(η-Penta-methyl-cyclo-penta-dien-yl)(η-toluene)-ruthenium(II) hexa-fluorido-phosphate.

In the title complex, [Ru(C(7)H(8))(C(10)H(15))]PF(6), the cation lies on a mirror plane and the anion lies on an inversion center. The distance between the Ru atom and the centroid of the benzene ring is 1.706 (5) Å and the distance between the Ru atom and the cyclo-penta-dienyl ring is 1.811 (5) Å. The crystal structure is stabilized by weak C-H⋯F hydrogen bonds. The H atoms of the methyl groups which lie on the mirror plane are disordered over two sites with equal occupancies.

Related literature

For reviews on half-sandwich complexes containing group 8 metals, see: Coville et al. (1992 ▶); Jiménez-Tenorio et al. (2004 ▶). For the synthesis and properties of the title complex, see: Arliguie et al. (1988 ▶); Schmid et al. (2003 ▶); Loughrey et al. (2008 ▶). For related structures, see: Fagan et al. (1989 ▶, 1990 ▶); He et al. (1991 ▶); Nolan et al. (1993 ▶). For bifunctional catalysts for the homogenous hydrogenation of polar bonds, see: Clapham et al. (2004 ▶); O et al. (2010 ▶).

Experimental

Crystal data

[Ru(C7H8)(C10H15)]PF6

M = 473.39

Orthorhombic,

a = 13.9735 (4) Å

b = 15.3266 (4) Å

c = 8.6576 (6) Å

V = 1854.17 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.99 mm−1

T = 150 K

0.22 × 0.15 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T min = 0.711, T max = 0.863

11870 measured reflections

2200 independent reflections

1611 reflections with I > 2σ(I)

R int = 0.062

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.131

S = 1.07

2200 reflections

128 parameters

H-atom parameters constrained

Δρmax = 2.11 e Å−3

Δρmin = −2.04 e Å−3

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810036299/pk2266sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036299/pk2266Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ru(C7H8)(C10H15)]PF6	F(000) = 952
Mr = 473.39	Dx = 1.696 Mg m−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 11870 reflections
a = 13.9735 (4) Å	θ = 2.7–27.5°
b = 15.3266 (4) Å	µ = 0.99 mm−1
c = 8.6576 (6) Å	T = 150 K
V = 1854.17 (15) Å3	Block, colourless
Z = 4	0.22 × 0.15 × 0.10 mm

Nonius KappaCCD diffractometer	2200 independent reflections
Radiation source: fine-focus sealed tube	1611 reflections with I > 2σ(I)
graphite	Rint = 0.062
Detector resolution: 9 pixels mm-1	θmax = 27.5°, θmin = 2.7°
φ scans and ω scans with κ offsets	h = −17→18
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −15→19
Tmin = 0.711, Tmax = 0.863	l = −11→11
11870 measured reflections

