034 (2)	0.031 (2)	−0.017 (2)	0.0028 (19)	−0.0040 (18)
C17	0.057 (3)	0.032 (2)	0.046 (3)	−0.013 (2)	0.002 (2)	−0.004 (2)
C18	0.064 (3)	0.034 (3)	0.049 (3)	−0.026 (2)	0.003 (2)	0.001 (2)
C19	0.053 (3)	0.045 (3)	0.043 (3)	−0.027 (2)	0.004 (2)	0.002 (2)
C20	0.042 (3)	0.041 (3)	0.037 (2)	−0.018 (2)	0.003 (2)	−0.002 (2)
C21	0.049 (3)	0.041 (3)	0.047 (3)	−0.019 (2)	−0.002 (2)	−0.003 (2)
C22	0.065 (4)	0.051 (3)	0.047 (3)	−0.021 (3)	−0.009 (3)	0.002 (2)
C23	0.065 (4)	0.047 (3)	0.044 (3)	−0.023 (3)	0.005 (3)	−0.003 (2)
C24	0.057 (3)	0.037 (3)	0.043 (3)	−0.024 (2)	0.010 (2)	−0.003 (2)
C25	0.058 (3)	0.041 (3)	0.042 (3)	−0.023 (2)	0.014 (2)	−0.004 (2)
C26	0.056 (3)	0.042 (3)	0.061 (3)	−0.017 (3)	0.019 (3)	−0.003 (2)
C27	0.054 (3)	0.035 (3)	0.050 (3)	−0.020 (2)	0.012 (2)	−0.002 (2)
C28	0.041 (3)	0.047 (3)	0.064 (4)	−0.014 (2)	0.005 (2)	0.003 (3)
C29	0.043 (3)	0.047 (3)	0.059 (3)	−0.014 (2)	0.003 (2)	0.005 (2)
C30	0.044 (3)	0.042 (3)	0.048 (3)	−0.018 (2)	0.001 (2)	0.004 (2)
C31	0.047 (3)	0.030 (2)	0.048 (3)	−0.018 (2)	0.009 (2)	0.003 (2)
C32	0.056 (3)	0.029 (2)	0.042 (3)	−0.021 (2)	0.014 (2)	−0.0019 (19)
C33	0.063 (3)	0.039 (3)	0.056 (3)	−0.022 (3)	0.014 (3)	−0.004 (2)
P1	0.0660 (14)	0.0391 (10)	0.0700 (14)	−0.0214 (10)	0.0305 (11)	−0.0011 (9)
F11	0.081 (3)	0.127 (4)	0.083 (3)	−0.028 (3)	0.022 (2)	−0.014 (3)
F12	0.088 (3)	0.057 (2)	0.107 (3)	−0.037 (2)	0.051 (2)	−0.008 (2)
F13	0.103 (3)	0.045 (2)	0.123 (4)	−0.022 (2)	0.060 (3)	−0.005 (2)
P2	0.0473 (10)	0.0392 (9)	0.0432 (10)	−0.0152 (8)	0.0076 (8)	−0.0015 (8)
F21	0.112 (4)	0.068 (3)	0.104 (3)	−0.028 (2)	0.058 (3)	0.008 (2)
F22	0.096 (4)	0.054 (3)	0.268 (8)	−0.002 (2)	0.091 (5)	0.028 (4)
F23	0.297 (10)	0.212 (8)	0.097 (4)	−0.193 (8)	−0.071 (5)	0.027 (4)
P3	0.0517 (8)	0.0431 (7)	0.0573 (9)	−0.0161 (6)	0.0128 (7)	−0.0050 (6)
F31	0.170 (5)	0.068 (3)	0.100 (3)	−0.032 (3)	0.080 (4)	−0.011 (2)
F32	0.066 (3)	0.074 (3)	0.248 (8)	−0.018 (2)	−0.009 (4)	−0.045 (4)
F33	0.223 (7)	0.065 (3)	0.073 (3)	−0.002 (3)	0.052 (4)	0.006 (2)
F34	0.073 (3)	0.094 (3)	0.176 (6)	−0.031 (3)	−0.002 (3)	−0.034 (4)
F35	0.079 (3)	0.050 (2)	0.102 (3)	−0.0215 (18)	0.034 (2)	−0.0191 (19)
F36	0.078 (2)	0.0481 (19)	0.083 (3)	−0.0129 (17)	0.027 (2)	−0.0085 (18)
C40	0.076 (5)	0.045 (3)	0.071 (4)	−0.032 (3)	0.005 (3)	−0.004 (3)
C41	0.086 (5)	0.063 (4)	0.079 (5)	−0.033 (4)	0.021 (4)	−0.006 (3)
N8	0.077 (4)	0.059 (3)	0.094 (5)	−0.027 (3)	0.002 (3)	−0.015 (3)

