(η5-Cyclo­penta­dien­yl)(η6-mesitylamine)ruthenium(II) hexa­fluorido­phosphate

Becker, E.; Kirchner, K.; Mereiter, K.

doi:10.1107/S1600536809016894

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page m631

doi:10.1107/S1600536809016894

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(η⁵-Cyclopentadienyl)(η⁶-mesitylamine)ruthenium(II) hexafluoridophosphate

Eva Becker,^a Karl Kirchner ^a and Kurt Mereiter ^b ^*

^aInstitute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9/163, A-1060 Vienna, Austria, and ^bInstitute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/164SC, A-1060 Vienna, Austria
^*Correspondence e-mail: kurt.mereiter@tuwien.ac.at

(Received 27 April 2009; accepted 5 May 2009; online 14 May 2009)

The title compound, [Ru(η⁵-C₅H₅){η⁶-C₆H₂(CH₃)₃NH₂}]PF₆, contains a sandwich complex with a mesitylamine unit which is significantly non-planar at the ipso-carbon of the amino group due to repulsive electronic effects with Ru. The ipso-carbon deviates by 0.107 (3) Å from the least-squares plane of the remaining five benzene ring atoms, which show an r.m.s. deviation of 0.005 Å. N—H⋯F hydrogen-bonding interactions help to consolidate the crystal packing.

Related literature

For general background and a related structure with —N(CH₃)₂ instead of —NH₂, see: Standfest-Hauser et al. (2003 ). For related chromium arene complexes, see: Djukic et al. (2000 ); Hunter et al. (1992 ). For synthetic details, see: Gill & Mann (1982 ); Kündig & Monnier (2004 ).

Experimental

Crystal data

[Ru(C₅H₅)(C₉H₁₃N)]PF₆
M_r = 446.33
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.5119 (4) Å
b = 10.2047 (6) Å
c = 21.1818 (12) Å
V = 1623.73 (16) Å³
Z = 4
Mo Kα radiation
μ = 1.12 mm⁻¹
T = 173 K
0.55 × 0.30 × 0.26 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.62, T_max = 0.75
24305 measured reflections
4741 independent reflections
4650 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.055
S = 1.12
4741 reflections
218 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.41 e Å⁻³
Absolute structure: Flack (1983 ), 2202 Friedel pairs
Flack parameter: 0.21 (3)

Table 1
Selected bond lengths (Å)

Ru—C1	2.179 (2)
Ru—C2	2.164 (2)
Ru—C3	2.179 (3)
Ru—C4	2.181 (3)
Ru—C5	2.187 (3)
Ru—C6	2.314 (2)
Ru—C7	2.212 (2)
Ru—C8	2.178 (2)
Ru—C9	2.214 (2)
Ru—C10	2.185 (2)
Ru—C11	2.229 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H1A⋯F1	0.87 (2)	2.26 (2)	3.106 (3)	163 (3)
N—H1B⋯F5ⁱ	0.87 (2)	2.43 (3)	3.174 (3)	143 (3)
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809016894/gk2208sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016894/gk2208Isup2.hkl

checkCIF report

Comment top

We have shown (Standfest-Hauser et al., 2003) that arene amines hapto-6-coordinated to a cyclopentadienylruthenium fragment (CpRu) are not planar but display a significant shift of the ipso-carbon bearing the amino substituent out of the mean aromatic plane away from the CpRu fragment by about 0.1 to 0.2 Å. This corresponds to a envelope-type folding of the ring by 7–15° for the interplanar angle. The same effect was previously reported for chromium arene complexes (Hunter et al., 1992; Djukic, et al., 2000). Recently, we obtained the title compound, (I), in a crystalline form. This offered the opportunity to study the mentioned effect for a compound with NH₂ instead of N(CH₃)₂. In (I) the cyclopentadienyl ring and the 5-membered ring segment C7—C8—C9—C10—C11 are almost perfectly planar (r.m.s. aplanarities 0.006 and 0.005 Å, respectively) and mutually inclined by 1.0 (1)° (Fig. 1). The ipso-carbon C6 and the amino nitrogen deviate by 0.107 (3) and 0.172 (4) Å, respectively, from ring segment plane and both are bent away from the CpRu fragment. Thus the envelope-type ring folding angle, measured between planes C7—C6—C11 and C7—C8—C9—C10—C11, is 8.3 (3)°. According to FT/B3LYP calculations (Standfest-Hauser et al., 2003) the reason for this envelope deformation of the benzene ring is that the surplus of π-electron density at C6 arising from the π-donor substituent NH₂ becomes less pronounced and a 8° folding was predicted for free [CpRu(η⁶-C₆H₅NH₂)]⁺. These quantities are comparable with the experimental data of [CpRu(η⁶-C₆H₅N(CH₃)₂)]PF₆ (Standfest-Hauser et al., 2003), 0.125 (3) Å (deviation of the ipso-C from the plane of the remaining ring atoms) and 10° (envelope-type ring folding angle), respectively. In this compound and its 2-dimethylamino-pyridine congener, the N-bound methyl groups are bent toward the CpRu moieties due to predicted orbital repulsion effects between dimethylamino nitrogen and ipso-carbon. This differs from (I), where the hydrogen atoms are bent off from the CpRu moiety and the nitrogen behaves more pyramidal. We attribute this deviation to the formation of two N—H···F hydrogen bonds (Fig. 1 and Table 2), absent in the dimethylamino compounds. As shown in Fig. 2, these bonds form zigzag chains along the b axis of (I). Further structural coherence is provided by π-π-stacking between Ru complexes, which form columns along the a axis with short stacking distances such as C4—C6(1 + x,y,z) = 3.482 (4) Å and C3—C7(1 + x,y,z) = 3.572 (4) Å. Weak C—H···F interactions donated by methyl, Cp and arene H-atoms stiffen the structure too, e.g. C3···F6(1 - x,-1/2 + y,1/2 - z) = 3.280 (4) Å.

