Bis(2-phenyl-4,6-di-2-pyridyl-1,3,5-triazine-κ3N4,N5,N6)ruthenium(II) bis(hexa­fluoridophosphate)

Polson, M.I.J.; Hanan, G.S.

doi:10.1107/S1600536807066883

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Pages m254-m255

https://doi.org/10.1107/S1600536807066883

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Bis(2-phenyl-4,6-di-2-pyridyl-1,3,5-triazine-κ³N⁴,N⁵,N⁶)ruthenium(II) bis(hexafluoridophosphate)

Matthew I. J. Polson ^a ^* and Garry S. Hanan ^b

^aChemistry Department, University of Canterbury, PO Box 4800, Christchurch, New Zealand, and ^bDépartement de Chimie, Université de Montréal, Montréal, Québec, H3T 1J4, Canada
^*Correspondence e-mail: matthew.polson@canterbury.ac.nz

(Received 9 November 2007; accepted 14 December 2007; online 21 December 2007)

The asymmetric unit of the title compound, [Ru(C₁₉H₁₃N₅)₂](PF₆)₂, consists of an Ru^II complex cation and two hexafluoridophosphate anions. The Ru^II atom is coordinated by three N atoms from the two outer pyridine and the central triazine rings of each of two tridentate ligands in a distorted octahedral environment. The ligands are approximately orthogonal to one another, with a dihedral angle of 88.34 (2)° between planes through the three six-membered rings of the two ligands. The pendant phenyl substituents are almost coplanar with the triazine rings to which they are bound, with dihedral angles of 5.41 (9) and 14.90 (10)°. This is reflected in the previously reported photophysical results with an increased lifetime of the triplet metal to ligand charge transfer (³MLCT) excited state [Fang, Taylor, Hanan, Loiseau, Passalacqua, Campagna, Nierengarten & Van Dorsselaer (2002). J. Am. Chem. Soc. 124, 7912–7913].

Related literature

For related synthetic details, see: Polson et al. (2002 , 2004 ). For related structures, see: Polson et al. (2002). For general background on the photophysics of ruthenium polypyridyl complexes, see: Kalyanasundaram (1991 ); Barigelletti et al. (1995 ). For background on C—H⋯N interactions in α-diimines, see: Fitchett et al. (2005 ). For related literature, see: Beley et al. (1991 ); Fang et al. (2002 ).

Experimental

Crystal data

[Ru(C₁₉H₁₃N₅)₂](PF₆)₂
M_r = 1013.70
Monoclinic, P 2₁ /n
a = 9.0995 (3) Å
b = 32.5979 (11) Å
c = 13.1451 (5) Å
β = 91.774 (2)°
V = 3897.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 93 (2) K
0.30 × 0.13 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.822, T_max = 0.950
75901 measured reflections
8114 independent reflections
6511 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.066
S = 0.99
8114 reflections
568 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Ru1—N10	2.0982 (16)
Ru1—N20	1.9773 (15)
Ru1—N30	2.0990 (16)
Ru1—N50	2.0967 (16)
Ru1—N60	1.9723 (15)
Ru1—N70	2.0939 (17)

N10—Ru1—N30	154.76 (6)
N60—Ru1—N20	179.28 (7)
N70—Ru1—N50	155.22 (6)
N20—Ru1—N70	103.31 (6)
N20—Ru1—N50	101.42 (6)
N20—Ru1—N10	77.77 (6)
N20—Ru1—N30	77.00 (6)
N50—Ru1—N10	91.99 (6)
N50—Ru1—N30	92.35 (6)
N60—Ru1—N50	77.85 (6)
N60—Ru1—N70	77.42 (6)
N60—Ru1—N10	102.25 (6)
N60—Ru1—N30	102.98 (6)
N70—Ru1—N10	91.67 (6)
N70—Ru1—N30	94.71 (6)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C41—H41⋯N21	0.95	2.47	2.793 (3)	100
C45—H45⋯N22	0.95	2.52	2.826 (3)	99
C81—H81⋯N61	0.95	2.47	2.797 (2)	100
C85—H85⋯N62	0.95	2.50	2.823 (3)	100

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807066883/sj2423sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807066883/sj2423Isup2.hkl

checkCIF report

Comment top

The structure of the title compound reveals the ruthenium(II) atom to be in a distorted octahedral environment, Table 1. The Ru—N bond lengths to the central triazine ring are significantly shortened when compared to those of the outer pyridine rings. The angles between the coordinating pyridine N atoms also deviate significantly from 180 ° indicating considerable distortion.