Geometric parameters (Å, º) top

Ru—N1	2.056 (4)	C17—H17	0.95
Ru—N3	2.059 (4)	C18—C19	1.360 (8)
Ru—N2	2.059 (4)	C18—H18	0.95
Ru—N4	2.064 (4)	C19—C20	1.381 (7)
Ru—N6	2.065 (4)	C19—H19	0.95
Ru—N5	2.072 (4)	C20—H20	0.95
S—C33	1.554 (6)	C21—C22	1.403 (8)
N1—C1	1.350 (6)	C21—H21	0.95
N1—C5	1.363 (6)	C22—C23	1.369 (8)
N2—C6	1.345 (6)	C22—H22	0.95
N2—C10	1.357 (6)	C23—C24	1.379 (8)
N3—C11	1.339 (6)	C23—H23	0.95
N3—C15	1.365 (6)	C24—C32	1.401 (7)
N4—C20	1.344 (6)	C24—C25	1.448 (8)
N4—C16	1.358 (6)	C25—C26	1.356 (8)
N5—C21	1.326 (7)	C26—C27	1.419 (8)
N5—C32	1.370 (6)	C26—H26	0.95
N6—C30	1.337 (7)	C27—C28	1.402 (8)
N6—C31	1.365 (6)	C27—C31	1.412 (7)
N7—C33	1.197 (7)	C28—C29	1.356 (8)
N7—C25	1.391 (7)	C28—H28	0.95
C1—C2	1.382 (7)	C29—C30	1.398 (8)
C1—H1	0.95	C29—H29	0.95
C2—C3	1.371 (9)	C30—H30	0.95
C2—H2	0.95	C31—C32	1.420 (8)
C3—C4	1.370 (9)	P1—F13ⁱ	1.578 (4)
C3—H3	0.95	P1—F13	1.578 (4)
C4—C5	1.383 (7)	P1—F11	1.588 (5)
C4—H4	0.95	P1—F11ⁱ	1.588 (5)
C5—C6	1.472 (7)	P1—F12	1.591 (3)
C6—C7	1.396 (7)	P1—F12ⁱ	1.591 (3)
C7—C8	1.366 (9)	P2—F23ⁱⁱ	1.526 (5)
C7—H7	0.95	P2—F23	1.526 (5)
C8—C9	1.376 (9)	P2—F22ⁱⁱ	1.531 (4)
C8—H8	0.95	P2—F22	1.531 (4)
C9—C10	1.374 (7)	P2—F21	1.589 (4)
C9—H9	0.95	P2—F21ⁱⁱ	1.589 (4)
C10—H10	0.95	P3—F34	1.540 (5)
C11—C12	1.381 (7)	P3—F33	1.549 (5)
C11—H11	0.95	P3—F32	1.571 (5)
C12—C13	1.370 (8)	P3—F31	1.585 (5)
C12—H12	0.95	P3—F35	1.589 (4)
C13—C14	1.388 (8)	P3—F36	1.600 (4)
C13—H13	0.95	C40—N8	1.125 (9)
C14—C15	1.372 (7)	C40—C41	1.445 (10)
C14—H14	0.95	C41—H41a	0.98
C15—C16	1.484 (7)	C41—H41b	0.98
C16—C17	1.383 (7)	C41—H41c	0.98
C17—C18	1.390 (8)