Related literature top

For general background, see: Djukic et al. (2000); Hunter et al. (1992); Standfest-Hauser et al. (2003); Gill & Mann (1982); Kündig & Monnier (2004).

Experimental top

To a solution of [CpRu(CH₃CN)₃]PF₆ (Gill, & Mann, 1982; Kündig & Monnier, 2004; 120 mg, 0.276 mmol) in CH₂Cl₂ (5 ml) mesitylamine (41 µL, 0.290 mmol) was added. After the mixture was stirred at room temperature for 1 h, the solvent was removed under vacuum and the resulting white solid of (I) was collected on a glass frit and washed twice with diethyl ether (10 ml). Yield: 118 mg (96%). ¹H NMR (δ, acetone-d₆, 20°C): 6.02 (s, 2H, Mes^3,5), 5.13 (bs, 2H, NH₂), 5.09 (s, 5H, Cp), 2.31 (s, 6H, Me^2,6), 2.17 (s, 3H, Me⁴). ¹³C{¹H} NMR (δ, acetone-d₆, 20°C): 123.3 (1 C, Mes¹), 94.9 (1 C, Mes⁴), 87.0 (2 C, Mes^2,6), 83.7 (2 C, Mes^3,5), 79.9 (5 C, Cp), 18.5 (1 C, Me⁴), 16.8 (2 C, Me^2,6). Colourless crystals of (I) were grown from CH₂Cl₂ using vapour diffusion of diethyl ether at room temperature.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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: SHELXTL (Sheldrick, 2008)'.

Figures top

	Fig. 1. Perspective view of (I). Displacement ellipsoids shown at the 40% probability level. The sideview of the Ru complex on the lower left depicts the out-of-plane displacements of C6 and N. The red numbers give the deviations (Å) of the respective atoms from the least-squares plane C7—C8—C9—C10—C11. F5A corresponds to F5ⁱ of Table 2.
	Fig. 2. Packing diagram of (I), viewed down a, with N—H···F bonds as dashed lines. Carbon-bound H atoms omitted.

(η⁵-Cyclopentadienyl)(η⁶-mesitylamine)ruthenium(II) hexafluoridophosphate top

Crystal data top

[Ru(C₅H₅)(C₉H₁₃N)]F₆P	F(000) = 888
M_r = 446.33	D_x = 1.826 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7583 reflections
a = 7.5119 (4) Å	θ = 2.2–30.0°
b = 10.2047 (6) Å	µ = 1.12 mm⁻¹
c = 21.1818 (12) Å	T = 173 K
V = 1623.73 (16) Å³	Prism, colourless
Z = 4	0.55 × 0.30 × 0.26 mm

Data collection top

Bruker SMART CCD diffractometer	4741 independent reflections
Radiation source: fine-focus sealed tube	4650 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω scans	θ_max = 30.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −10→10
T_min = 0.62, T_max = 0.75	k = −14→14
24305 measured reflections	l = −29→29

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.055	w = 1/[σ²(F_o²) + (0.0228P)² + 0.8717P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max = 0.001
4741 reflections	Δρ_max = 0.65 e Å⁻³
218 parameters	Δρ_min = −0.41 e Å⁻³
1 restraint	Absolute structure: Flack, (1983), 2202 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.21 (3)

Crystal data top

[Ru(C₅H₅)(C₉H₁₃N)]F₆P	V = 1623.73 (16) Å³
M_r = 446.33	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.5119 (4) Å	µ = 1.12 mm⁻¹
b = 10.2047 (6) Å	T = 173 K
c = 21.1818 (12) Å	0.55 × 0.30 × 0.26 mm

Data collection top

Bruker SMART CCD diffractometer	4741 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	4650 reflections with I > 2σ(I)
T_min = 0.62, T_max = 0.75	R_int = 0.026
24305 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.055	Δρ_max = 0.65 e Å⁻³
S = 1.12	Δρ_min = −0.41 e Å⁻³
4741 reflections	Absolute structure: Flack, (1983), 2202 Friedel pairs
218 parameters	Absolute structure parameter: 0.21 (3)
1 restraint