Ruthenium complexes of this type have long been known to exhibit surprisingly short lived excited states. This is due to rapid deactivation of the excited state through a low lying metal centred state (Kalyanasundaram, 1991; Barigelletti et al., 1995). By lowering the energy of the triplet metal to ligand charge transfer ³MLCT state, this exchange can be slowed and the lifetime of the excited state is extended (Fang et al., 2002). In the title compound (1) replacement of a the central pyridine ring with a triazine ring in complex with a 4-phenyl substituent allows the pendant phenyl ring to adopt an arrangement in which it is approximately co-planar with the rest of the ligand. This results from the removal of stericically conflicting C—H···H—C interactions and the addition of attractive intramolecular C—H···N interactions. Although the C—H···N angles are acute (approximately 100 °) they are typical of interactions in molecules of this kind (Fitchett et al., 2005) with N···H lengths of 2.47 to 2.52 Å, Table 2. The greater overall planarity of the ligands extends the HOMO orbital (predominately π^* in nature) over more of the ligand surface, decreasing the energy of the ³MLCT state (Beley et al., 1991; Polson et al., 2002).

Related literature top

For related synthetic details see: Polson et al. (2002, 2004). For related structures, see: Polson et al. (2002). For general background on the photophysics of ruthenium polypyridyl complexes, see: Kalyanasundaram (1991); Barigelletti et al. (1995). For background on C—H···N interactions in α-diimines, see: Fitchett et al. (2005).

For related literature, see: Beley et al. (1991); Fang et al. (2002).

Experimental top

The complex was prepared as described by Polson et al. (2004). Crystals suitable for X-ray crystallography were prepared by the diffusion of diisopropyl ether into an acetonitrile solution of the complex over a week.

Structure description top

For related literature, see: Beley et al. (1991); Fang et al. (2002).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

Fig. 1. The molecular structure of (1), showing displacement ellipsoids at the 50% probability level. All H atoms have been omitted for clarity.

Bis(2-phenyl-4,6-di-2-pyridyl-1,3,5-triazine- κ³N⁴,N⁵,N⁶)ruthenium(II) bis(hexafluoridophosphate) top

Crystal data top

[Ru(C₁₉H₁₃N₅)₂](PF₆)₂	F(000) = 2024
M_r = 1013.70	D_x = 1.728 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7650 reflections
a = 9.0995 (3) Å	θ = 4.7–53.0°
b = 32.5979 (11) Å	µ = 0.59 mm⁻¹
c = 13.1451 (5) Å	T = 93 K
β = 91.774 (2)°	Needle, red
V = 3897.3 (2) Å³	0.30 × 0.13 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	8114 independent reflections
Radiation source: sealed tube	6511 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
ω scans	θ_max = 26.6°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −11→11
T_min = 0.822, T_max = 0.950	k = −40→40
75901 measured reflections	l = −16→15

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.066	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0562P)² + 0.5007P] where P = (F_o² + 2F_c²)/3
8114 reflections	(Δ/σ)_max < 0.001
568 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

[Ru(C₁₉H₁₃N₅)₂](PF₆)₂	V = 3897.3 (2) Å³
M_r = 1013.70	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.0995 (3) Å	µ = 0.59 mm⁻¹
b = 32.5979 (11) Å	T = 93 K
c = 13.1451 (5) Å	0.30 × 0.13 × 0.08 mm
β = 91.774 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	8114 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	6511 reflections with I > 2σ(I)
T_min = 0.822, T_max = 0.950	R_int = 0.060
75901 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.066	H-atom parameters constrained
S = 0.99	Δρ_max = 0.55 e Å⁻³
8114 reflections	Δρ_min = −0.57 e Å⁻³
568 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.