N1—Ru—N3	96.28 (15)	N4—C20—H20	118.9
N1—Ru—N2	79.03 (16)	C19—C20—H20	118.9
N3—Ru—N2	88.79 (16)	N5—C21—C22	122.5 (5)
N1—Ru—N4	174.09 (15)	N5—C21—H21	118.7
N3—Ru—N4	78.91 (15)	C22—C21—H21	118.7
N2—Ru—N4	97.32 (15)	C23—C22—C21	118.6 (5)
N1—Ru—N6	88.69 (15)	C23—C22—H22	120.7
N3—Ru—N6	174.60 (15)	C21—C22—H22	120.7
N2—Ru—N6	94.23 (16)	C22—C23—C24	120.8 (5)
N4—Ru—N6	96.25 (15)	C22—C23—H23	119.6
N1—Ru—N5	94.83 (15)	C24—C23—H23	119.6
N3—Ru—N5	97.41 (16)	C23—C24—C32	117.4 (5)
N2—Ru—N5	171.75 (16)	C23—C24—C25	125.1 (5)
N4—Ru—N5	89.23 (14)	C32—C24—C25	117.5 (5)
N6—Ru—N5	80.03 (16)	C26—C25—N7	121.2 (5)
C1—N1—C5	118.4 (4)	C26—C25—C24	122.4 (5)
C1—N1—RU	126.2 (3)	N7—C25—C24	116.4 (5)
C5—N1—RU	115.4 (3)	C25—C26—C27	120.5 (5)
C6—N2—C10	118.9 (4)	C25—C26—H26	119.7
C6—N2—RU	115.5 (3)	C27—C26—H26	119.7
C10—N2—RU	125.6 (3)	C28—C27—C31	117.4 (5)
C11—N3—C15	117.9 (4)	C28—C27—C26	124.4 (5)
C11—N3—RU	126.1 (3)	C31—C27—C26	118.3 (5)
C15—N3—RU	115.9 (3)	C29—C28—C27	120.3 (5)
C20—N4—C16	118.5 (4)	C29—C28—H28	119.9
C20—N4—RU	125.6 (3)	C27—C28—H28	119.9
C16—N4—RU	115.9 (3)	C28—C29—C30	119.2 (5)
C21—N5—C32	118.1 (4)	C28—C29—H29	120.4
C21—N5—RU	129.4 (4)	C30—C29—H29	120.4
C32—N5—RU	112.4 (3)	N6—C30—C29	122.9 (5)
C30—N6—C31	118.0 (4)	N6—C30—H30	118.6
C30—N6—RU	128.5 (3)	C29—C30—H30	118.6
C31—N6—RU	113.5 (3)	N6—C31—C27	122.3 (5)
C33—N7—C25	144.9 (6)	N6—C31—C32	116.4 (4)
N1—C1—C2	121.7 (5)	C27—C31—C32	121.3 (5)
N1—C1—H1	119.1	N5—C32—C24	122.5 (5)
C2—C1—H1	119.1	N5—C32—C31	117.5 (4)
C3—C2—C1	119.6 (6)	C24—C32—C31	119.9 (5)
C3—C2—H2	120.2	N7—C33—S	174.4 (6)
C1—C2—H2	120.2	F13ⁱ—P1—F13	180.0 (4)
C4—C3—C2	119.3 (5)	F13ⁱ—P1—F11	89.6 (3)
C4—C3—H3	120.4	F13—P1—F11	90.4 (3)
C2—C3—H3	120.4	F13ⁱ—P1—F11ⁱ	90.4 (3)
C3—C4—C5	119.7 (5)	F13—P1—F11ⁱ	89.6 (3)
C3—C4—H4	120.2	F11—P1—F11ⁱ	180.000 (2)
C5—C4—H4	120.2	F13ⁱ—P1—F12	90.9 (2)
