Crystal structure of aceto­nitrile­[η6-1-methyl-4-(1-methyl­eth­yl)benzene][1-(pyrimidin-2-yl)-3H-indol-1-ium-2-yl-κ2N,C]ruthenium(II) bis­(hexa­fluorido­anti­monate)

Sollert, C.; Orthaber, A.; Pilarski, L.T.

doi:10.1107/S2056989015016710

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 10| October 2015| Pages 1190-1192

doi:10.1107/S2056989015016710

Open

access

Crystal structure of acetonitrile[η⁶-1-methyl-4-(1-methylethyl)benzene][1-(pyrimidin-2-yl)-3H-indol-1-ium-2-yl-κ²N,C]ruthenium(II) bis(hexafluoridoantimonate)

Carina Sollert,^a Andreas Orthaber ^b ^* and Lukasz T. Pilarski ^a ^*

^aUppsala University, Department of Chemistry – BMC, Box 576, 75123 Uppsala, Sweden, and ^bUppsala University, Department of Chemistry – Ångström Laboratories, Box 523, 75120 Uppsala, Sweden
^*Correspondence e-mail: andreas.orthaber@kemi.uu.se, lukasz.pilarski@kemi.uu.se

Edited by H. Ishida, Okayama University, Japan (Received 12 August 2015; accepted 7 September 2015; online 17 September 2015)

In the title compound, [Ru(C₁₀H₁₄)(C₁₂H₉N₃)(CH₃CN)][SbF₆]₂, the ruthenium(II) cation is η⁶-coordinated by the para-cymene ligand with a Ru–centroid(η⁶-benzene) distance of 1.746 (2) Å. Furthermore, ruthenium coordinations to the C and N atoms of the pyrimidyl indole ligand are found to be 1.986 (4) and 2.082 (3) Å, respectively. The typical piano-stool coordination environment is saturated with an acetonitrile solvent molecule with a Ru—N distance of 2.044 (3) Å. The indolyl ligand is protonated at the C3 position with the N=C imine bond length appropriate to that of related 3H-indole-based complexes. In the crystal, the complex cation is linked to the SbF₆⁻ ions through weak C—H⋯F hydrogen bonds.

Keywords: crystal structure; cyclometalated Ru^II; pyrimidyl-3H-indole; para-cymene; C—H⋯F hydrogen bonds.

CCDC reference: 1027878

1. Chemical context

Cyclometalated ruthenium compounds are well known catalytic intermediates in the C—H activation of various substrates (Arockiam et al., 2012 ; Li et al., 2012 ; Ferrer Flegeau et al., 2011 ). In a recent study on oxidative Ru-catalysed heteroarene C—H arylation (Wang et al., 2015 ; Ackermann & Lygin, 2011 ), we demonstrated that [{RuCl₂(p-cymene)}₂] in the presence of AgSbF₆ selectively ruthenates the C2—H bond of N-pyrimidine-substituted pyrroles and indoles (Sollert et al., 2015 ). We concluded that in our catalytic system, the resulting ruthenacyclic species likely act as precursors rather than on-cycle intermediates. In the course of our studies we observed the unusual formation of the title complex, which shows protonation at the C3 position. The title compound and related cyclometalated ruthenium complexes are shown schematically in Fig. 1.

Figure 1
The title compound (I)

and related cyclometalated ruthenium complexes (II) (Sollert et al., 2015

) and (III) (Chiang et al., 2010

2. Structural commentary

In the title compound (Fig. 2), the ruthenium(II) cation is coordinated in an η⁶ fashion by a para-cymene unit. The Ru—C_p-cymene distances range from 2.197 (4) to 2.298 (4) Å. The centroid of the para-cymene benzene ring (Cg) shows an Ru1—Cg distance of 1.746 (2) Å. Furthermore, ruthenium coordinations to C2 and N3 of the pyrimidyl indole are found to be 1.986 (4) and 2.082 (3) Å, respectively. The coordination environment is saturated with one acetonitrile solvent molecule, with an Ru1—N5 distance of 2.044 (3) Å. The least-squares planes of the 3H-indole ring system [r.m.s. deviation = 0.026 (4) Å] and the pyrimidine heterocycle [r.m.s. deviation = 0.013 (4) Å] are almost co-planar, making a dihedral angle of 2.6 (2)°. The Ru atom deviates by only 0.056 (1) Å from the 3H-indole plane. The 3H-indole shows a clear C2—N1 double bond of 1.345 (5) Å in the typical range for this class of compounds. The coordinating acetonitrile solvent molecule shows slight deviation from a linear arrangement [C27—N5—Ru1 = 170.4 (3)°].

Figure 2
ORTEP representation of the molecular components of the title compound, showing 50% probability displacement ellipsoids.

3. Supramolecular features

The packing allows no direct interaction of equivalent ruthenium complexes. The crystal packing shows a complex pattern in which two crystallographically independent SbF₆⁻ counter-ions occupy a void formed by symmetry-equivalent metal complexes. C—⋯H hydrogen bonds of the pyrimidylindole and para-cymene ligands with the SbF₆⁻ ions mainly account for the observed packing pattern (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯F7ⁱ	0.95	2.54	3.398 (6)	151
C12—H12⋯F1	0.95	2.39	3.157 (5)	138
C13—H13⋯F2	0.95	2.30	3.229 (5)	167
C51—H51⋯F11ⁱⁱ	0.95	2.54	3.485 (6)	174
C52—H52⋯F2	0.95	2.50	3.337 (5)	147
C54—H54⋯F5ⁱⁱⁱ	0.95	2.26	3.110 (5)	148
C59—H59B⋯F6	0.98	2.32	3.253 (6)	158
C59—H59C⋯F5ⁱⁱⁱ	0.98	2.45	3.270 (6)	141
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ .

4. Database survey

This structure is related to chloro(η⁶-para-cymene)[κ²-N,C-1-(pyrimidin-2-yl)-1H-indole]ruthenium (Sollert et al., 2015), in which the double bond is at C2=C3. The Ru1—C2 and Ru1-cymene distances, however, are almost unaltered. This is consistent with the development of a positive charge at N1 to effect the C3 protonation rather than at the Ru^II atom. The C2 atom in the title compound is therefore formally an anionic ligand, and not a carbene carbon. A similar cyclometalated pyrrolinyl complex (2) Buil et al., 2015 ; Fig. 1) was obtained through HBF₄-mediated rearrangement of N-allylic substituents. The Ru—C distances of 2.077 (4) Å (Buil et al., 2003) are comparable to the Ru1—C2 distance of the title compound. The Ru-catalysed rearrangement of a 1,7-eneyne afforded the C2-cyclometalated 3H-indole (3) (Chiang et al., 2010 ; Fig. 1). Structural parameters of this cyclopentadienyl-coordinated ruthenium complex are in good agreement with the title compound.

5. Synthesis and crystallization

A pre-dried Young's tube was charged with chlorido(η⁶-para-cymene)[κ²-N,C-1-(pyrimidin-2-yl)-1H-indole]ruthenium (50 mg, 1.0 equiv., 0.11 mmol) and AgSbF₆ (76 mg, 2.0 equiv., 0.22 mmol). The tube was evacuated and backfilled with argon three times. The tube was equipped with a rubber septum and anhydrous MeCN (2 mL) was added via a syringe. The septum was removed, the tube sealed and wrapped in aluminium foil to protect the reaction mixture from light. The mixture was left stirring at room temperature for 18 h, after which the resulting precipitate was filtered off rapidly under air and the filtrate transferred immediately into a pre-dried round-bottom flask under argon. The solvent was evaporated under reduced pressure and a green solid was obtained. The solid was dissolved in d₈-THF and transferred into a NMR tube under argon. The title compound was obtained as green crystals upon slow evaporation of the solvent.

6. Refinement

Crystal data, data collection and refinement details are summarized in Table 2. All H atoms on carbon were placed at calculated positions [C—H = 0.95 (aromatic), 0.98 (methyl), 0.99 (methylene) and 1.00 (methine) Å] using a riding model with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C_methyl). The Ru—C bonds were ignored in the ideal placement of the aromatic H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	[Ru(C₁₀H₁₄)(C₁₂H₉N₃)(C₂H₃N)][SbF₆]₂
M_r	943.06
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	16.6046 (8), 15.5955 (7), 23.2786 (12)
V (Å³)	6028.2 (5)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	2.37
Crystal size (mm)	0.18 × 0.17 × 0.08

Data collection
Diffractometer	BrukerAPEXII with CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 )
T_min, T_max	0.578, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	27645, 6643, 4920
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.643

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.074, 1.01
No. of reflections	6643
No. of parameters	392
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.89, −1.00
Computer programs: APEX2 and SAINT (Bruker, 2012 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and ORTEP-3 for Windows (Farrugia, 2012 ).

Supporting information

CCDC reference: 1027878

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2056989015016710/is5413sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015016710/is5413Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015016710/is5413Isup3.mol

checkCIF report

Chemical context top

Cyclometalated ruthenium compounds are well known catalytic intermediates in the C—H activation of various substrates (Arockiam et al., 2012; Li et al., 2012; Ferrer Flegeau et al., 2011). In a recent study on oxidative Ru-catalysed heteroarene C—H arylation (Wang et al., 2015; Ackermann & Lygin, 2011), we demonstrated that [{RuCl₂(p-cymene)}₂] in the presence of AgSbF₆ selectively ruthenates the C2—H bond of N-pyrimidine-substituted pyrroles and indoles (Sollert et al., 2015). We concluded that in our catalytic system, the resulting ruthenacyclic species likely act as precursors rather than on-cycle intermediates. In the course of our studies we observed the unusual formation of the title complex, which shows protonation at the C3 position.

Structural commentary top

In the title compound, the ruthenium cation is coordinated in an η⁶ fashion by a para-cymene unit. The Ru—C_p_-cymene distances range from 2.197 (4) to 2.298 (4) Å. The centroid of the para-cymene benzene ring (Cg) shows a Ru1—Cg distance of 1.746 (2) Å. Furthermore, ruthenium coordinations to C2 and N3 of the pyrimidyl indole are found to be 1.986 (4) and 2.082 (3) Å, respectively. The coordination environment is saturated with one acetonitrile solvent molecule, with an Ru1—N5 distance of 2.044 (3) Å. The least-squares planes of the 3H-indole ring system [r.m.s. deviation = 0.026 (4) Å] and the pyrimidine heterocycle [r.m.s. deviation = 0.013 (4) Å] are almost co-planar, making a dihedral angle of 2.6 (2)°. The Ru atom deviates by only 0.056 (1) Å from the 3H-indole plane. The 3H-indole shows a clear C2—N1 double bond of 1.345 (5) Å in the typical range for this class of compounds. The coordinated acetonitrile solvent molecule shows slight deviation from a linear arrangement [C27—N5—Ru1 = 170.4 (3)°].