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

	x	y	z	U_iso*/U_eq
Ru1	0.511004 (17)	0.118305 (4)	0.711838 (12)	0.01108 (5)
N10	0.71581 (17)	0.12419 (5)	0.64422 (12)	0.0136 (4)
C10	0.8068 (2)	0.09472 (6)	0.61281 (16)	0.0179 (5)
H10	0.7805	0.0669	0.6231	0.021*
C11	0.9375 (2)	0.10327 (6)	0.56596 (17)	0.0232 (5)
H11	0.9978	0.0815	0.5433	0.028*
C12	0.9798 (2)	0.14335 (6)	0.55231 (17)	0.0240 (5)
H12	1.0700	0.1496	0.5212	0.029*
C13	0.8884 (2)	0.17461 (6)	0.58476 (16)	0.0192 (5)
H13	0.9150	0.2026	0.5765	0.023*
C14	0.7588 (2)	0.16422 (5)	0.62909 (15)	0.0141 (4)
N20	0.53678 (17)	0.17849 (5)	0.70707 (12)	0.0123 (3)
N21	0.67356 (18)	0.23500 (5)	0.65306 (13)	0.0158 (4)
N22	0.44719 (18)	0.24472 (5)	0.73807 (12)	0.0148 (4)
C20	0.6545 (2)	0.19520 (6)	0.66416 (15)	0.0137 (4)
C21	0.5662 (2)	0.25871 (6)	0.69099 (15)	0.0147 (4)
C22	0.4357 (2)	0.20427 (6)	0.74240 (15)	0.0132 (4)
N30	0.31752 (18)	0.14032 (5)	0.77547 (12)	0.0130 (3)
C30	0.2009 (2)	0.11839 (6)	0.80597 (16)	0.0177 (4)
H30	0.2042	0.0893	0.8016	0.021*
C31	0.0766 (2)	0.13690 (6)	0.84348 (17)	0.0220 (5)
H31	−0.0040	0.1205	0.8633	0.026*
C32	0.0698 (2)	0.17918 (6)	0.85204 (17)	0.0221 (5)
H32	−0.0141	0.1921	0.8790	0.027*
C33	0.1878 (2)	0.20221 (6)	0.82050 (15)	0.0180 (4)
H33	0.1858	0.2313	0.8247	0.022*
C34	0.3083 (2)	0.18235 (6)	0.78291 (15)	0.0133 (4)
C40	0.5820 (2)	0.30342 (6)	0.67733 (16)	0.0172 (4)
C41	0.6825 (2)	0.31883 (6)	0.60975 (17)	0.0223 (5)
H41	0.7451	0.3007	0.5747	0.027*
C42	0.6911 (3)	0.36089 (6)	0.59355 (18)	0.0268 (5)
H42	0.7585	0.3715	0.5464	0.032*
C43	0.6018 (3)	0.38746 (6)	0.64602 (18)	0.0263 (5)
H43	0.6081	0.4162	0.6349	0.032*
C44	0.5033 (2)	0.37218 (6)	0.71460 (18)	0.0237 (5)
H44	0.4433	0.3905	0.7513	0.028*
C45	0.4920 (2)	0.33042 (6)	0.72995 (17)	0.0207 (5)
H45	0.4232	0.3200	0.7763	0.025*
N50	0.40436 (17)	0.10703 (5)	0.57094 (12)	0.0124 (3)
C50	0.3662 (2)	0.13390 (6)	0.49749 (15)	0.0141 (4)
H50	0.3903	0.1620	0.5073	0.017*
C51	0.2932 (2)	0.12242 (6)	0.40811 (16)	0.0162 (4)
H51	0.2681	0.1424	0.3579	0.019*
C52	0.2572 (2)	0.08161 (6)	0.39243 (16)	0.0172 (4)
H52	0.2063	0.0732	0.3318	0.021*
C53	0.2965 (2)	0.05329 (6)	0.46646 (15)	0.0161 (4)
H53	0.2732	0.0251	0.4572	0.019*
C54	0.3700 (2)	0.06633 (5)	0.55407 (15)	0.0120 (4)
N60	0.48400 (17)	0.05829 (5)	0.71489 (12)	0.0129 (3)
N61	0.40078 (18)	−0.00188 (5)	0.63404 (12)	0.0143 (4)
N62	0.51801 (18)	−0.00465 (5)	0.79959 (13)	0.0147 (4)
C60	0.4180 (2)	0.03841 (6)	0.63663 (15)	0.0137 (4)
C61	0.4496 (2)	−0.02227 (6)	0.71801 (15)	0.0148 (4)
C62	0.5347 (2)	0.03559 (6)	0.79454 (15)	0.0143 (4)
N70	0.61068 (17)	0.10207 (5)	0.85180 (12)	0.0136 (4)
C70	0.6809 (2)	0.12700 (6)	0.91947 (15)	0.0158 (4)
H70	0.6798	0.1557	0.9076	0.019*
C71	0.7543 (2)	0.11210 (6)	1.00527 (16)	0.0187 (4)
H71	0.8037	0.1305	1.0508	0.022*
C72	0.7560 (2)	0.07045 (6)	1.02492 (16)	0.0197 (5)
H72	0.8068	0.0599	1.0835	0.024*
C73	0.6820 (2)	0.04436 (6)	0.95750 (16)	0.0173 (4)
H73	0.6803	0.0156	0.9695	0.021*
C74	0.6111 (2)	0.06077 (6)	0.87298 (15)	0.0145 (4)