N1—C5—C4	121.3 (5)	F13—P1—F12	89.1 (2)
N1—C5—C6	114.6 (4)	F11—P1—F12	90.3 (3)
C4—C5—C6	124.1 (5)	F11ⁱ—P1—F12	89.7 (3)
N2—C6—C7	120.8 (5)	F13ⁱ—P1—F12ⁱ	89.1 (2)
N2—C6—C5	115.5 (4)	F13—P1—F12ⁱ	90.9 (2)
C7—C6—C5	123.7 (5)	F11—P1—F12ⁱ	89.7 (3)
C8—C7—C6	119.7 (5)	F11ⁱ—P1—F12ⁱ	90.3 (3)
C8—C7—H7	120.2	F12—P1—F12ⁱ	180.000 (1)
C6—C7—H7	120.2	F23ⁱⁱ—P2—F23	180.0 (6)
C7—C8—C9	119.6 (5)	F23ⁱⁱ—P2—F22ⁱⁱ	89.3 (5)
C7—C8—H8	120.2	F23—P2—F22ⁱⁱ	90.7 (5)
C9—C8—H8	120.2	F23ⁱⁱ—P2—F22	90.7 (5)
C10—C9—C8	119.0 (5)	F23—P2—F22	89.3 (5)
C10—C9—H9	120.5	F22ⁱⁱ—P2—F22	180.0 (6)
C8—C9—H9	120.5	F23ⁱⁱ—P2—F21	91.9 (4)
N2—C10—C9	122.1 (5)	F23—P2—F21	88.1 (4)
N2—C10—H10	118.9	F22ⁱⁱ—P2—F21	91.9 (3)
C9—C10—H10	118.9	F22—P2—F21	88.1 (3)
N3—C11—C12	122.6 (5)	F23ⁱⁱ—P2—F21ⁱⁱ	88.1 (4)
N3—C11—H11	118.7	F23—P2—F21ⁱⁱ	91.9 (4)
C12—C11—H11	118.7	F22ⁱⁱ—P2—F21ⁱⁱ	88.1 (3)
C13—C12—C11	119.5 (5)	F22—P2—F21ⁱⁱ	91.9 (3)
C13—C12—H12	120.2	F21—P2—F21ⁱⁱ	180.000 (2)
C11—C12—H12	120.2	F34—P3—F33	90.6 (4)
C12—C13—C14	118.6 (5)	F34—P3—F32	176.7 (4)
C12—C13—H13	120.7	F33—P3—F32	92.6 (4)
C14—C13—H13	120.7	F34—P3—F31	90.3 (4)
C15—C14—C13	119.6 (5)	F33—P3—F31	178.0 (3)
C15—C14—H14	120.2	F32—P3—F31	86.6 (4)
C13—C14—H14	120.2	F34—P3—F35	91.2 (3)
N3—C15—C14	121.7 (5)	F33—P3—F35	90.9 (2)
N3—C15—C16	114.5 (4)	F32—P3—F35	89.8 (2)
C14—C15—C16	123.7 (4)	F31—P3—F35	90.9 (2)
N4—C16—C17	121.5 (5)	F34—P3—F36	88.8 (3)
N4—C16—C15	114.7 (4)	F33—P3—F36	90.2 (2)
C17—C16—C15	123.8 (5)	F32—P3—F36	90.1 (2)
C16—C17—C18	119.0 (5)	F31—P3—F36	88.0 (2)
C16—C17—H17	120.5	F35—P3—F36	178.9 (2)
C18—C17—H17	120.5	N8—C40—C41	179.0 (8)
C19—C18—C17	119.2 (5)	C40—C41—H41A	109.5
C19—C18—H18	120.4	C40—C41—H41B	109.5
C17—C18—H18	120.4	H41A—C41—H41B	109.5
C18—C19—C20	119.7 (5)	C40—C41—H41C	109.5
C18—C19—H19	120.2	H41A—C41—H41C	109.5
C20—C19—H19	120.2	H41B—C41—H41C	109.5
N4—C20—C19	122.1 (5)