Supramolecular features top

The packing allows no direct interaction of equivalent ruthenium complexes. The crystal packing shows a complex pattern in which two crystallographically independent SbF₆^- counter-ions occupy a void formed by symmetry-equivalent metal complexes. The hydrogen bonds of the pyrimidylindole and para-cymene ligands with the SbF₆^- ions mainly account for the observed packing pattern (Table 1).

Database survey top

This structure is related to chloro(η⁶-para-cymene)[κ²-N,C-1-(pyrimidin-2-yl)-1H-indole]ruthenium, in which the double bond is at C2═C3. The Ru1—C2 and Ru1-cymene distances, however, are almost unaltered. This is consistent with the development of a positive charge at N1 to effect the C3 protonation rather than at the Ru centre. The C2 atom in the title compound is therefore formally an anionic ligand, and not a carbene carbon. A similar cyclometalated pyrrolinyl complex (2) (Sollert et al., 2015) was obtained through HBF₄-mediated rearrangement of N-allylic substituents. The Ru—C distances of 2.077 (4) Å (Buil et al., 2003) are comparable to the Ru1—C2 distance of the title compound. The Ru-catalysed rearrangement of a 1,7-eneyne afforded the C2-cyclometalated 3H-indole (3) (Chiang et al., 2010). Structural parameters of this cyclopentadienyl-coordinated ruthenium complex are in good agreement with the title compound.

Synthesis and crystallization top

A pre-dried Young's tube was charged with chloro(η⁶-para-cymene)[κ²-N,C-1-(pyrimidin-2-yl)-1H-indole]ruthenium (50 mg, 1.0 equiv., 0.11 mmol) and AgSbF₆ (76 mg, 2.0 equiv., 0.22 mmol). The tube was evacuated and backfilled with argon three times. The tube was equipped with a rubber septum and anhydrous MeCN (2 mL) was added via a syringe. The septum was removed, the tube sealed and wrapped in aluminium foil to protect the reaction mixture from light. The mixture was left stirring at room temperature for 18 h, after which the resulting precipitate was filtered off rapidly under air and the filtrate transferred immediately into a pre-dried round-bottom flask under argon. The solvent was evaporated under reduced pressure and a green solid was obtained. The solid was dissolved in d₈-THF and transferred into a NMR tube under argon. The title compound was obtained as green crystals upon slow evaporation of the solvent.

Refinement top

Crystal data, data collection and refinement details are summarized in Table 2. All H atoms on carbon were placed at calculated positions [C—H = 0.95 (aromatic), 0.98 (methyl), 0.99 (methylene) and 1.00 (methine) Å] using a riding model with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C_methyl) . The Ru—C bonds were ignored in the ideal placement of the aromatic H-atoms.

Related literature top

For related literature, see: Ackermann & Lygin (2011); Arockiam et al. (2012); Buil et al. (2003); Chiang et al. (2010); Ferrer Flegeau et al. (2011); Li et al. (2012); Sollert et al. (2015); Wang et al. (2015).

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures top

	Fig. 1. Title compound (I) and related cyclometalated ruthenium complexes (II) (Sollert et al., 2015) and (III) (Chiang et al., 2010).
	Fig. 2. ORTEP representation of the molecular structure of the title compound, showing 50% probability displacement ellipsoids.

Acetonitrile[η⁶-1-methyl-4-(1-methylethyl)benzene][1-(pyrimidin-2-yl)-3H-indol-1-ium-2-yl-κ²N,C]ruthenium(II) bis(hexafluoridoantimonate) top

Crystal data top

[Ru(C₁₀H₁₄)(C₁₂H₉N₃)(C₂H₃N)][SbF₆]₂	D_x = 2.078 Mg m⁻³
M_r = 943.06	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 4920 reflections
a = 16.6046 (8) Å	θ = 1.8–25.2°
b = 15.5955 (7) Å	µ = 2.37 mm⁻¹
c = 23.2786 (12) Å	T = 100 K
V = 6028.2 (5) Å³	Plate, green
Z = 8	0.18 × 0.17 × 0.08 mm
F(000) = 3616

Data collection top

BrukerAPEXII with CCD diffractometer	6643 independent reflections
Radiation source: fine-focus sealed tube	4920 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ω scans	θ_max = 27.2°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→20
T_min = 0.578, T_max = 0.746	k = −19→19
27645 measured reflections	l = −29→27

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.0294P)² + 2.8958P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.002
6643 reflections	Δρ_max = 0.89 e Å⁻³
392 parameters	Δρ_min = −1.00 e Å⁻³

Crystal data top

[Ru(C₁₀H₁₄)(C₁₂H₉N₃)(C₂H₃N)][SbF₆]₂	V = 6028.2 (5) Å³
M_r = 943.06	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 16.6046 (8) Å	µ = 2.37 mm⁻¹
b = 15.5955 (7) Å	T = 100 K
c = 23.2786 (12) Å	0.18 × 0.17 × 0.08 mm

Data collection top

BrukerAPEXII with CCD diffractometer	6643 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4920 reflections with I > 2σ(I)
T_min = 0.578, T_max = 0.746	R_int = 0.054
27645 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 1.01	Δρ_max = 0.89 e Å⁻³
6643 reflections	Δρ_min = −1.00 e Å⁻³
392 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 equipped 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.