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
Ru	0.62135 (2)	0.480064 (16)	0.128280 (7)	0.02275 (4)
C1	0.7945 (3)	0.6499 (2)	0.11758 (13)	0.0375 (5)
H1	0.7526	0.7358	0.1088	0.045*
C2	0.8399 (3)	0.5545 (3)	0.07219 (14)	0.0401 (6)
H2	0.8323	0.5645	0.0277	0.048*
C3	0.8987 (4)	0.4415 (3)	0.10452 (14)	0.0431 (6)
H3	0.9400	0.3629	0.0855	0.052*
C4	0.8854 (4)	0.4655 (3)	0.17054 (13)	0.0427 (6)
H4	0.9136	0.4057	0.2034	0.051*
C5	0.8217 (3)	0.5963 (3)	0.17799 (13)	0.0388 (6)
H5	0.8012	0.6397	0.2170	0.047*
N	0.2758 (3)	0.6420 (2)	0.19495 (11)	0.0374 (5)
H1A	0.237 (4)	0.625 (3)	0.2330 (10)	0.045*
H1B	0.219 (4)	0.699 (3)	0.1717 (13)	0.045*
C6	0.3383 (3)	0.5357 (2)	0.16198 (11)	0.0284 (4)
C7	0.3543 (3)	0.5395 (2)	0.09480 (11)	0.0293 (5)
C8	0.4115 (3)	0.4252 (2)	0.06244 (11)	0.0308 (5)
H8	0.4138	0.4263	0.0176	0.037*
C9	0.4649 (3)	0.3105 (2)	0.09396 (11)	0.0299 (5)
C10	0.4628 (3)	0.3137 (2)	0.16078 (11)	0.0278 (4)
H10	0.5012	0.2384	0.1833	0.033*
C11	0.4056 (3)	0.4246 (2)	0.19536 (10)	0.0265 (4)
C12	0.3062 (4)	0.6610 (3)	0.05839 (14)	0.0426 (6)
H12A	0.1773	0.6752	0.0607	0.064*
H12B	0.3416	0.6503	0.0142	0.064*
H12C	0.3683	0.7366	0.0765	0.064*
C13	0.5281 (4)	0.1920 (3)	0.05904 (13)	0.0418 (6)
H13A	0.4266	0.1347	0.0500	0.063*
H13B	0.6149	0.1446	0.0849	0.063*
H13C	0.5840	0.2190	0.0193	0.063*
C14	0.4080 (4)	0.4215 (3)	0.26627 (10)	0.0373 (5)
H14A	0.2864	0.4101	0.2821	0.056*
H14B	0.4570	0.5041	0.2823	0.056*
H14C	0.4822	0.3484	0.2806	0.056*
P	−0.05498 (8)	0.52386 (6)	0.36805 (3)	0.02999 (11)
F1	0.0612 (3)	0.6046 (2)	0.31902 (9)	0.0629 (6)
F2	−0.1653 (4)	0.4427 (2)	0.41838 (11)	0.0828 (8)
F3	−0.2304 (3)	0.5675 (2)	0.33379 (11)	0.0746 (7)
F4	0.1256 (3)	0.4786 (2)	0.40177 (8)	0.0631 (5)
F5	−0.0414 (3)	0.39806 (18)	0.32320 (9)	0.0553 (5)
F6	−0.0659 (3)	0.64704 (17)	0.41381 (8)	0.0499 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru	0.02249 (6)	0.02258 (7)	0.02320 (7)	−0.00058 (6)	0.00164 (6)	−0.00027 (6)
C1	0.0313 (11)	0.0299 (11)	0.0513 (16)	−0.0078 (9)	0.0047 (11)	−0.0006 (10)
C2	0.0343 (13)	0.0432 (15)	0.0427 (14)	−0.0109 (10)	0.0131 (10)	−0.0033 (11)
C3	0.0276 (12)	0.0408 (13)	0.0611 (16)	0.0041 (10)	0.0135 (11)	−0.0093 (11)
C4	0.0251 (10)	0.0511 (16)	0.0518 (14)	−0.0046 (14)	−0.0064 (11)	0.0103 (12)
C5	0.0288 (11)	0.0484 (16)	0.0390 (13)	−0.0084 (10)	−0.0021 (10)	−0.0113 (12)
N	0.0328 (11)	0.0345 (11)	0.0448 (13)	0.0059 (9)	0.0059 (9)	−0.0055 (9)
C6	0.0225 (9)	0.0272 (11)	0.0355 (11)	−0.0014 (8)	0.0028 (7)	−0.0007 (9)
C7	0.0233 (10)	0.0301 (12)	0.0345 (11)	0.0011 (9)	−0.0039 (8)	0.0036 (8)
C8	0.0309 (12)	0.0350 (11)	0.0264 (10)	−0.0030 (9)	−0.0019 (8)	−0.0008 (9)
C9	0.0309 (12)	0.0277 (11)	0.0310 (11)	−0.0055 (9)	−0.0006 (9)	−0.0031 (9)
C10	0.0296 (11)	0.0227 (10)	0.0309 (11)	−0.0029 (9)	0.0028 (9)	0.0036 (8)
C11	0.0226 (10)	0.0294 (10)	0.0275 (10)	−0.0026 (8)	0.0025 (8)	−0.0007 (8)
C12	0.0407 (14)	0.0400 (14)	0.0472 (15)	0.0078 (12)	−0.0066 (12)	0.0126 (12)
C13	0.0531 (16)	0.0315 (13)	0.0407 (14)	−0.0017 (12)	0.0040 (12)	−0.0098 (10)
C14	0.0424 (14)	0.0413 (13)	0.0282 (11)	0.0009 (11)	0.0072 (9)	0.0003 (9)
P	0.0352 (3)	0.0283 (2)	0.0265 (2)	−0.0024 (2)	0.0010 (2)	−0.0034 (3)
F1	0.0797 (14)	0.0524 (11)	0.0566 (11)	−0.0027 (10)	0.0338 (10)	0.0086 (9)
F2	0.113 (2)	0.0541 (12)	0.0812 (14)	−0.0239 (12)	0.0484 (15)	0.0043 (10)
F3	0.0539 (11)	0.0992 (17)	0.0708 (13)	0.0344 (12)	−0.0239 (10)	−0.0324 (12)
F4	0.0666 (11)	0.0686 (12)	0.0541 (10)	0.0186 (13)	−0.0253 (9)	−0.0099 (9)
F5	0.0627 (11)	0.0458 (10)	0.0574 (11)	0.0050 (9)	−0.0066 (9)	−0.0271 (9)
F6	0.0722 (12)	0.0392 (8)	0.0381 (8)	−0.0013 (8)	0.0039 (8)	−0.0153 (7)