N3—RU—N1—C1	−92.9 (4)	C6—N2—C10—C9	−0.5 (8)
N2—RU—N1—C1	179.6 (4)	RU—N2—C10—C9	178.9 (4)
N6—RU—N1—C1	85.0 (4)	C8—C9—C10—N2	1.6 (9)
N5—RU—N1—C1	5.1 (4)	C15—N3—C11—C12	−0.8 (7)
N3—RU—N1—C5	87.3 (3)	RU—N3—C11—C12	−176.9 (4)
N2—RU—N1—C5	−0.2 (3)	N3—C11—C12—C13	−1.0 (8)
N6—RU—N1—C5	−94.8 (3)	C11—C12—C13—C14	1.2 (8)
N5—RU—N1—C5	−174.7 (3)	C12—C13—C14—C15	0.5 (7)
N1—RU—N2—C6	0.4 (3)	C11—N3—C15—C14	2.6 (7)
N3—RU—N2—C6	−96.2 (4)	RU—N3—C15—C14	179.0 (3)
N4—RU—N2—C6	−174.9 (3)	C11—N3—C15—C16	−176.1 (4)
N6—RU—N2—C6	88.3 (4)	RU—N3—C15—C16	0.3 (5)
N1—RU—N2—C10	−179.0 (4)	C13—C14—C15—N3	−2.5 (7)
N3—RU—N2—C10	84.4 (4)	C13—C14—C15—C16	176.1 (4)
N4—RU—N2—C10	5.7 (4)	C20—N4—C16—C17	3.4 (7)
N6—RU—N2—C10	−91.2 (4)	RU—N4—C16—C17	−178.3 (4)
N1—RU—N3—C11	0.1 (4)	C20—N4—C16—C15	−176.4 (4)
N2—RU—N3—C11	78.9 (4)	RU—N4—C16—C15	1.9 (5)
N4—RU—N3—C11	176.6 (4)	N3—C15—C16—N4	−1.4 (6)
N5—RU—N3—C11	−95.6 (4)	C14—C15—C16—N4	179.9 (4)
N1—RU—N3—C15	−176.0 (3)	N3—C15—C16—C17	178.8 (4)
N2—RU—N3—C15	−97.2 (3)	C14—C15—C16—C17	0.1 (7)
N4—RU—N3—C15	0.5 (3)	N4—C16—C17—C18	−3.2 (7)
N5—RU—N3—C15	88.3 (3)	C15—C16—C17—C18	176.5 (5)
N3—RU—N4—C20	176.8 (4)	C16—C17—C18—C19	1.6 (8)
N2—RU—N4—C20	−95.9 (4)	C17—C18—C19—C20	−0.3 (8)
N6—RU—N4—C20	−0.8 (4)	C16—N4—C20—C19	−2.1 (7)
N5—RU—N4—C20	79.1 (4)	RU—N4—C20—C19	179.9 (4)
N3—RU—N4—C16	−1.3 (3)	C18—C19—C20—N4	0.6 (8)
N2—RU—N4—C16	86.0 (3)	C32—N5—C21—C22	−0.8 (7)
N6—RU—N4—C16	−178.9 (3)	RU—N5—C21—C22	176.3 (4)
N5—RU—N4—C16	−99.0 (3)	N5—C21—C22—C23	0.6 (8)
N1—RU—N5—C21	−93.1 (4)	C21—C22—C23—C24	−0.2 (8)
N3—RU—N5—C21	3.9 (4)	C22—C23—C24—C32	−0.1 (8)
N4—RU—N5—C21	82.6 (4)	C22—C23—C24—C25	178.8 (5)
N6—RU—N5—C21	179.1 (4)	C33—N7—C25—C26	5.7 (12)
N1—RU—N5—C32	84.1 (3)	C33—N7—C25—C24	−172.5 (8)
N3—RU—N5—C32	−178.9 (3)	C23—C24—C25—C26	−178.5 (5)
N4—RU—N5—C32	−100.2 (3)	C32—C24—C25—C26	0.3 (7)
N6—RU—N5—C32	−3.7 (3)	C23—C24—C25—N7	−0.4 (8)
N1—RU—N6—C30	87.0 (4)	C32—C24—C25—N7	178.5 (4)
N2—RU—N6—C30	8.1 (4)	N7—C25—C26—C27	−177.5 (5)
N4—RU—N6—C30	−89.8 (4)	C24—C25—C26—C27	0.6 (8)
N5—RU—N6—C30	−177.9 (4)	C25—C26—C27—C28	179.5 (5)
N1—RU—N6—C31	−91.9 (3)	C25—C26—C27—C31	−2.0 (8)
N2—RU—N6—C31	−170.8 (3)	C31—C27—C28—C29	0.7 (8)
N4—RU—N6—C31	91.4 (3)	C26—C27—C28—C29	179.2 (5)