C80	0.4271 (2)	−0.06706 (6)	0.71991 (15)	0.0155 (4)
C81	0.3459 (2)	−0.08622 (6)	0.64177 (16)	0.0194 (5)
H81	0.3037	−0.0703	0.5878	0.023*
C82	0.3265 (2)	−0.12824 (6)	0.64252 (18)	0.0236 (5)
H82	0.2722	−0.1411	0.5886	0.028*
C83	0.3860 (2)	−0.15176 (6)	0.72169 (18)	0.0237 (5)
H83	0.3720	−0.1806	0.7221	0.028*
C84	0.4651 (2)	−0.13302 (6)	0.79949 (17)	0.0227 (5)
H84	0.5049	−0.1490	0.8541	0.027*
C85	0.4873 (2)	−0.09084 (6)	0.79877 (16)	0.0197 (5)
H85	0.5435	−0.0782	0.8522	0.024*
P10	0.21119 (6)	0.252045 (16)	0.48554 (4)	0.02011 (13)
F10	0.18421 (15)	0.22740 (4)	0.58837 (10)	0.0386 (4)
F11	0.26219 (15)	0.29172 (4)	0.54874 (10)	0.0327 (3)
F12	0.04573 (14)	0.26820 (4)	0.48256 (10)	0.0362 (3)
F13	0.23965 (14)	0.27617 (3)	0.38108 (9)	0.0250 (3)
F14	0.16179 (15)	0.21244 (4)	0.42100 (10)	0.0339 (3)
F15	0.37791 (14)	0.23611 (4)	0.48793 (11)	0.0353 (3)
P20	0.01052 (6)	0.008488 (16)	0.76644 (5)	0.02301 (14)
F20	−0.05493 (16)	−0.01201 (4)	0.86490 (11)	0.0395 (4)
F21	−0.04478 (14)	0.05249 (3)	0.80299 (10)	0.0278 (3)
F22	−0.14343 (15)	0.00207 (4)	0.70590 (11)	0.0369 (4)
F23	0.07743 (16)	0.02936 (4)	0.66771 (11)	0.0399 (4)
F24	0.06484 (16)	−0.03543 (4)	0.72907 (12)	0.0396 (4)
F25	0.16550 (15)	0.01533 (4)	0.82574 (13)	0.0452 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.01126 (9)	0.00884 (8)	0.01317 (9)	−0.00001 (6)	0.00056 (6)	−0.00003 (6)
N10	0.0122 (9)	0.0126 (8)	0.0159 (9)	0.0005 (6)	−0.0007 (7)	0.0005 (7)
C10	0.0173 (11)	0.0149 (10)	0.0214 (12)	0.0028 (8)	−0.0001 (9)	0.0018 (8)
C11	0.0189 (12)	0.0222 (11)	0.0288 (13)	0.0087 (9)	0.0053 (10)	0.0020 (9)
C12	0.0129 (11)	0.0274 (12)	0.0320 (14)	0.0020 (9)	0.0074 (10)	0.0044 (10)
C13	0.0155 (11)	0.0182 (10)	0.0240 (12)	−0.0028 (8)	0.0010 (9)	0.0028 (9)
C14	0.0149 (11)	0.0135 (9)	0.0135 (11)	−0.0004 (8)	−0.0032 (8)	−0.0011 (8)
N20	0.0124 (9)	0.0125 (8)	0.0120 (9)	−0.0001 (6)	−0.0015 (7)	−0.0014 (6)
N21	0.0170 (9)	0.0124 (8)	0.0178 (10)	−0.0018 (7)	−0.0025 (7)	−0.0012 (7)
N22	0.0182 (9)	0.0106 (8)	0.0153 (9)	0.0016 (7)	−0.0031 (7)	−0.0012 (7)
C20	0.0127 (10)	0.0152 (10)	0.0130 (11)	−0.0019 (8)	−0.0031 (8)	−0.0006 (8)
C21	0.0166 (11)	0.0133 (9)	0.0140 (11)	−0.0020 (8)	−0.0047 (8)	−0.0014 (8)
C22	0.0112 (10)	0.0144 (9)	0.0136 (11)	0.0006 (8)	−0.0033 (8)	−0.0012 (8)
N30	0.0139 (9)	0.0137 (8)	0.0114 (9)	−0.0001 (7)	−0.0002 (7)	−0.0005 (6)
C30	0.0181 (11)	0.0163 (10)	0.0189 (11)	−0.0040 (8)	0.0010 (9)	−0.0006 (8)
C31	0.0174 (12)	0.0256 (11)	0.0234 (13)	−0.0048 (9)	0.0069 (9)	−0.0032 (9)
C32	0.0176 (11)	0.0258 (11)	0.0233 (13)	0.0045 (9)	0.0055 (9)	−0.0038 (9)
C33	0.0198 (11)	0.0168 (10)	0.0174 (11)	0.0017 (8)	0.0010 (9)	−0.0008 (8)
C34	0.0149 (10)	0.0131 (9)	0.0116 (10)	−0.0011 (8)	−0.0022 (8)	0.0004 (8)
C40	0.0189 (11)	0.0118 (9)	0.0203 (12)	−0.0021 (8)	−0.0091 (9)	0.0007 (8)
C41	0.0276 (13)	0.0157 (10)	0.0233 (13)	−0.0021 (9)	−0.0030 (10)	−0.0006 (9)
C42	0.0321 (14)	0.0194 (11)	0.0283 (14)	−0.0084 (10)	−0.0078 (11)	0.0061 (9)