Geometric parameters (Å, º) top

Ru—C1	2.179 (2)	C4—C5	1.427 (4)
Ru—C2	2.164 (2)	C4—H4	0.9500
Ru—C3	2.179 (3)	C5—H5	0.9500
Ru—C4	2.181 (3)	N—H1A	0.87 (2)
Ru—C5	2.187 (3)	N—H1B	0.87 (2)
Ru—C6	2.314 (2)	C7—C12	1.505 (3)
Ru—C7	2.212 (2)	C8—H8	0.9500
Ru—C8	2.178 (2)	C9—C13	1.495 (3)
Ru—C9	2.214 (2)	C10—H10	0.9500
Ru—C10	2.185 (2)	C11—C14	1.503 (3)
Ru—C11	2.229 (2)	C12—H12A	0.9800
C6—N	1.373 (3)	C12—H12B	0.9800
C6—C7	1.429 (3)	C12—H12C	0.9800
C6—C11	1.428 (3)	C13—H13A	0.9800
C7—C8	1.419 (3)	C13—H13B	0.9800
C11—C10	1.415 (3)	C13—H13C	0.9800
C8—C9	1.406 (3)	C14—H14A	0.9800
C10—C9	1.416 (3)	C14—H14B	0.9800
C1—C5	1.406 (4)	C14—H14C	0.9800
C1—C2	1.410 (4)	P—F3	1.569 (2)
C1—H1	0.9500	P—F2	1.584 (2)
C2—C3	1.412 (4)	P—F1	1.5876 (18)
C2—H2	0.9500	P—F6	1.5894 (16)
C3—C4	1.423 (4)	P—F5	1.6002 (17)
C3—H3	0.9500	P—F4	1.6014 (19)