N5—RU—N6—C31	3.2 (3)	C27—C28—C29—C30	−0.8 (8)
C5—N1—C1—C2	−0.1 (7)	C31—N6—C30—C29	−0.2 (7)
RU—N1—C1—C2	−179.9 (4)	RU—N6—C30—C29	−179.0 (4)
N1—C1—C2—C3	0.8 (8)	C28—C29—C30—N6	0.5 (8)
C1—C2—C3—C4	−0.7 (8)	C30—N6—C31—C27	0.1 (6)
C2—C3—C4—C5	0.0 (8)	RU—N6—C31—C27	179.1 (3)
C1—N1—C5—C4	−0.7 (7)	C30—N6—C31—C32	178.8 (4)
RU—N1—C5—C4	179.2 (4)	RU—N6—C31—C32	−2.2 (5)
C1—N1—C5—C6	−179.8 (4)	C28—C27—C31—N6	−0.3 (7)
RU—N1—C5—C6	0.0 (5)	C26—C27—C31—N6	−178.9 (4)
C3—C4—C5—N1	0.7 (8)	C28—C27—C31—C32	−178.9 (4)
C3—C4—C5—C6	179.8 (5)	C26—C27—C31—C32	2.4 (7)
C10—N2—C6—C7	−1.6 (7)	C21—N5—C32—C24	0.5 (7)
RU—N2—C6—C7	178.9 (4)	RU—N5—C32—C24	−177.1 (3)
C10—N2—C6—C5	178.9 (4)	C21—N5—C32—C31	−178.7 (4)
RU—N2—C6—C5	−0.6 (5)	RU—N5—C32—C31	3.8 (5)
N1—C5—C6—N2	0.4 (6)	C23—C24—C32—N5	−0.1 (7)
C4—C5—C6—N2	−178.7 (5)	C25—C24—C32—N5	−179.0 (4)
N1—C5—C6—C7	−179.1 (5)	C23—C24—C32—C31	179.1 (4)
C4—C5—C6—C7	1.8 (8)	C25—C24—C32—C31	0.1 (7)
N2—C6—C7—C8	2.7 (8)	N6—C31—C32—N5	−1.1 (6)
C5—C6—C7—C8	−177.9 (5)	C27—C31—C32—N5	177.6 (4)
C6—C7—C8—C9	−1.6 (9)	N6—C31—C32—C24	179.8 (4)
C7—C8—C9—C10	−0.5 (9)	C27—C31—C32—C24	−1.5 (7)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	[Ru(C₁₀H₈N₂)₂(C₁₃H₇N₃S)](PF₆)₂·C₂H₃N
M_r	981.71
Crystal system, space group	Triclinic, P1
Temperature (K)	150
a, b, c (Å)	9.129 (3), 12.397 (4), 17.084 (5)
α, β, γ (°)	88.618 (4), 89.704 (5), 72.870 (4)
V (Å³)	1847.1 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.67
Crystal size (mm)	0.24 × 0.13 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.83, 0.95
No. of measured, independent and observed [I > 2σ(I)] reflections	178384, 6687, 6155
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.152, 1.18
No. of reflections	6687
No. of parameters	536
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.45, −0.86

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), UdMX (Maris, 2004).

Selected bond lengths (Å) top

Ru—N1	2.056 (4)	Ru—N4	2.064 (4)
Ru—N3	2.059 (4)	Ru—N6	2.065 (4)
Ru—N2	2.059 (4)	Ru—N5	2.072 (4)

Acknowledgements

The authors are greatful to the Natural Sciences and Engineering Research Council of Canada and the Université de Montréal for financial support.

References

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