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	0.93384 (2)	0.22549 (2)	0.87058 (2)	0.01738 (8)
Sb1	0.85442 (2)	−0.13417 (2)	0.94657 (2)	0.02309 (8)
Sb2	0.78888 (2)	0.49530 (2)	0.71378 (2)	0.02768 (8)
F1	0.89213 (19)	−0.09995 (16)	1.01877 (12)	0.0461 (8)
F2	0.93350 (14)	−0.06576 (14)	0.91106 (11)	0.0282 (6)
F3	0.77479 (15)	−0.20299 (16)	0.98028 (12)	0.0372 (7)
F4	0.92598 (15)	−0.22620 (14)	0.94954 (12)	0.0359 (6)
F5	0.82004 (18)	−0.1684 (2)	0.87420 (12)	0.0517 (8)
F6	0.78500 (18)	−0.04062 (18)	0.94558 (15)	0.0605 (10)
F7	0.7883 (2)	0.37969 (16)	0.69278 (13)	0.0558 (9)
F8	0.7572 (2)	0.46434 (18)	0.78733 (12)	0.0538 (9)
F9	0.79200 (19)	0.61114 (16)	0.73516 (12)	0.0464 (8)
F10	0.6831 (2)	0.5081 (2)	0.69167 (18)	0.0795 (12)
F11	0.89525 (19)	0.48324 (19)	0.73806 (18)	0.0732 (11)
F12	0.8239 (3)	0.5243 (2)	0.64075 (14)	0.0872 (14)
N1	0.90603 (19)	0.3372 (2)	0.96626 (14)	0.0178 (7)
N2	0.8897 (2)	0.2522 (2)	1.04905 (14)	0.0214 (8)
N3	0.91640 (18)	0.1923 (2)	0.95632 (14)	0.0176 (7)
N5	1.0551 (2)	0.2291 (2)	0.88533 (14)	0.0210 (8)
C2	0.9204 (2)	0.3380 (3)	0.90940 (18)	0.0206 (9)
C3	0.9232 (3)	0.4290 (2)	0.89077 (17)	0.0223 (9)
H3A	0.8806	0.4410	0.8621	0.027*
H3B	0.9762	0.4431	0.8738	0.027*
C4	0.9091 (2)	0.4796 (2)	0.94537 (18)	0.0214 (9)
C5	0.9052 (3)	0.5662 (3)	0.95639 (19)	0.0263 (10)
H5	0.9146	0.6068	0.9267	0.032*
C6	0.8872 (3)	0.5931 (3)	1.0116 (2)	0.0281 (10)
H6	0.8847	0.6528	1.0196	0.034*
C7	0.8729 (3)	0.5347 (3)	1.05571 (19)	0.0267 (10)
H7	0.8592	0.5549	1.0930	0.032*
C8	0.8786 (2)	0.4467 (3)	1.04542 (18)	0.0223 (9)
H8	0.8703	0.4058	1.0751	0.027*
C9	0.8969 (2)	0.4222 (2)	0.99016 (18)	0.0191 (9)
C10	0.9032 (2)	0.2573 (2)	0.99352 (18)	0.0190 (9)
C11	0.8882 (2)	0.1724 (3)	1.07022 (18)	0.0230 (9)
H11	0.8788	0.1650	1.1102	0.028*
C12	0.8997 (2)	0.1006 (3)	1.03687 (17)	0.0229 (9)
H12	0.8967	0.0446	1.0527	0.028*
C13	0.9157 (2)	0.1136 (2)	0.97918 (18)	0.0219 (9)
H13	0.9264	0.0655	0.9553	0.026*
C27	1.1233 (3)	0.2267 (2)	0.88601 (17)	0.0209 (9)
C28	1.2103 (3)	0.2249 (3)	0.8860 (2)	0.0326 (11)
H28A	1.2303	0.2392	0.8476	0.049*
H28B	1.2289	0.1674	0.8967	0.049*
H28C	1.2307	0.2668	0.9138	0.049*
C50	0.9606 (3)	0.2124 (3)	0.77680 (18)	0.0247 (10)
C51	0.9519 (3)	0.1264 (3)	0.79863 (17)	0.0241 (10)
H51	0.9932	0.0856	0.7916	0.029*
C52	0.8850 (3)	0.1023 (3)	0.82936 (17)	0.0227 (9)
H52	0.8808	0.0452	0.8433	0.027*
C53	0.8216 (2)	0.1625 (3)	0.84050 (18)	0.0207 (9)
C54	0.8274 (2)	0.2446 (2)	0.81594 (16)	0.0196 (9)
H54	0.7842	0.2840	0.8205	0.024*
C55	0.8962 (2)	0.2697 (3)	0.78465 (17)	0.0213 (9)
H55	0.8990	0.3257	0.7687	0.026*
C56	1.0360 (3)	0.2354 (3)	0.74384 (19)	0.0305 (11)
H56	1.0823	0.2063	0.7631	0.037*
C57	1.0281 (3)	0.1975 (3)	0.6834 (2)	0.0448 (14)
H57A	1.0189	0.1355	0.6861	0.067*
H57B	1.0777	0.2083	0.6617	0.067*
H57C	0.9825	0.2244	0.6635	0.067*
C58	1.0541 (3)	0.3316 (3)	0.7425 (2)	0.0445 (13)
H58A	1.1071	0.3411	0.7252	0.067*
H58C	1.0539	0.3542	0.7818	0.067*
H58B	1.0129	0.3611	0.7198	0.067*
C59	0.7499 (3)	0.1355 (3)	0.87511 (19)	0.0283 (10)
H59C	0.7273	0.1855	0.8949	0.042*
H59B	0.7664	0.0926	0.9035	0.042*
H59A	0.7091	0.1108	0.8496	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.01528 (16)	0.01805 (16)	0.01879 (17)	0.00165 (13)	0.00117 (14)	−0.00097 (14)
Sb1	0.01982 (15)	0.02391 (15)	0.02554 (16)	0.00207 (12)	0.00044 (13)	0.00291 (13)
Sb2	0.03160 (17)	0.02741 (16)	0.02404 (16)	0.00270 (13)	0.00236 (13)	−0.00066 (13)
F1	0.073 (2)	0.0358 (15)	0.0295 (16)	−0.0094 (15)	0.0018 (15)	−0.0053 (13)
F2	0.0254 (13)	0.0237 (12)	0.0354 (15)	−0.0027 (11)	−0.0018 (12)	0.0042 (11)
F3	0.0258 (15)	0.0391 (15)	0.0466 (17)	−0.0006 (12)	0.0117 (13)	0.0062 (13)
F4	0.0288 (15)	0.0234 (13)	0.0557 (18)	0.0042 (11)	0.0071 (13)	0.0046 (13)
F5	0.0488 (19)	0.075 (2)	0.0315 (17)	−0.0302 (17)	−0.0106 (14)	0.0072 (15)
F6	0.0386 (18)	0.0464 (17)	0.096 (3)	0.0217 (14)	0.0235 (18)	0.0285 (18)
F7	0.089 (3)	0.0309 (16)	0.0481 (19)	0.0035 (15)	0.0041 (18)	−0.0131 (14)
F8	0.082 (2)	0.0438 (17)	0.0351 (17)	−0.0126 (17)	0.0162 (16)	0.0004 (14)
F9	0.068 (2)	0.0297 (15)	0.0410 (17)	−0.0018 (14)	0.0026 (16)	0.0015 (13)
F10	0.055 (2)	0.085 (3)	0.098 (3)	0.011 (2)	−0.041 (2)	−0.017 (2)
F11	0.0317 (18)	0.0531 (19)	0.135 (4)	0.0016 (15)	−0.007 (2)	0.019 (2)
F12	0.164 (4)	0.055 (2)	0.042 (2)	0.028 (2)	0.048 (2)	0.0118 (17)
N1	0.0178 (17)	0.0198 (17)	0.0158 (18)	0.0006 (14)	0.0008 (14)	−0.0036 (14)
N2	0.0171 (18)	0.0243 (19)	0.023 (2)	0.0003 (15)	−0.0010 (15)	−0.0002 (16)
N3	0.0131 (17)	0.0188 (17)	0.0209 (19)	0.0016 (13)	0.0025 (14)	−0.0020 (15)
N5	0.023 (2)	0.0222 (18)	0.0182 (19)	0.0017 (15)	0.0006 (15)	−0.0003 (15)
C2	0.010 (2)	0.027 (2)	0.024 (2)	0.0011 (16)	−0.0018 (17)	−0.0022 (18)
C3	0.025 (2)	0.025 (2)	0.017 (2)	−0.0011 (18)	0.0005 (18)	0.0039 (18)
C4	0.014 (2)	0.023 (2)	0.027 (2)	0.0000 (16)	−0.0017 (18)	−0.0017 (19)
C5	0.022 (2)	0.027 (2)	0.030 (3)	0.0025 (18)	−0.0022 (19)	0.003 (2)
C6	0.024 (2)	0.025 (2)	0.035 (3)	0.0022 (19)	−0.002 (2)	−0.009 (2)
C7	0.025 (2)	0.028 (2)	0.027 (2)	−0.0029 (19)	0.002 (2)	−0.008 (2)
C8	0.020 (2)	0.022 (2)	0.024 (2)	−0.0023 (17)	0.0005 (18)	−0.0019 (19)
C9	0.013 (2)	0.019 (2)	0.025 (2)	−0.0008 (16)	−0.0015 (17)	−0.0016 (18)
C10	0.0097 (19)	0.025 (2)	0.022 (2)	−0.0012 (16)	−0.0028 (17)	−0.0017 (18)
C11	0.020 (2)	0.030 (2)	0.020 (2)	0.0007 (18)	−0.0028 (18)	0.0031 (19)
C12	0.022 (2)	0.027 (2)	0.020 (2)	−0.0031 (18)	−0.0039 (18)	0.0056 (19)
C13	0.020 (2)	0.020 (2)	0.026 (2)	0.0012 (16)	−0.0060 (19)	−0.0006 (18)
C27	0.026 (2)	0.020 (2)	0.017 (2)	−0.0017 (18)	0.0019 (18)	−0.0029 (17)
C28	0.020 (2)	0.043 (3)	0.035 (3)	−0.005 (2)	0.002 (2)	−0.007 (2)
C50	0.024 (2)	0.032 (2)	0.018 (2)	0.0057 (19)	−0.0021 (18)	−0.0047 (19)
C51	0.026 (2)	0.027 (2)	0.019 (2)	0.0100 (18)	−0.0035 (18)	−0.0101 (19)
C52	0.027 (2)	0.022 (2)	0.020 (2)	−0.0010 (18)	−0.0037 (19)	−0.0070 (18)
C53	0.015 (2)	0.025 (2)	0.022 (2)	0.0001 (17)	−0.0028 (18)	−0.0043 (18)
C54	0.016 (2)	0.025 (2)	0.017 (2)	0.0041 (17)	−0.0047 (17)	−0.0043 (18)
C55	0.024 (2)	0.024 (2)	0.016 (2)	0.0022 (18)	−0.0005 (18)	0.0024 (18)
C56	0.026 (2)	0.043 (3)	0.022 (2)	0.005 (2)	0.007 (2)	0.003 (2)
C57	0.045 (3)	0.066 (4)	0.023 (3)	0.003 (3)	0.014 (2)	0.001 (3)
C58	0.036 (3)	0.053 (3)	0.045 (3)	−0.004 (3)	0.013 (3)	0.001 (3)
C59	0.026 (2)	0.028 (2)	0.031 (3)	−0.006 (2)	−0.001 (2)	−0.001 (2)