C43	0.0321 (14)	0.0129 (10)	0.0329 (14)	−0.0011 (9)	−0.0184 (11)	0.0019 (9)
C44	0.0225 (12)	0.0155 (10)	0.0326 (14)	0.0019 (9)	−0.0093 (10)	−0.0031 (9)
C45	0.0195 (12)	0.0162 (10)	0.0260 (13)	−0.0004 (8)	−0.0067 (9)	−0.0020 (9)
N50	0.0096 (8)	0.0120 (8)	0.0156 (9)	0.0008 (6)	0.0028 (7)	−0.0017 (6)
C50	0.0124 (10)	0.0136 (9)	0.0164 (11)	0.0022 (8)	0.0038 (8)	0.0010 (8)
C51	0.0140 (10)	0.0165 (10)	0.0182 (11)	0.0045 (8)	0.0019 (8)	0.0029 (8)
C52	0.0164 (11)	0.0210 (10)	0.0143 (11)	0.0026 (8)	0.0006 (9)	−0.0026 (8)
C53	0.0138 (10)	0.0142 (9)	0.0202 (12)	0.0006 (8)	0.0016 (9)	−0.0032 (8)
C54	0.0087 (10)	0.0133 (9)	0.0142 (11)	0.0018 (7)	0.0041 (8)	−0.0002 (8)
N60	0.0119 (9)	0.0139 (8)	0.0128 (9)	0.0010 (6)	0.0019 (7)	0.0000 (7)
N61	0.0152 (9)	0.0123 (8)	0.0154 (9)	0.0002 (7)	0.0028 (7)	0.0004 (7)
N62	0.0139 (9)	0.0123 (8)	0.0180 (10)	−0.0002 (6)	0.0026 (7)	0.0007 (7)
C60	0.0100 (10)	0.0145 (9)	0.0168 (11)	−0.0007 (8)	0.0033 (8)	−0.0020 (8)
C61	0.0127 (10)	0.0142 (9)	0.0177 (11)	0.0010 (8)	0.0047 (8)	0.0004 (8)
C62	0.0114 (10)	0.0148 (9)	0.0171 (11)	0.0019 (8)	0.0032 (8)	0.0028 (8)
N70	0.0125 (9)	0.0119 (8)	0.0166 (9)	−0.0002 (7)	0.0021 (7)	−0.0002 (7)
C70	0.0156 (11)	0.0142 (10)	0.0177 (11)	−0.0022 (8)	0.0016 (9)	−0.0021 (8)
C71	0.0185 (11)	0.0209 (11)	0.0165 (11)	−0.0018 (9)	−0.0016 (9)	−0.0021 (8)
C72	0.0212 (12)	0.0219 (10)	0.0160 (12)	0.0020 (9)	−0.0003 (9)	0.0026 (9)
C73	0.0180 (11)	0.0146 (10)	0.0194 (12)	−0.0006 (8)	0.0024 (9)	0.0024 (8)
C74	0.0140 (10)	0.0142 (9)	0.0154 (11)	0.0001 (8)	0.0040 (8)	0.0005 (8)
C80	0.0138 (11)	0.0124 (9)	0.0208 (12)	0.0015 (8)	0.0069 (9)	0.0002 (8)
C81	0.0175 (11)	0.0166 (10)	0.0242 (12)	0.0018 (8)	0.0020 (9)	0.0008 (9)
C82	0.0228 (12)	0.0163 (10)	0.0318 (14)	−0.0018 (9)	0.0008 (10)	−0.0053 (9)
C83	0.0224 (12)	0.0108 (10)	0.0382 (15)	−0.0009 (9)	0.0062 (10)	0.0008 (9)
C84	0.0247 (13)	0.0158 (10)	0.0280 (14)	0.0038 (9)	0.0044 (10)	0.0068 (9)
C85	0.0194 (11)	0.0171 (10)	0.0228 (13)	−0.0001 (9)	0.0034 (9)	0.0005 (9)
P10	0.0221 (3)	0.0165 (3)	0.0213 (3)	−0.0062 (2)	−0.0066 (2)	0.0052 (2)
F10	0.0444 (9)	0.0439 (8)	0.0267 (8)	−0.0221 (7)	−0.0129 (7)	0.0191 (6)
F11	0.0482 (9)	0.0203 (6)	0.0289 (8)	−0.0060 (6)	−0.0121 (7)	−0.0017 (6)
F12	0.0238 (8)	0.0526 (9)	0.0321 (8)	0.0031 (6)	−0.0023 (6)	0.0042 (7)
F13	0.0325 (8)	0.0205 (6)	0.0221 (7)	−0.0048 (5)	−0.0007 (6)	0.0061 (5)
F14	0.0488 (9)	0.0168 (6)	0.0350 (8)	−0.0108 (6)	−0.0161 (7)	0.0028 (6)
F15	0.0278 (8)	0.0266 (7)	0.0510 (9)	0.0031 (6)	−0.0085 (7)	0.0075 (6)
P20	0.0197 (3)	0.0132 (3)	0.0362 (4)	0.0013 (2)	0.0028 (3)	0.0045 (2)
F20	0.0471 (9)	0.0261 (7)	0.0462 (9)	0.0023 (6)	0.0159 (7)	0.0127 (6)
F21	0.0287 (7)	0.0152 (6)	0.0396 (8)	−0.0012 (5)	0.0023 (6)	−0.0028 (5)
F22	0.0330 (8)	0.0214 (7)	0.0556 (10)	−0.0009 (6)	−0.0114 (7)	−0.0082 (6)
F23	0.0446 (9)	0.0280 (7)	0.0483 (10)	0.0128 (6)	0.0215 (7)	0.0156 (7)
F24	0.0415 (9)	0.0165 (6)	0.0616 (10)	0.0101 (6)	0.0152 (7)	0.0042 (6)
F25	0.0277 (8)	0.0321 (8)	0.0746 (12)	−0.0004 (6)	−0.0156 (8)	0.0129 (8)