C2—Ru—C8	106.72 (10)	C1—C5—C4	108.2 (2)
C2—Ru—C1	37.90 (10)	C1—C5—Ru	70.90 (14)
C8—Ru—C1	124.74 (10)	C4—C5—Ru	70.72 (16)
C2—Ru—C3	37.94 (11)	C1—C5—H5	125.9
C8—Ru—C3	119.84 (10)	C4—C5—H5	125.9
C1—Ru—C3	63.19 (10)	Ru—C5—H5	124.1
C2—Ru—C4	63.86 (11)	C6—N—H1A	115 (2)
C8—Ru—C4	154.62 (10)	C6—N—H1B	114 (2)
C1—Ru—C4	63.52 (10)	H1A—N—H1B	120 (3)
C3—Ru—C4	38.10 (11)	N—C6—C11	119.8 (2)
C2—Ru—C10	149.22 (10)	N—C6—C7	120.9 (2)
C8—Ru—C10	66.89 (9)	C11—C6—C7	119.0 (2)
C1—Ru—C10	167.48 (9)	N—C6—Ru	131.66 (17)
C3—Ru—C10	116.98 (10)	C11—C6—Ru	68.45 (12)
C4—Ru—C10	108.27 (10)	C7—C6—Ru	67.78 (13)
C2—Ru—C5	63.38 (10)	C8—C7—C6	119.0 (2)
C8—Ru—C5	161.08 (10)	C8—C7—C12	120.2 (2)
C1—Ru—C5	37.59 (10)	C6—C7—C12	120.9 (2)
C3—Ru—C5	63.34 (10)	C8—C7—Ru	69.83 (13)
C4—Ru—C5	38.14 (11)	C6—C7—Ru	75.51 (13)
C10—Ru—C5	130.17 (10)	C12—C7—Ru	127.45 (17)
C2—Ru—C7	114.56 (11)	C9—C8—C7	122.7 (2)
C8—Ru—C7	37.71 (9)	C9—C8—Ru	72.73 (13)
C1—Ru—C7	106.85 (9)	C7—C8—Ru	72.46 (13)
C3—Ru—C7	147.39 (11)	C9—C8—H8	118.6
C4—Ru—C7	167.10 (10)	C7—C8—H8	118.6
C10—Ru—C7	79.60 (9)	Ru—C8—H8	128.6
C5—Ru—C7	129.03 (10)	C8—C9—C10	116.9 (2)
C2—Ru—C9	119.77 (10)	C8—C9—C13	121.9 (2)
C8—Ru—C9	37.34 (9)	C10—C9—C13	121.1 (2)
C1—Ru—C9	154.73 (10)	C8—C9—Ru	69.93 (13)
C3—Ru—C9	106.88 (10)	C10—C9—Ru	70.12 (14)
C4—Ru—C9	124.33 (10)	C13—C9—Ru	128.78 (18)
C10—Ru—C9	37.54 (8)	C11—C10—C9	122.7 (2)
C5—Ru—C9	161.32 (10)	C11—C10—Ru	72.98 (13)
C7—Ru—C9	68.15 (9)	C9—C10—Ru	72.34 (14)
C2—Ru—C11	172.26 (10)	C11—C10—H10	118.7
C8—Ru—C11	79.43 (8)	C9—C10—H10	118.7
C1—Ru—C11	134.63 (9)	Ru—C10—H10	128.4
C3—Ru—C11	142.82 (10)	C10—C11—C6	119.1 (2)
C4—Ru—C11	112.48 (10)	C10—C11—C14	119.8 (2)
C10—Ru—C11	37.37 (8)	C6—C11—C14	121.0 (2)
C5—Ru—C11	109.35 (9)	C10—C11—Ru	69.65 (12)
C7—Ru—C11	67.32 (8)	C6—C11—Ru	74.95 (12)
C9—Ru—C11	67.97 (9)	C14—C11—Ru	129.33 (16)
C2—Ru—C6	141.31 (11)	C7—C12—H12A	109.5
C8—Ru—C6	66.13 (8)	C7—C12—H12B	109.5
C1—Ru—C6	112.69 (9)	H12A—C12—H12B	109.5
C3—Ru—C6	173.84 (10)	C7—C12—H12C	109.5
C4—Ru—C6	136.54 (10)	H12A—C12—H12C	109.5
C10—Ru—C6	65.93 (9)	H12B—C12—H12C	109.5
C5—Ru—C6	110.54 (10)	C9—C13—H13A	109.5
C7—Ru—C6	36.71 (8)	C9—C13—H13B	109.5
C9—Ru—C6	78.77 (9)	H13A—C13—H13B	109.5
C11—Ru—C6	36.59 (8)	C9—C13—H13C	109.5
C5—C1—C2	108.5 (2)	H13A—C13—H13C	109.5
C5—C1—Ru	71.51 (14)	H13B—C13—H13C	109.5
C2—C1—Ru	70.50 (13)	C11—C14—H14A	109.5
C5—C1—H1	125.8	C11—C14—H14B	109.5
C2—C1—H1	125.8	H14A—C14—H14B	109.5
Ru—C1—H1	123.8	C11—C14—H14C	109.5
C1—C2—C3	108.0 (2)	H14A—C14—H14C	109.5
C1—C2—Ru	71.60 (14)	H14B—C14—H14C	109.5
C3—C2—Ru	71.60 (15)	F3—P—F2	91.16 (15)
C1—C2—H2	126.0	F3—P—F1	90.68 (13)
C3—C2—H2	126.0	F2—P—F1	178.11 (15)
Ru—C2—H2	122.5	F3—P—F6	90.80 (11)
C2—C3—C4	108.3 (2)	F2—P—F6	88.61 (11)
C2—C3—Ru	70.46 (15)	F1—P—F6	90.95 (10)
C4—C3—Ru	71.02 (17)	F3—P—F5	90.39 (11)
C2—C3—H3	125.8	F2—P—F5	90.78 (12)
C4—C3—H3	125.8	F1—P—F5	89.62 (11)
Ru—C3—H3	124.3	F6—P—F5	178.67 (11)
C3—C4—C5	107.1 (2)	F3—P—F4	178.94 (11)
C3—C4—Ru	70.88 (16)	F2—P—F4	89.55 (13)
C5—C4—Ru	71.14 (15)	F1—P—F4	88.61 (12)
C3—C4—H4	126.5	F6—P—F4	90.00 (10)
C5—C4—H4	126.5	F5—P—F4	88.81 (10)
Ru—C4—H4	123.2