Geometric parameters (Å, º) top

Ru1—C2	1.986 (4)	C56—C57	1.533 (6)
Ru1—N3	2.082 (3)	C56—H56	1.0000
Ru1—N5	2.044 (3)	C57—H57A	0.9800
Ru1—C50	2.237 (4)	C57—H57B	0.9800
Ru1—C51	2.298 (4)	C57—H57C	0.9800
Ru1—C52	2.296 (4)	C58—H58A	0.9800
Ru1—C53	2.220 (4)	C58—H58C	0.9800
Ru1—C54	2.197 (4)	C58—H58B	0.9800
Ru1—C55	2.206 (4)	C2—N1	1.345 (5)
Sb1—F1	1.871 (3)	C2—C3	1.485 (5)
Sb1—F2	1.883 (2)	C3—C4	1.514 (5)
Sb1—F3	1.875 (2)	C3—H3A	0.9900
Sb1—F4	1.865 (2)	C3—H3B	0.9900
Sb1—F5	1.857 (3)	C4—C5	1.377 (6)
Sb1—F6	1.860 (3)	C4—C9	1.388 (5)
Sb2—F7	1.868 (3)	C9—C8	1.376 (5)
Sb2—F8	1.855 (3)	C9—N1	1.447 (5)
Sb2—F9	1.875 (3)	C8—C7	1.396 (6)
Sb2—F10	1.841 (3)	C8—H8	0.9500
Sb2—F11	1.864 (3)	C7—C6	1.393 (6)
Sb2—F12	1.853 (3)	C7—H7	0.9500
N5—C27	1.133 (5)	C6—C5	1.384 (6)
C50—C55	1.406 (6)	C6—H6	0.9500
C50—C51	1.442 (6)	C5—H5	0.9500
C50—C56	1.510 (6)	N1—C10	1.399 (5)
C51—C52	1.373 (6)	C10—N2	1.314 (5)
C51—H51	0.9500	C10—N3	1.351 (5)
C52—C53	1.436 (5)	N2—C11	1.339 (5)
C52—H52	0.9500	C11—C12	1.375 (6)
C53—C54	1.406 (5)	C11—H11	0.9500
C53—C59	1.497 (6)	C12—C13	1.384 (6)
C54—C55	1.409 (6)	C12—H12	0.9500
C54—H54	0.9500	C13—N3	1.338 (5)
C55—H55	0.9500	C13—H13	0.9500
C59—H59C	0.9800	C27—C28	1.444 (6)
C59—H59B	0.9800	C28—H28A	0.9800
C59—H59A	0.9800	C28—H28B	0.9800
C56—C58	1.531 (6)	C28—H28C	0.9800

C2—Ru1—N5	90.54 (14)	C59—C53—Ru1	128.4 (3)
C2—Ru1—N3	76.59 (15)	C53—C54—C55	121.3 (4)
N5—Ru1—N3	89.02 (13)	C53—C54—Ru1	72.3 (2)
C2—Ru1—C54	93.05 (15)	C55—C54—Ru1	71.7 (2)
N5—Ru1—C54	152.34 (14)	C53—C54—H54	119.4
N3—Ru1—C54	118.48 (14)	C55—C54—H54	119.4
C2—Ru1—C55	96.00 (16)	Ru1—C54—H54	129.0
N5—Ru1—C55	115.03 (14)	C50—C55—C54	120.5 (4)
N3—Ru1—C55	155.13 (14)	C50—C55—Ru1	72.7 (2)
C54—Ru1—C55	37.32 (15)	C54—C55—Ru1	71.0 (2)
C2—Ru1—C53	116.11 (15)	C50—C55—H55	119.8
N5—Ru1—C53	153.20 (14)	C54—C55—H55	119.8
N3—Ru1—C53	94.33 (14)	Ru1—C55—H55	128.8
C54—Ru1—C53	37.11 (14)	C53—C59—H59C	109.5
C55—Ru1—C53	67.31 (15)	C53—C59—H59B	109.5
C2—Ru1—C50	123.14 (16)	H59C—C59—H59B	109.5
N5—Ru1—C50	88.31 (14)	C53—C59—H59A	109.5
N3—Ru1—C50	160.11 (14)	H59C—C59—H59A	109.5
C54—Ru1—C50	66.88 (15)	H59B—C59—H59A	109.5
C55—Ru1—C50	36.89 (14)	C50—C56—C58	113.9 (4)
C53—Ru1—C50	79.57 (15)	C50—C56—C57	107.7 (4)
C2—Ru1—C52	152.89 (15)	C58—C56—C57	112.1 (4)
N5—Ru1—C52	116.18 (14)	C50—C56—H56	107.6
N3—Ru1—C52	98.24 (14)	C58—C56—H56	107.6
C54—Ru1—C52	65.67 (15)	C57—C56—H56	107.6
C55—Ru1—C52	77.44 (15)	C56—C57—H57A	109.5
C53—Ru1—C52	37.03 (14)	C56—C57—H57B	109.5
C50—Ru1—C52	65.55 (15)	H57A—C57—H57B	109.5
C2—Ru1—C51	160.05 (16)	C56—C57—H57C	109.5
N5—Ru1—C51	90.72 (14)	H57A—C57—H57C	109.5
N3—Ru1—C51	123.34 (14)	H57B—C57—H57C	109.5
C54—Ru1—C51	76.96 (15)	C56—C58—H58A	109.5
C55—Ru1—C51	65.56 (15)	C56—C58—H58C	109.5
C53—Ru1—C51	65.32 (15)	H58A—C58—H58C	109.5
C50—Ru1—C51	37.03 (15)	C56—C58—H58B	109.5
C52—Ru1—C51	34.79 (15)	H58A—C58—H58B	109.5
F5—Sb1—F6	91.35 (15)	H58C—C58—H58B	109.5
F5—Sb1—F4	90.48 (13)	N1—C2—C3	107.6 (3)
F6—Sb1—F4	178.08 (15)	N1—C2—Ru1	117.3 (3)
F5—Sb1—F1	178.35 (14)	C3—C2—Ru1	135.1 (3)
F6—Sb1—F1	89.71 (14)	C2—C3—C4	104.4 (3)
F4—Sb1—F1	88.45 (12)	C2—C3—H3A	110.9
F5—Sb1—F3	89.91 (12)	C4—C3—H3A	110.9
F6—Sb1—F3	90.98 (12)	C2—C3—H3B	110.9
F4—Sb1—F3	89.61 (11)	C4—C3—H3B	110.9
F1—Sb1—F3	91.34 (12)	H3A—C3—H3B	108.9
F5—Sb1—F2	88.79 (11)	C5—C4—C9	119.0 (4)
F6—Sb1—F2	88.99 (11)	C5—C4—C3	132.5 (4)
F4—Sb1—F2	90.46 (10)	C9—C4—C3	108.5 (3)
F1—Sb1—F2	89.96 (12)	C8—C9—C4	123.8 (4)
F3—Sb1—F2	178.70 (12)	C8—C9—N1	129.6 (4)
F10—Sb2—F12	91.0 (2)	C4—C9—N1	106.7 (3)
F10—Sb2—F8	90.89 (17)	C9—C8—C7	116.6 (4)
F12—Sb2—F8	178.02 (18)	C9—C8—H8	121.7
F10—Sb2—F11	178.52 (18)	C7—C8—H8	121.7
F12—Sb2—F11	90.30 (19)	C6—C7—C8	120.3 (4)
F8—Sb2—F11	87.86 (17)	C6—C7—H7	119.8
F10—Sb2—F7	91.56 (15)	C8—C7—H7	119.8
F12—Sb2—F7	89.85 (14)	C5—C6—C7	121.5 (4)
F8—Sb2—F7	89.37 (13)	C5—C6—H6	119.2
F11—Sb2—F7	89.24 (15)	C7—C6—H6	119.2
F10—Sb2—F9	89.76 (14)	C4—C5—C6	118.7 (4)
F12—Sb2—F9	89.97 (14)	C4—C5—H5	120.6
F8—Sb2—F9	90.77 (12)	C6—C5—H5	120.6
F11—Sb2—F9	89.45 (14)	C2—N1—C10	117.4 (3)
F7—Sb2—F9	178.67 (15)	C2—N1—C9	112.8 (3)
C27—N5—Ru1	170.4 (3)	C10—N1—C9	129.7 (3)
C55—C50—C51	117.9 (4)	N2—C10—N3	127.8 (4)
C55—C50—C56	123.1 (4)	N2—C10—N1	120.4 (4)
C51—C50—C56	118.9 (4)	N3—C10—N1	111.8 (3)
C55—C50—Ru1	70.4 (2)	C10—N2—C11	114.9 (4)
C51—C50—Ru1	73.8 (2)	N2—C11—C12	123.1 (4)
C56—C50—Ru1	129.7 (3)	N2—C11—H11	118.5
C52—C51—C50	121.4 (4)	C12—C11—H11	118.5
C52—C51—Ru1	72.5 (2)	C11—C12—C13	117.1 (4)
C50—C51—Ru1	69.2 (2)	C11—C12—H12	121.4
C52—C51—H51	119.3	C13—C12—H12	121.4
C50—C51—H51	119.3	N3—C13—C12	121.4 (4)
Ru1—C51—H51	132.0	N3—C13—H13	119.3
C51—C52—C53	120.5 (4)	C12—C13—H13	119.3
C51—C52—Ru1	72.7 (2)	C13—N3—C10	115.6 (3)
C53—C52—Ru1	68.6 (2)	C13—N3—Ru1	127.6 (3)
C51—C52—H52	119.7	C10—N3—Ru1	116.8 (3)
C53—C52—H52	119.7	N5—C27—C28	178.9 (5)
Ru1—C52—H52	131.8	C27—C28—H28A	109.5
C54—C53—C52	118.2 (4)	C27—C28—H28B	109.5
C54—C53—C59	122.0 (4)	H28A—C28—H28B	109.5
C52—C53—C59	119.8 (4)	C27—C28—H28C	109.5
C54—C53—Ru1	70.6 (2)	H28A—C28—H28C	109.5
C52—C53—Ru1	74.3 (2)	H28B—C28—H28C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···F7ⁱ	0.95	2.54	3.398 (6)	151
C12—H12···F1	0.95	2.39	3.157 (5)	138
C13—H13···F2	0.95	2.30	3.229 (5)	167
C51—H51···F11ⁱⁱ	0.95	2.54	3.485 (6)	174
C52—H52···F2	0.95	2.50	3.337 (5)	147
C54—H54···F5ⁱⁱⁱ	0.95	2.26	3.110 (5)	148
C59—H59B···F6	0.98	2.32	3.253 (6)	158
C59—H59C···F5ⁱⁱⁱ	0.98	2.45	3.270 (6)	141