Geometric parameters (Å, º) top

Ru1—N10	2.0982 (16)	C50—H50	0.9500
Ru1—N20	1.9773 (15)	C51—C52	1.384 (3)
Ru1—N30	2.0990 (16)	C51—H51	0.9500
Ru1—N50	2.0967 (16)	C52—C53	1.380 (3)
Ru1—N60	1.9723 (15)	C52—H52	0.9500
Ru1—N70	2.0939 (17)	C53—C54	1.381 (3)
N10—C10	1.342 (2)	C53—H53	0.9500
N10—C14	1.378 (2)	C54—C60	1.472 (3)
C10—C11	1.385 (3)	N60—C60	1.342 (2)
C10—H10	0.9500	N60—C62	1.351 (2)
C11—C12	1.375 (3)	N61—C60	1.323 (2)
C11—H11	0.9500	N61—C61	1.352 (2)
C12—C13	1.390 (3)	N62—C62	1.323 (2)
C12—H12	0.9500	N62—C61	1.351 (3)
C13—C14	1.374 (3)	C61—C80	1.475 (3)
C13—H13	0.9500	C62—C74	1.475 (3)
C14—C20	1.470 (3)	N70—C70	1.351 (2)
N20—C22	1.340 (2)	N70—C74	1.375 (2)
N20—C20	1.341 (2)	C70—C71	1.381 (3)
N21—C20	1.318 (2)	C70—H70	0.9500
N21—C21	1.353 (3)	C71—C72	1.382 (3)
N22—C22	1.324 (2)	C71—H71	0.9500
N22—C21	1.344 (3)	C72—C73	1.388 (3)
C21—C40	1.476 (3)	C72—H72	0.9500
C22—C34	1.475 (3)	C73—C74	1.376 (3)
N30—C30	1.351 (2)	C73—H73	0.9500
N30—C34	1.376 (2)	C80—C85	1.393 (3)
C30—C31	1.386 (3)	C80—C81	1.394 (3)
C30—H30	0.9500	C81—C82	1.381 (3)
C31—C32	1.384 (3)	C81—H81	0.9500
C31—H31	0.9500	C82—C83	1.389 (3)
C32—C33	1.385 (3)	C82—H82	0.9500
C32—H32	0.9500	C83—C84	1.376 (3)
C33—C34	1.378 (3)	C83—H83	0.9500
C33—H33	0.9500	C84—C85	1.390 (3)
C40—C41	1.388 (3)	C84—H84	0.9500
C40—C45	1.400 (3)	C85—H85	0.9500
C41—C42	1.390 (3)	P10—F12	1.5943 (14)
C41—H41	0.9500	P10—F10	1.5980 (13)
C42—C43	1.386 (3)	P10—F11	1.5981 (13)
C42—H42	0.9500	P10—F14	1.6015 (13)
C43—C44	1.383 (3)	P10—F15	1.6029 (14)
C43—H43	0.9500	P10—F13	1.6104 (13)
C44—C45	1.380 (3)	P20—F20	1.5887 (14)
C44—H44	0.9500	P20—F24	1.5970 (13)
C45—H45	0.9500	P20—F21	1.5988 (13)
N50—C50	1.341 (2)	P20—F23	1.6022 (14)
N50—C54	1.380 (2)	P20—F22	1.6033 (15)
C50—C51	1.383 (3)	P20—F25	1.6056 (15)

N10—Ru1—N30	154.76 (6)	C52—C51—H51	120.3
N60—Ru1—N20	179.28 (7)	C53—C52—C51	118.88 (19)
N70—Ru1—N50	155.22 (6)	C53—C52—H52	120.6
N20—Ru1—N70	103.31 (6)	C51—C52—H52	120.6
N20—Ru1—N50	101.42 (6)	C52—C53—C54	119.35 (18)
N20—Ru1—N10	77.77 (6)	C52—C53—H53	120.3
N20—Ru1—N30	77.00 (6)	C54—C53—H53	120.3
N50—Ru1—N10	91.99 (6)	N50—C54—C53	122.12 (18)
N50—Ru1—N30	92.35 (6)	N50—C54—C60	114.54 (17)
N60—Ru1—N50	77.85 (6)	C53—C54—C60	123.34 (17)
N60—Ru1—N70	77.42 (6)	C60—N60—C62	117.61 (16)
N60—Ru1—N10	102.25 (6)	C60—N60—Ru1	121.10 (13)
N60—Ru1—N30	102.98 (6)	C62—N60—Ru1	121.27 (13)
N70—Ru1—N10	91.67 (6)	C60—N61—C61	115.55 (17)
N70—Ru1—N30	94.71 (6)	C62—N62—C61	115.62 (17)
C10—N10—C14	116.93 (17)	N61—C60—N60	123.30 (18)
C10—N10—Ru1	129.03 (13)	N61—C60—C54	124.22 (18)
C14—N10—Ru1	114.03 (12)	N60—C60—C54	112.47 (16)
N10—C10—C11	122.65 (18)	N62—C61—N61	124.81 (17)
N10—C10—H10	118.7	N62—C61—C80	117.91 (18)
C11—C10—H10	118.7	N61—C61—C80	117.28 (18)
C12—C11—C10	119.80 (19)	N62—C62—N60	123.03 (18)
C12—C11—H11	120.1	N62—C62—C74	124.68 (18)
C10—C11—H11	120.1	N60—C62—C74	112.28 (16)
C11—C12—C13	118.93 (19)	C70—N70—C74	117.23 (17)
C11—C12—H12	120.5	C70—N70—Ru1	127.56 (13)
C13—C12—H12	120.5	C74—N70—Ru1	115.09 (13)
C14—C13—C12	118.61 (19)	N70—C70—C71	122.21 (18)
C14—C13—H13	120.7	N70—C70—H70	118.9
C12—C13—H13	120.7	C71—C70—H70	118.9
C13—C14—N10	123.06 (18)	C70—C71—C72	120.02 (19)
C13—C14—C20	122.33 (17)	C70—C71—H71	120.0
N10—C14—C20	114.62 (17)	C72—C71—H71	120.0
C22—N20—C20	117.20 (16)	C71—C72—C73	118.71 (19)
C22—N20—Ru1	121.87 (13)	C71—C72—H72	120.6
C20—N20—Ru1	120.87 (12)	C73—C72—H72	120.6
C20—N21—C21	114.99 (17)	C74—C73—C72	118.93 (18)
C22—N22—C21	115.08 (16)	C74—C73—H73	120.5
N21—C20—N20	123.77 (18)	C72—C73—H73	120.5
N21—C20—C14	123.59 (18)	C73—C74—N70	122.87 (18)
N20—C20—C14	112.63 (16)	C73—C74—C62	123.19 (17)
N22—C21—N21	125.27 (17)	N70—C74—C62	113.88 (17)
N22—C21—C40	118.31 (17)	C85—C80—C81	119.08 (18)
N21—C21—C40	116.42 (18)	C85—C80—C61	120.80 (19)
N22—C22—N20	123.61 (18)	C81—C80—C61	120.12 (18)
N22—C22—C34	124.21 (17)	C82—C81—C80	120.3 (2)
N20—C22—C34	112.13 (16)	C82—C81—H81	119.9
C30—N30—C34	117.11 (16)	C80—C81—H81	119.9
C30—N30—Ru1	127.86 (13)	C81—C82—C83	120.4 (2)
C34—N30—Ru1	114.98 (12)	C81—C82—H82	119.8
N30—C30—C31	122.18 (18)	C83—C82—H82	119.8
N30—C30—H30	118.9	C84—C83—C82	119.66 (19)
C31—C30—H30	118.9	C84—C83—H83	120.2
C32—C31—C30	120.11 (19)	C82—C83—H83	120.2
C32—C31—H31	119.9	C83—C84—C85	120.5 (2)
C30—C31—H31	119.9	C83—C84—H84	119.8
C33—C32—C31	118.56 (19)	C85—C84—H84	119.8
C33—C32—H32	120.7	C84—C85—C80	120.1 (2)
C31—C32—H32	120.7	C84—C85—H85	119.9
C34—C33—C32	119.07 (18)	C80—C85—H85	119.9
C34—C33—H33	120.5	F12—P10—F10	90.99 (8)
C32—C33—H33	120.5	F12—P10—F11	90.25 (8)
N30—C34—C33	122.95 (17)	F10—P10—F11	90.97 (7)
N30—C34—C22	114.00 (16)	F12—P10—F14	90.22 (8)
C33—C34—C22	122.99 (17)	F10—P10—F14	89.70 (7)
C41—C40—C45	119.70 (18)	F11—P10—F14	179.17 (9)
C41—C40—C21	120.25 (18)	F12—P10—F15	179.52 (9)
C45—C40—C21	120.01 (19)	F10—P10—F15	89.46 (8)
C40—C41—C42	119.8 (2)	F11—P10—F15	89.57 (7)
C40—C41—H41	120.1	F14—P10—F15	89.95 (8)
C42—C41—H41	120.1	F12—P10—F13	89.68 (7)
C43—C42—C41	120.2 (2)	F10—P10—F13	178.99 (8)
C43—C42—H42	119.9	F11—P10—F13	89.79 (7)
C41—C42—H42	119.9	F14—P10—F13	89.53 (7)
C44—C43—C42	120.07 (19)	F15—P10—F13	89.87 (7)
C44—C43—H43	120.0	F20—P20—F24	90.05 (7)
C42—C43—H43	120.0	F20—P20—F21	90.18 (7)
C45—C44—C43	120.2 (2)	F24—P20—F21	179.50 (9)
C45—C44—H44	119.9	F20—P20—F23	179.55 (10)
C43—C44—H44	119.9	F24—P20—F23	90.15 (7)
C44—C45—C40	120.0 (2)	F21—P20—F23	89.63 (7)
C44—C45—H45	120.0	F20—P20—F22	90.33 (8)
C40—C45—H45	120.0	F24—P20—F22	90.25 (8)
C50—N50—C54	117.38 (17)	F21—P20—F22	89.31 (7)
C50—N50—Ru1	128.60 (13)	F23—P20—F22	90.08 (8)
C54—N50—Ru1	114.01 (13)	F20—P20—F25	90.50 (9)
N50—C50—C51	122.80 (18)	F24—P20—F25	89.90 (8)
N50—C50—H50	118.6	F21—P20—F25	90.54 (7)
C51—C50—H50	118.6	F23—P20—F25	89.10 (9)
C50—C51—C52	119.45 (19)	F22—P20—F25	179.16 (9)
C50—C51—H51	120.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C41—H41···N21	0.95	2.47	2.793 (3)	100
C45—H45···N22	0.95	2.52	2.826 (3)	99
C81—H81···N61	0.95	2.47	2.797 (2)	100
C85—H85···N62	0.95	2.50	2.823 (3)	100

Experimental details

Crystal data
Chemical formula	[Ru(C₁₉H₁₃N₅)₂](PF₆)₂
M_r	1013.70
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	93
a, b, c (Å)	9.0995 (3), 32.5979 (11), 13.1451 (5)
β (°)	91.774 (2)
V (Å³)	3897.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.59
Crystal size (mm)	0.30 × 0.13 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.822, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	75901, 8114, 6511
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.629

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.066, 0.99
No. of reflections	8114
No. of parameters	568
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.57

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), publCIF (Westrip, 2008).

Selected geometric parameters (Å, º) top

Ru1—N10	2.0982 (16)	Ru1—N50	2.0967 (16)
Ru1—N20	1.9773 (15)	Ru1—N60	1.9723 (15)
Ru1—N30	2.0990 (16)	Ru1—N70	2.0939 (17)

N10—Ru1—N30	154.76 (6)	N50—Ru1—N30	92.35 (6)
N60—Ru1—N20	179.28 (7)	N60—Ru1—N50	77.85 (6)
N70—Ru1—N50	155.22 (6)	N60—Ru1—N70	77.42 (6)
N20—Ru1—N70	103.31 (6)	N60—Ru1—N10	102.25 (6)
N20—Ru1—N50	101.42 (6)	N60—Ru1—N30	102.98 (6)
N20—Ru1—N10	77.77 (6)	N70—Ru1—N10	91.67 (6)
N20—Ru1—N30	77.00 (6)	N70—Ru1—N30	94.71 (6)
N50—Ru1—N10	91.99 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C41—H41···N21	0.95	2.47	2.793 (3)	99.6
C45—H45···N22	0.95	2.52	2.826 (3)	99.1
C81—H81···N61	0.95	2.47	2.797 (2)	100.2
C85—H85···N62	0.95	2.50	2.823 (3)	99.7

Acknowledgements

MIJP thanks the New Zealand Foundation of Research Science and Technology for funding.

References

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