C2—Ru—C1—C5	−118.2 (2)	C9—Ru—C7—C8	−28.13 (13)
C8—Ru—C1—C5	170.50 (15)	C11—Ru—C7—C8	−102.44 (14)
C3—Ru—C1—C5	−80.34 (18)	C6—Ru—C7—C8	−128.9 (2)
C4—Ru—C1—C5	−37.51 (16)	C2—Ru—C7—C6	−145.36 (16)
C10—Ru—C1—C5	13.6 (5)	C8—Ru—C7—C6	128.9 (2)
C7—Ru—C1—C5	133.24 (16)	C1—Ru—C7—C6	−105.54 (16)
C9—Ru—C1—C5	−152.4 (2)	C3—Ru—C7—C6	−171.90 (18)
C11—Ru—C1—C5	58.7 (2)	C4—Ru—C7—C6	−65.4 (5)
C6—Ru—C1—C5	94.62 (17)	C10—Ru—C7—C6	63.41 (15)
C8—Ru—C1—C2	−71.3 (2)	C5—Ru—C7—C6	−70.65 (19)
C3—Ru—C1—C2	37.87 (17)	C9—Ru—C7—C6	100.76 (16)
C4—Ru—C1—C2	80.71 (19)	C11—Ru—C7—C6	26.45 (14)
C10—Ru—C1—C2	131.8 (4)	C2—Ru—C7—C12	−27.4 (3)
C5—Ru—C1—C2	118.2 (2)	C8—Ru—C7—C12	−113.1 (3)
C7—Ru—C1—C2	−108.54 (18)	C1—Ru—C7—C12	12.5 (2)
C9—Ru—C1—C2	−34.2 (3)	C3—Ru—C7—C12	−53.9 (3)
C11—Ru—C1—C2	176.94 (17)	C4—Ru—C7—C12	52.6 (5)
C6—Ru—C1—C2	−147.16 (17)	C10—Ru—C7—C12	−178.6 (2)
C5—C1—C2—C3	−1.0 (3)	C5—Ru—C7—C12	47.3 (3)
Ru—C1—C2—C3	−62.76 (18)	C9—Ru—C7—C12	−141.3 (2)
C5—C1—C2—Ru	61.77 (17)	C11—Ru—C7—C12	144.4 (2)
C8—Ru—C2—C1	125.65 (17)	C6—Ru—C7—C12	118.0 (3)
C3—Ru—C2—C1	−117.0 (2)	C6—C7—C8—C9	−4.4 (3)
C4—Ru—C2—C1	−79.74 (18)	C12—C7—C8—C9	177.4 (2)
C10—Ru—C2—C1	−161.60 (18)	Ru—C7—C8—C9	55.0 (2)
C5—Ru—C2—C1	−36.96 (16)	C6—C7—C8—Ru	−59.47 (19)
C7—Ru—C2—C1	86.09 (18)	C12—C7—C8—Ru	122.4 (2)
C9—Ru—C2—C1	163.97 (15)	C2—Ru—C8—C9	117.45 (16)
C6—Ru—C2—C1	53.2 (2)	C1—Ru—C8—C9	154.86 (14)
C8—Ru—C2—C3	−117.38 (16)	C3—Ru—C8—C9	78.45 (17)
C1—Ru—C2—C3	117.0 (2)	C4—Ru—C8—C9	53.6 (3)
C4—Ru—C2—C3	37.23 (17)	C10—Ru—C8—C9	−30.45 (14)
C10—Ru—C2—C3	−44.6 (3)	C5—Ru—C8—C9	172.9 (3)
C5—Ru—C2—C3	80.01 (18)	C7—Ru—C8—C9	−133.8 (2)
C7—Ru—C2—C3	−156.94 (16)	C11—Ru—C8—C9	−67.38 (14)
C9—Ru—C2—C3	−79.06 (18)	C6—Ru—C8—C9	−103.23 (15)
C6—Ru—C2—C3	170.13 (16)	C2—Ru—C8—C7	−108.73 (15)
C1—C2—C3—C4	1.5 (3)	C1—Ru—C8—C7	−71.33 (16)
Ru—C2—C3—C4	−61.3 (2)	C3—Ru—C8—C7	−147.74 (14)
C1—C2—C3—Ru	62.76 (17)	C4—Ru—C8—C7	−172.6 (2)
C8—Ru—C3—C2	78.66 (18)	C10—Ru—C8—C7	103.36 (15)
C1—Ru—C3—C2	−37.84 (16)	C5—Ru—C8—C7	−53.2 (3)
C4—Ru—C3—C2	−118.3 (2)	C9—Ru—C8—C7	133.8 (2)
C10—Ru—C3—C2	156.21 (15)	C11—Ru—C8—C7	66.43 (13)
C5—Ru—C3—C2	−80.13 (18)	C6—Ru—C8—C7	30.58 (13)
C7—Ru—C3—C2	41.4 (3)	C7—C8—C9—C10	−1.1 (4)
C9—Ru—C3—C2	117.05 (16)	Ru—C8—C9—C10	53.8 (2)
C11—Ru—C3—C2	−167.35 (16)	C7—C8—C9—C13	−178.8 (2)
C2—Ru—C3—C4	118.3 (2)	Ru—C8—C9—C13	−123.9 (2)
C8—Ru—C3—C4	−163.01 (16)	C7—C8—C9—Ru	−54.9 (2)
C1—Ru—C3—C4	80.49 (18)	C2—Ru—C9—C8	−78.26 (18)
C10—Ru—C3—C4	−85.46 (18)	C1—Ru—C9—C8	−54.8 (3)
C5—Ru—C3—C4	38.20 (17)	C3—Ru—C9—C8	−117.37 (16)
C7—Ru—C3—C4	159.71 (16)	C4—Ru—C9—C8	−155.31 (15)
C9—Ru—C3—C4	−124.62 (16)	C10—Ru—C9—C8	130.1 (2)
C11—Ru—C3—C4	−49.0 (2)	C5—Ru—C9—C8	−172.9 (3)
C2—C3—C4—C5	−1.4 (3)	C7—Ru—C9—C8	28.40 (13)
Ru—C3—C4—C5	−62.34 (18)	C11—Ru—C9—C8	101.79 (14)
C2—C3—C4—Ru	60.90 (19)	C6—Ru—C9—C8	65.17 (14)
C2—Ru—C4—C3	−37.07 (16)	C2—Ru—C9—C10	151.65 (16)
C8—Ru—C4—C3	36.3 (3)	C8—Ru—C9—C10	−130.1 (2)
C1—Ru—C4—C3	−79.55 (17)	C1—Ru—C9—C10	175.1 (2)
C10—Ru—C4—C3	110.69 (16)	C3—Ru—C9—C10	112.54 (17)
C5—Ru—C4—C3	−116.5 (2)	C4—Ru—C9—C10	74.59 (19)
C7—Ru—C4—C3	−123.1 (4)	C5—Ru—C9—C10	57.1 (4)
C9—Ru—C4—C3	72.48 (19)	C7—Ru—C9—C10	−101.70 (17)
C11—Ru—C4—C3	150.41 (16)	C11—Ru—C9—C10	−28.30 (15)
C6—Ru—C4—C3	−175.33 (16)	C6—Ru—C9—C10	−64.92 (16)
C2—Ru—C4—C5	79.45 (17)	C2—Ru—C9—C13	37.1 (3)
C8—Ru—C4—C5	152.8 (2)	C8—Ru—C9—C13	115.4 (3)
C1—Ru—C4—C5	36.97 (16)	C1—Ru—C9—C13	60.6 (3)
C3—Ru—C4—C5	116.5 (2)	C3—Ru—C9—C13	−2.0 (3)
C10—Ru—C4—C5	−132.79 (16)	C4—Ru—C9—C13	−39.9 (3)
C7—Ru—C4—C5	−6.6 (5)	C10—Ru—C9—C13	−114.5 (3)
C9—Ru—C4—C5	−171.01 (15)	C5—Ru—C9—C13	−57.5 (4)
C11—Ru—C4—C5	−93.07 (17)	C7—Ru—C9—C13	143.8 (2)
C6—Ru—C4—C5	−58.8 (2)	C11—Ru—C9—C13	−142.8 (3)
C2—C1—C5—C4	0.1 (3)	C6—Ru—C9—C13	−179.4 (2)
Ru—C1—C5—C4	61.23 (18)	C8—C9—C10—C11	1.7 (4)
C2—C1—C5—Ru	−61.13 (17)	C13—C9—C10—C11	179.4 (2)
C3—C4—C5—C1	0.8 (3)	Ru—C9—C10—C11	55.3 (2)
Ru—C4—C5—C1	−61.34 (17)	C8—C9—C10—Ru	−53.7 (2)
C3—C4—C5—Ru	62.16 (19)	C13—C9—C10—Ru	124.0 (2)
C2—Ru—C5—C1	37.26 (16)	C2—Ru—C10—C11	172.73 (19)
C8—Ru—C5—C1	−24.7 (4)	C8—Ru—C10—C11	−103.31 (14)
C3—Ru—C5—C1	79.91 (17)	C1—Ru—C10—C11	56.2 (5)
C4—Ru—C5—C1	118.1 (2)	C3—Ru—C10—C11	143.74 (15)
C10—Ru—C5—C1	−176.17 (15)	C4—Ru—C10—C11	103.37 (15)
C7—Ru—C5—C1	−63.83 (19)	C5—Ru—C10—C11	66.99 (18)
C9—Ru—C5—C1	141.8 (3)	C7—Ru—C10—C11	−66.08 (14)
C11—Ru—C5—C1	−139.86 (15)	C9—Ru—C10—C11	−133.6 (2)
C6—Ru—C5—C1	−100.86 (16)	C6—Ru—C10—C11	−30.24 (13)
C2—Ru—C5—C4	−80.81 (17)	C2—Ru—C10—C9	−53.7 (3)
C8—Ru—C5—C4	−142.8 (3)	C8—Ru—C10—C9	30.29 (15)
C1—Ru—C5—C4	−118.1 (2)	C1—Ru—C10—C9	−170.2 (4)
C3—Ru—C5—C4	−38.16 (16)	C3—Ru—C10—C9	−82.65 (18)
C10—Ru—C5—C4	65.76 (19)	C4—Ru—C10—C9	−123.03 (17)
C7—Ru—C5—C4	178.10 (15)	C5—Ru—C10—C9	−159.41 (16)
C9—Ru—C5—C4	23.8 (4)	C7—Ru—C10—C9	67.52 (16)
C11—Ru—C5—C4	102.07 (16)	C11—Ru—C10—C9	133.6 (2)
C6—Ru—C5—C4	141.07 (16)	C6—Ru—C10—C9	103.36 (17)
C2—Ru—C6—N	−56.5 (3)	C9—C10—C11—C6	3.4 (4)
C8—Ru—C6—N	−143.7 (3)	Ru—C10—C11—C6	58.46 (18)
C1—Ru—C6—N	−24.3 (3)	C9—C10—C11—C14	−179.6 (2)
C4—Ru—C6—N	50.5 (3)	Ru—C10—C11—C14	−124.5 (2)
C10—Ru—C6—N	142.1 (3)	C9—C10—C11—Ru	−55.0 (2)
C5—Ru—C6—N	16.2 (3)	N—C6—C11—C10	177.5 (2)
C7—Ru—C6—N	−112.3 (3)	C7—C6—C11—C10	−9.0 (3)
C9—Ru—C6—N	179.3 (3)	Ru—C6—C11—C10	−55.84 (18)
C11—Ru—C6—N	111.3 (3)	N—C6—C11—C14	0.5 (3)
C2—Ru—C6—C11	−167.79 (16)	C7—C6—C11—C14	174.0 (2)
C8—Ru—C6—C11	105.04 (14)	Ru—C6—C11—C14	127.2 (2)
C1—Ru—C6—C11	−135.59 (14)	N—C6—C11—Ru	−126.7 (2)
C4—Ru—C6—C11	−60.7 (2)	C7—C6—C11—Ru	46.86 (19)
C10—Ru—C6—C11	30.85 (13)	C8—Ru—C11—C10	65.58 (14)
C5—Ru—C6—C11	−95.09 (15)	C1—Ru—C11—C10	−165.34 (15)
C7—Ru—C6—C11	136.4 (2)	C3—Ru—C11—C10	−60.7 (2)
C9—Ru—C6—C11	68.03 (13)	C4—Ru—C11—C10	−90.98 (15)
C2—Ru—C6—C7	55.8 (2)	C5—Ru—C11—C10	−131.80 (15)
C8—Ru—C6—C7	−31.37 (15)	C7—Ru—C11—C10	102.99 (15)
C1—Ru—C6—C7	88.00 (17)	C9—Ru—C11—C10	28.42 (14)
C4—Ru—C6—C7	162.84 (15)	C6—Ru—C11—C10	129.52 (19)
C10—Ru—C6—C7	−105.56 (16)	C8—Ru—C11—C6	−63.94 (13)
C5—Ru—C6—C7	128.49 (16)	C1—Ru—C11—C6	65.14 (18)
C9—Ru—C6—C7	−68.38 (15)	C3—Ru—C11—C6	169.78 (16)
C11—Ru—C6—C7	−136.4 (2)	C4—Ru—C11—C6	139.50 (15)
N—C6—C7—C8	−177.1 (2)	C10—Ru—C11—C6	−129.52 (19)
C11—C6—C7—C8	9.5 (3)	C5—Ru—C11—C6	98.68 (15)
Ru—C6—C7—C8	56.62 (18)	C7—Ru—C11—C6	−26.53 (13)
N—C6—C7—C12	1.1 (4)	C9—Ru—C11—C6	−101.10 (14)
C11—C6—C7—C12	−172.4 (2)	C8—Ru—C11—C14	178.0 (2)
Ru—C6—C7—C12	−125.3 (2)	C1—Ru—C11—C14	−52.9 (3)
N—C6—C7—Ru	126.3 (2)	C3—Ru—C11—C14	51.7 (3)
C11—C6—C7—Ru	−47.15 (19)	C4—Ru—C11—C14	21.5 (2)
C2—Ru—C7—C8	85.75 (15)	C10—Ru—C11—C14	112.4 (3)
C1—Ru—C7—C8	125.57 (14)	C5—Ru—C11—C14	−19.3 (2)
C3—Ru—C7—C8	59.2 (2)	C7—Ru—C11—C14	−144.6 (2)
C4—Ru—C7—C8	165.7 (4)	C9—Ru—C11—C14	140.9 (2)
C10—Ru—C7—C8	−65.48 (14)	C6—Ru—C11—C14	−118.0 (3)
C5—Ru—C7—C8	160.46 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H1A···F1	0.87 (2)	2.26 (2)	3.106 (3)	163 (3)
N—H1B···F5ⁱ	0.87 (2)	2.43 (3)	3.174 (3)	143 (3)

Symmetry code: (i) −x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Ru(C₅H₅)(C₉H₁₃N)]F₆P
M_r	446.33
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	173
a, b, c (Å)	7.5119 (4), 10.2047 (6), 21.1818 (12)
V (Å³)	1623.73 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.12
Crystal size (mm)	0.55 × 0.30 × 0.26

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.62, 0.75
No. of measured, independent and observed [I > 2σ(I)] reflections	24305, 4741, 4650
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.055, 1.12
No. of reflections	4741
No. of parameters	218
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.41
Absolute structure	Flack, (1983), 2202 Friedel pairs
Absolute structure parameter	0.21 (3)

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008)'.

Selected bond lengths (Å) top

Ru—C1	2.179 (2)	Ru—C10	2.185 (2)
Ru—C2	2.164 (2)	Ru—C11	2.229 (2)
Ru—C3	2.179 (3)	C6—N	1.373 (3)
Ru—C4	2.181 (3)	C6—C7	1.429 (3)
Ru—C5	2.187 (3)	C6—C11	1.428 (3)
Ru—C6	2.314 (2)	C7—C8	1.419 (3)
Ru—C7	2.212 (2)	C11—C10	1.415 (3)
Ru—C8	2.178 (2)	C8—C9	1.406 (3)
Ru—C9	2.214 (2)	C10—C9	1.416 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H1A···F1	0.87 (2)	2.26 (2)	3.106 (3)	163 (3)
N—H1B···F5ⁱ	0.87 (2)	2.43 (3)	3.174 (3)	143 (3)

Symmetry code: (i) −x, y+1/2, −z+1/2.

Acknowledgements

Financial support by the FWF Austrian Science Fund (project No. P16600-N11) is gratefully acknowledged.

References

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