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.065P)2 + 3.7819P] where P = (Fo2 + 2Fc2)/3
2200 reflections	(Δ/σ)max = 0.003
128 parameters	Δρmax = 2.11 e Å−3
0 restraints	Δρmin = −2.03 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ru1	0.09419 (3)	0.2500	0.05036 (5)	0.02470 (18)
C1	−0.0364 (4)	0.2500	0.1948 (8)	0.0364 (15)
H1	−0.0414	0.2500	0.3042	0.044*
C2	−0.0326 (3)	0.1709 (3)	0.1144 (5)	0.0329 (10)
H2A	−0.0235	0.1153	0.1730	0.040*
C3	−0.0226 (3)	0.1708 (3)	−0.0472 (5)	0.0318 (10)
H3A	−0.0065	0.1147	−0.1005	0.038*
C4	−0.0174 (4)	0.2500	−0.1323 (7)	0.0300 (13)
C5	0.2303 (3)	0.2969 (3)	−0.0428 (5)	0.0266 (9)
C6	0.2204 (3)	0.3259 (3)	0.1143 (5)	0.0266 (9)
C7	0.2144 (4)	0.2500	0.2112 (7)	0.0267 (13)
C8	−0.0027 (5)	0.2500	−0.3057 (7)	0.0393 (16)
H8A	−0.0634	0.2363	−0.3571	0.059*	0.50
H8B	0.0452	0.2060	−0.3333	0.059*	0.50
H8C	0.0194	0.3077	−0.3389	0.059*	0.50
C9	0.2427 (3)	0.3550 (3)	−0.1801 (6)	0.0391 (11)
H9A	0.3097	0.3733	−0.1875	0.059*
H9B	0.2018	0.4065	−0.1689	0.059*
H9C	0.2247	0.3232	−0.2739	0.059*
C10	0.2220 (3)	0.4184 (3)	0.1676 (6)	0.0405 (12)
H10A	0.2883	0.4368	0.1846	0.061*
H10B	0.1860	0.4235	0.2644	0.061*
H10C	0.1926	0.4557	0.0888	0.061*
C11	0.2061 (4)	0.2500	0.3875 (8)	0.0399 (16)
H11A	0.1816	0.3066	0.4224	0.060*	0.50
H11B	0.2692	0.2397	0.4331	0.060*	0.50
H11C	0.1620	0.2037	0.4200	0.060*	0.50
P1	0.0000	0.5000	0.5000	0.0282 (4)
F1	−0.09922 (18)	0.5503 (2)	0.4824 (4)	0.0454 (7)
F2	0.0208 (2)	0.51551 (18)	0.3204 (3)	0.0450 (7)
F3	−0.0520 (2)	0.40978 (18)	0.4592 (3)	0.0435 (7)

	U11	U22	U33	U12	U13	U23
Ru1	0.0238 (3)	0.0249 (3)	0.0255 (3)	0.000	0.00149 (19)	0.000
C1	0.024 (3)	0.052 (4)	0.033 (4)	0.000	0.005 (3)	0.000
C2	0.026 (2)	0.034 (2)	0.039 (3)	−0.0065 (18)	−0.0021 (19)	0.011 (2)
C3	0.028 (2)	0.031 (2)	0.036 (3)	−0.0049 (18)	−0.0049 (18)	−0.002 (2)
C4	0.026 (3)	0.038 (4)	0.025 (3)	0.000	−0.004 (2)	0.000
C5	0.023 (2)	0.029 (2)	0.028 (2)	−0.0033 (17)	0.0042 (16)	0.0022 (18)
C6	0.0190 (19)	0.033 (2)	0.028 (2)	−0.0030 (17)	0.0053 (16)	−0.0073 (18)
C7	0.021 (3)	0.040 (3)	0.019 (3)	0.000	−0.001 (2)	0.000
C8	0.042 (4)	0.052 (4)	0.024 (3)	0.000	−0.003 (3)	0.000
C9	0.041 (3)	0.042 (3)	0.035 (3)	−0.001 (2)	0.007 (2)	0.012 (2)
C10	0.037 (2)	0.036 (3)	0.049 (3)	−0.005 (2)	0.011 (2)	−0.011 (2)
C11	0.025 (3)	0.046 (4)	0.049 (4)	0.000	0.011 (3)	0.000
P1	0.0331 (8)	0.0276 (8)	0.0240 (8)	0.0019 (6)	0.0018 (7)	−0.0006 (7)
F1	0.0403 (16)	0.0456 (18)	0.0502 (18)	0.0127 (12)	−0.0027 (13)	−0.0017 (14)
F2	0.0653 (18)	0.0425 (16)	0.0273 (14)	−0.0008 (14)	0.0050 (13)	−0.0005 (13)
F3	0.0556 (18)	0.0311 (15)	0.0438 (17)	−0.0070 (13)	−0.0045 (13)	−0.0018 (12)