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+2, y−1/2, −z+3/2; (iii) −x+3/2, y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···F7ⁱ	0.95	2.54	3.398 (6)	151
C12—H12···F1	0.95	2.39	3.157 (5)	138
C13—H13···F2	0.95	2.30	3.229 (5)	167
C51—H51···F11ⁱⁱ	0.95	2.54	3.485 (6)	174
C52—H52···F2	0.95	2.50	3.337 (5)	147
C54—H54···F5ⁱⁱⁱ	0.95	2.26	3.110 (5)	148
C59—H59B···F6	0.98	2.32	3.253 (6)	158
C59—H59C···F5ⁱⁱⁱ	0.98	2.45	3.270 (6)	141

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+2, y−1/2, −z+3/2; (iii) −x+3/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	[Ru(C₁₀H₁₄)(C₁₂H₉N₃)(C₂H₃N)][SbF₆]₂
M_r	943.06
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	16.6046 (8), 15.5955 (7), 23.2786 (12)
V (Å³)	6028.2 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.37
Crystal size (mm)	0.18 × 0.17 × 0.08

Data collection
Diffractometer	BrukerAPEXII with CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.578, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	27645, 6643, 4920
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.643

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.074, 1.01
No. of reflections	6643
No. of parameters	392
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.89, −1.00

Computer programs: APEX2 (Bruker, 2012), SAINT (Bruker, 2012), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012).

Acknowledgements

The authors would like to thank the Swedish research council (Vetenskapsrådet) for support.

References

Ackermann, L. & Lygin, A. V. (2011). Org. Lett. 13, 3332–3335. CrossRef CAS PubMed Google Scholar
Arockiam, P. B., Bruneau, C. & Dixneuf, P. H. (2012). Chem. Rev. 112, 5879–5918. CrossRef CAS PubMed Google Scholar
Bruker (2012). APEX2 and SAINT. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Buil, M. L., Esteruelas, M. A., López, A. M. & Oñate, E. (2003). Organometallics, 22, 5274–5284. CSD CrossRef CAS Google Scholar
Chiang, P.-Y., Lin, Y.-C., Wang, Y. & Liu, Y.-H. (2010). Organometallics, 29, 5776–5782. CSD CrossRef CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ferrer Flegeau, E., Bruneau, C., Dixneuf, P. H. & Jutand, A. (2011). J. Am. Chem. Soc. 133, 10161–10170. CrossRef PubMed Google Scholar
Li, B., Roisnel, T., Darcel, C. & Dixneuf, P. H. (2012). Dalton Trans. 41, 10934–10937. CSD CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sollert, C., Devaraj, K., Orthaber, A., Gates, P. J. & Pilarski, L. T. (2015). Chem. Eur. J. 21, 5380–5386. CSD CrossRef CAS PubMed Google Scholar
Wang, L., Yang, D., Han, F., Li, D., Zhao, D. & Wang, R. (2015). Org. Lett. 17, 176–179. CrossRef CAS PubMed Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 10| October 2015| Pages 1190-1192

doi:10.1107/S2056989015016710

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)