Ru1—C7	2.181 (5)	C6—C7	1.436 (5)
Ru1—C6	2.184 (4)	C6—C10	1.491 (6)
Ru1—C6i	2.184 (4)	C7—C6i	1.436 (5)
Ru1—C5	2.187 (4)	C7—C11	1.531 (9)
Ru1—C5i	2.187 (4)	C8—H8A	0.9800
Ru1—C3	2.203 (4)	C8—H8B	0.9800
Ru1—C3i	2.203 (4)	C8—H8C	0.9800
Ru1—C1	2.211 (6)	C9—H9A	0.9800
Ru1—C2	2.217 (4)	C9—H9B	0.9800
Ru1—C2i	2.217 (4)	C9—H9C	0.9800
Ru1—C4	2.220 (6)	C10—H10A	0.9800
C1—C2	1.398 (6)	C10—H10B	0.9800
C1—C2i	1.398 (6)	C10—H10C	0.9800
C1—H1	0.9500	C11—H11A	0.9800
C2—C3	1.406 (6)	C11—H11B	0.9800
C2—H2A	1.0000	C11—H11C	0.9800
C3—C4	1.422 (6)	P1—F1ii	1.594 (3)
C3—H3A	1.0000	P1—F1	1.594 (3)
C4—C3i	1.422 (6)	P1—F2ii	1.599 (3)
C4—C8	1.515 (9)	P1—F2	1.599 (3)
C5—C6	1.437 (6)	P1—F3ii	1.601 (3)
C5—C5i	1.437 (9)	P1—F3	1.601 (3)
C5—C9	1.495 (6)
C7—Ru1—C6	38.42 (14)	C2—C3—Ru1	72.0 (2)
C7—Ru1—C6i	38.42 (14)	C4—C3—Ru1	71.9 (3)
C6—Ru1—C6i	64.3 (2)	C2—C3—H3A	118.9
C7—Ru1—C5	64.28 (17)	C4—C3—H3A	118.9
C6—Ru1—C5	38.40 (15)	Ru1—C3—H3A	118.9
C6i—Ru1—C5	64.29 (15)	C3i—C4—C3	117.3 (6)
C7—Ru1—C5i	64.28 (17)	C3i—C4—C8	121.3 (3)
C6—Ru1—C5i	64.29 (15)	C3—C4—C8	121.3 (3)
C6i—Ru1—C5i	38.40 (15)	C3i—C4—Ru1	70.6 (3)
C5—Ru1—C5i	38.4 (2)	C3—C4—Ru1	70.6 (3)
C7—Ru1—C3	144.60 (13)	C8—C4—Ru1	127.7 (4)
C6—Ru1—C3	171.56 (16)	C6—C5—C5i	108.0 (2)
C6i—Ru1—C3	113.71 (17)	C6—C5—C9	125.4 (4)
C5—Ru1—C3	133.16 (16)	C5i—C5—C9	126.5 (3)
C5i—Ru1—C3	108.77 (17)	C6—C5—Ru1	70.7 (2)
C7—Ru1—C3i	144.60 (13)	C5i—C5—Ru1	70.81 (11)
C6—Ru1—C3i	113.71 (17)	C9—C5—Ru1	126.1 (3)
C6i—Ru1—C3i	171.56 (16)	C5—C6—C7	107.9 (4)
C5—Ru1—C3i	108.77 (17)	C5—C6—C10	125.8 (4)
C5i—Ru1—C3i	133.16 (16)	C7—C6—C10	126.2 (4)
C3—Ru1—C3i	66.9 (2)	C5—C6—Ru1	70.9 (2)
C7—Ru1—C1	105.9 (2)	C7—C6—Ru1	70.7 (3)
C6—Ru1—C1	121.52 (17)	C10—C6—Ru1	126.6 (3)
C6i—Ru1—C1	121.52 (17)	C6i—C7—C6	108.1 (5)
C5—Ru1—C1	157.77 (14)	C6i—C7—C11	125.9 (2)
C5i—Ru1—C1	157.77 (14)	C6—C7—C11	125.9 (2)
C3—Ru1—C1	66.77 (19)	C6i—C7—Ru1	70.9 (3)
C3i—Ru1—C1	66.77 (19)	C6—C7—Ru1	70.9 (3)
C7—Ru1—C2	117.11 (16)	C11—C7—Ru1	125.3 (4)
C6—Ru1—C2	150.82 (17)	C4—C8—H8A	109.5
C6i—Ru1—C2	106.93 (16)	C4—C8—H8B	109.5
C5—Ru1—C2	165.19 (17)	H8A—C8—H8B	109.5
C5i—Ru1—C2	127.41 (17)	C4—C8—H8C	109.5
C3—Ru1—C2	37.09 (17)	H8A—C8—H8C	109.5
C3i—Ru1—C2	78.75 (17)	H8B—C8—H8C	109.5
C1—Ru1—C2	36.81 (14)	C5—C9—H9A	109.5
C7—Ru1—C2i	117.11 (16)	C5—C9—H9B	109.5
C6—Ru1—C2i	106.93 (16)	H9A—C9—H9B	109.5
C6i—Ru1—C2i	150.82 (17)	C5—C9—H9C	109.5
C5—Ru1—C2i	127.41 (17)	H9A—C9—H9C	109.5
C5i—Ru1—C2i	165.19 (17)	H9B—C9—H9C	109.5
C3—Ru1—C2i	78.75 (17)	C6—C10—H10A	109.5
C3i—Ru1—C2i	37.09 (17)	C6—C10—H10B	109.5
C1—Ru1—C2i	36.81 (14)	H10A—C10—H10B	109.5
C2—Ru1—C2i	66.3 (2)	C6—C10—H10C	109.5
C7—Ru1—C4	174.3 (2)	H10A—C10—H10C	109.5
C6—Ru1—C4	138.37 (15)	H10B—C10—H10C	109.5
C6i—Ru1—C4	138.37 (15)	C7—C11—H11A	109.5
C5—Ru1—C4	110.35 (18)	C7—C11—H11B	109.5
C5i—Ru1—C4	110.35 (18)	H11A—C11—H11B	109.5
C3—Ru1—C4	37.51 (13)	C7—C11—H11C	109.5
C3i—Ru1—C4	37.51 (13)	H11A—C11—H11C	109.5
C1—Ru1—C4	79.8 (2)	H11B—C11—H11C	109.5
C2—Ru1—C4	67.48 (17)	F1ii—P1—F1	180.000 (1)
C2i—Ru1—C4	67.48 (17)	F1ii—P1—F2ii	89.60 (15)
C2—C1—C2i	120.1 (6)	F1—P1—F2ii	90.40 (15)
C2—C1—Ru1	71.8 (3)	F1ii—P1—F2	90.40 (15)
C2i—C1—Ru1	71.8 (3)	F1—P1—F2	89.60 (15)
C2—C1—H1	119.9	F2ii—P1—F2	180.000 (1)
C2i—C1—H1	119.9	F1ii—P1—F3ii	90.12 (16)
Ru1—C1—H1	128.7	F1—P1—F3ii	89.88 (16)
C1—C2—C3	120.1 (4)	F2ii—P1—F3ii	89.79 (14)
C1—C2—Ru1	71.4 (3)	F2—P1—F3ii	90.21 (14)
C3—C2—Ru1	70.9 (2)	F1ii—P1—F3	89.88 (16)
C1—C2—H2A	119.4	F1—P1—F3	90.12 (16)
C3—C2—H2A	119.4	F2ii—P1—F3	90.21 (14)
Ru1—C2—H2A	119.4	F2—P1—F3	89.79 (14)
C2—C3—C4	121.2 (4)	F3ii—P1—F3	180.0

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···F2i	1.00	2.46	3.450 (4)	173
C2—H2A···F3i	1.00	2.54	3.243 (5)	127
C3—H3A···F2iii	1.00	2.44	3.356 (5)	151
C8—H8C···F3iv	0.98	2.55	3.258 (5)	129
C10—H10B···F1ii	0.98	2.54	3.515 (6)	175

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯F2i	1.00	2.46	3.450 (4)	173
C2—H2A⋯F3i	1.00	2.54	3.243 (5)	127
C3—H3A⋯F2ii	1.00	2.44	3.356 (5)	151
C8—H8C⋯F3iii	0.98	2.55	3.258 (5)	129
C10—H10B⋯F1iv	0.98	2.54	3.515 (6)	175

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .