Dichlorido(η-p-cymene)(4-fluoro-aniline-κN)ruthenium(II).

The title compound, [RuCl(2)(C(10)H(14))(C(6)H(6)FN)], a pseudo-octa-hedral d(6) complex, has the expected piano-stool geometry around the Ru(II) atom. The fluoro-aniline ring forms a dihedral angle of 19.3 (2)° with the p-cymene ring. In the crystal, two mol-ecules form an inversion dimer via a pair of N-H⋯Cl hydrogen bonds. Weak inter-molecular C-H⋯Cl inter-actions involving the p-cymene ring consolidate the crystal packing.

Related literature

For applications of (η6-p-cymene)Ru(II) dihalides in organic synthesis, see: Boutadla et al. (2010 ▶). For studies of (η6-arene)Ru(II) dihalides in bioinorganic chemistry, see: den Heeten et al. (2010 ▶). For anti-tumor medical applications of (η6-arene)Ru(II) systems, see: Hanif et al. (2010 ▶). For conversion of [(η6-p-cymene)RuCl2]2 with two molar equivalents of neutral unidentate nitro­gen ligands into monomeric pseudo-octa­hedral piano-stool complexes of general formula (η6-p-cymene)Ru(N-ligand)Cl2, see: Burrell & Steedman (1997 ▶); Govindaswamy & Kollipara (2006 ▶); Begley et al. (1991 ▶). For crystal structures of Ni-triad complexes of 4-fluoro­aniline, see: Randell et al. (2006 ▶); Fawcett et al. (2005 ▶); Padmanabhan et al. (1985 ▶). For applications of 19F-NMR reporter moieties in monitoring ligand-substitution equilibria, see: Hoffman et al. (2009 ▶); Carter et al. (2004 ▶).

Experimental

Crystal data

[RuCl2(C10H14)(C6H6FN)]

M = 417.30

Monoclinic,

a = 8.6492 (9) Å

b = 12.2458 (13) Å

c = 15.6471 (16) Å

β = 93.271 (8)°

V = 1654.6 (3) Å3

Z = 4

Mo Kα radiation

μ = 1.27 mm−1

T = 290 K

0.26 × 0.25 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.635, T max = 0.779

3234 measured reflections

3027 independent reflections

2284 reflections with I > 2σ(I)

R int = 0.048

3 standard reflections every 120 min intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.090

S = 1.00

3027 reflections

193 parameters

H-atom parameters constrained

Δρmax = 0.57 e Å−3

Δρmin = −0.67 e Å−3

Data collection: CAD-4-PC (Enraf–Nonius, 1993 ▶); cell refinement: CAD-4-PC; data reduction: XCAD-4PC (Harms & Wocadlo, 1995) ▶; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810051962/is2638sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810051962/is2638Isup2.hkl

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

[RuCl2(C10H14)(C6H6FN)]	F(000) = 840
Mr = 417.30	Dx = 1.675 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 8.6492 (9) Å	θ = 8.5–13.2°
b = 12.2458 (13) Å	µ = 1.27 mm−1
c = 15.6471 (16) Å	T = 290 K
β = 93.271 (8)°	Prism, red
V = 1654.6 (3) Å3	0.26 × 0.25 × 0.20 mm
Z = 4

Enraf–Nonius CAD-4 diffractometer	2284 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.048
graphite	θmax = 25.4°, θmin = 2.1°
θ/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = 0→14
Tmin = 0.635, Tmax = 0.779	l = −18→18
3234 measured reflections	3 standard reflections every 120 min
3027 independent 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0435P)2] where P = (Fo2 + 2Fc2)/3
3027 reflections	(Δ/σ)max < 0.001
193 parameters	Δρmax = 0.57 e Å−3
0 restraints	Δρmin = −0.67 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 > 2σ(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
Ru1	0.22499 (3)	0.59291 (3)	0.611377 (18)	0.02585 (12)
Cl1	0.24408 (14)	0.39815 (9)	0.63052 (7)	0.0442 (3)
Cl2	0.29626 (13)	0.56893 (9)	0.46564 (6)	0.0391 (3)
F1	0.8394 (4)	0.9472 (3)	0.6880 (2)	0.0811 (10)
N1	0.4725 (4)	0.5795 (3)	0.6397 (2)	0.0335 (8)
H1A	0.4864	0.5382	0.6871	0.040*
H1B	0.5116	0.5417	0.5966	0.040*
C1	0.0988 (5)	0.6207 (3)	0.7270 (2)	0.0322 (9)
C2	−0.0055 (5)	0.5901 (4)	0.6567 (3)	0.0353 (9)
H2	−0.0712	0.5309	0.6631	0.042*
C3	−0.0120 (5)	0.6456 (4)	0.5792 (3)	0.0381 (10)
H3	−0.0833	0.6247	0.5356	0.046*
C4	0.0905 (5)	0.7347 (3)	0.5664 (3)	0.0359 (10)
C5	0.1936 (5)	0.7656 (3)	0.6343 (3)	0.0377 (10)
H5	0.2593	0.8247	0.6275	0.045*
C6	0.2000 (5)	0.7087 (3)	0.7133 (2)	0.0337 (9)
H6	0.2719	0.7295	0.7568	0.040*
C7	0.1003 (5)	0.5586 (4)	0.8103 (2)	0.0375 (10)
H7	0.0686	0.4832	0.7979	0.045*
C8	−0.0172 (6)	0.6100 (5)	0.8675 (3)	0.0607 (15)
H8A	−0.0165	0.5711	0.9208	0.091*
H8B	−0.1187	0.6062	0.8395	0.091*
H8C	0.0098	0.6850	0.8783	0.091*
C9	0.2608 (6)	0.5567 (5)	0.8572 (3)	0.0513 (13)
H9A	0.3347	0.5265	0.8203	0.077*
H9B	0.2572	0.5127	0.9078	0.077*
H9C	0.2908	0.6298	0.8729	0.077*
C10	0.0887 (6)	0.7916 (4)	0.4821 (3)	0.0530 (13)
H10A	0.0348	0.8598	0.4858	0.079*
H10B	0.0372	0.7466	0.4390	0.079*
H10C	0.1932	0.8050	0.4671	0.079*
C11	0.5666 (4)	0.6756 (3)	0.6529 (2)	0.0312 (9)
C12	0.6131 (5)	0.7101 (4)	0.7343 (3)	0.0406 (10)
H12	0.5832	0.6705	0.7813	0.049*
C13	0.7024 (6)	0.8016 (4)	0.7471 (3)	0.0510 (13)
H13	0.7326	0.8251	0.8021	0.061*
C14	0.7458 (5)	0.8573 (4)	0.6771 (4)	0.0508 (12)
C15	0.7011 (5)	0.8263 (4)	0.5954 (3)	0.0539 (13)
H15	0.7319	0.8665	0.5489	0.065*
C16	0.6102 (5)	0.7351 (4)	0.5829 (3)	0.0424 (11)
H16	0.5781	0.7133	0.5278	0.051*

	U11	U22	U33	U12	U13	U23
Ru1	0.02827 (18)	0.02503 (18)	0.02404 (17)	0.00145 (14)	−0.00045 (12)	−0.00363 (13)
Cl1	0.0591 (7)	0.0273 (5)	0.0457 (6)	0.0016 (5)	−0.0001 (5)	0.0026 (4)
Cl2	0.0435 (6)	0.0486 (7)	0.0252 (5)	0.0095 (5)	0.0027 (4)	−0.0046 (4)
F1	0.074 (2)	0.057 (2)	0.111 (3)	−0.0266 (18)	−0.011 (2)	0.001 (2)
N1	0.0335 (18)	0.035 (2)	0.0319 (17)	0.0073 (16)	0.0001 (14)	−0.0108 (15)
C1	0.032 (2)	0.034 (2)	0.031 (2)	0.0024 (17)	0.0060 (17)	−0.0075 (17)
C2	0.028 (2)	0.040 (2)	0.037 (2)	0.0000 (19)	0.0018 (16)	−0.0040 (19)
C3	0.029 (2)	0.045 (3)	0.040 (2)	0.013 (2)	−0.0053 (18)	−0.006 (2)
C4	0.036 (2)	0.034 (2)	0.038 (2)	0.0137 (19)	0.0031 (18)	0.0016 (18)
C5	0.046 (2)	0.026 (2)	0.041 (2)	0.0058 (19)	0.0048 (19)	−0.0049 (18)
C6	0.034 (2)	0.035 (2)	0.032 (2)	0.0024 (18)	−0.0010 (17)	−0.0111 (18)
C7	0.046 (3)	0.039 (2)	0.028 (2)	−0.007 (2)	0.0020 (18)	−0.0046 (18)
C8	0.062 (3)	0.082 (4)	0.039 (3)	0.008 (3)	0.013 (2)	−0.003 (3)
C9	0.059 (3)	0.057 (3)	0.037 (2)	−0.002 (3)	−0.007 (2)	0.007 (2)
C10	0.064 (3)	0.049 (3)	0.046 (3)	0.015 (3)	0.001 (2)	0.012 (2)
C11	0.026 (2)	0.036 (2)	0.032 (2)	0.0046 (18)	0.0015 (16)	−0.0056 (17)
C12	0.042 (2)	0.046 (3)	0.034 (2)	−0.001 (2)	−0.0034 (18)	−0.003 (2)
C13	0.051 (3)	0.056 (3)	0.044 (3)	−0.002 (3)	−0.008 (2)	−0.017 (2)
C14	0.035 (2)	0.042 (3)	0.074 (4)	0.003 (2)	−0.006 (2)	−0.007 (3)
C15	0.044 (3)	0.055 (3)	0.063 (3)	−0.003 (2)	0.013 (2)	0.015 (3)
C16	0.041 (2)	0.052 (3)	0.034 (2)	0.003 (2)	0.0025 (18)	−0.004 (2)

Ru1—C2	2.154 (4)	C6—H6	0.9300
Ru1—C6	2.154 (4)	C7—C8	1.528 (6)
Ru1—C5	2.165 (4)	C7—C9	1.533 (6)
Ru1—N1	2.167 (3)	C7—H7	0.9800
Ru1—C3	2.180 (4)	C8—H8A	0.9600
Ru1—C4	2.184 (4)	C8—H8B	0.9600
Ru1—C1	2.192 (4)	C8—H8C	0.9600
Ru1—Cl1	2.4082 (11)	C9—H9A	0.9600
Ru1—Cl2	2.4138 (10)	C9—H9B	0.9600
F1—C14	1.372 (6)	C9—H9C	0.9600
N1—C11	1.439 (5)	C10—H10A	0.9600
N1—H1A	0.9000	C10—H10B	0.9600
N1—H1B	0.9000	C10—H10C	0.9600
C1—C6	1.412 (6)	C11—C12	1.381 (5)
C1—C2	1.433 (6)	C11—C16	1.384 (6)
C1—C7	1.508 (6)	C12—C13	1.369 (6)
C2—C3	1.388 (6)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.361 (7)
C3—C4	1.427 (6)	C13—H13	0.9300
C3—H3	0.9300	C14—C15	1.367 (7)
C4—C5	1.401 (6)	C15—C16	1.374 (7)
C4—C10	1.491 (6)	C15—H15	0.9300
C5—C6	1.418 (6)	C16—H16	0.9300
C5—H5	0.9300
C2—Ru1—C6	68.48 (15)	C5—C4—C3	118.3 (4)
C2—Ru1—C5	80.44 (17)	C5—C4—C10	121.3 (4)
C6—Ru1—C5	38.32 (16)	C3—C4—C10	120.4 (4)
C2—Ru1—N1	148.59 (14)	C5—C4—Ru1	70.5 (2)
C6—Ru1—N1	92.17 (14)	C3—C4—Ru1	70.8 (2)
C5—Ru1—N1	99.88 (15)	C10—C4—Ru1	129.4 (3)
C2—Ru1—C3	37.34 (16)	C4—C5—C6	121.4 (4)
C6—Ru1—C3	80.99 (16)	C4—C5—Ru1	72.0 (2)
C5—Ru1—C3	67.91 (17)	C6—C5—Ru1	70.4 (2)
N1—Ru1—C3	166.94 (15)	C4—C5—H5	119.3
C2—Ru1—C4	68.45 (16)	C6—C5—H5	119.3
C6—Ru1—C4	69.00 (15)	Ru1—C5—H5	131.2
C5—Ru1—C4	37.57 (16)	C1—C6—C5	120.9 (4)
N1—Ru1—C4	128.89 (15)	C1—C6—Ru1	72.5 (2)
C3—Ru1—C4	38.16 (16)	C5—C6—Ru1	71.2 (2)
C2—Ru1—C1	38.48 (15)	C1—C6—H6	119.5
C6—Ru1—C1	37.91 (15)	C5—C6—H6	119.5
C5—Ru1—C1	68.81 (16)	Ru1—C6—H6	129.1
N1—Ru1—C1	112.05 (14)	C1—C7—C8	109.0 (4)
C3—Ru1—C1	68.83 (15)	C1—C7—C9	112.6 (4)
C4—Ru1—C1	82.05 (15)	C8—C7—C9	109.9 (4)
C2—Ru1—Cl1	90.08 (12)	C1—C7—H7	108.4
C6—Ru1—Cl1	124.65 (12)	C8—C7—H7	108.4
C5—Ru1—Cl1	162.78 (12)	C9—C7—H7	108.4
N1—Ru1—Cl1	80.78 (9)	C7—C8—H8A	109.5
C3—Ru1—Cl1	112.26 (13)	C7—C8—H8B	109.5
C4—Ru1—Cl1	149.19 (12)	H8A—C8—H8B	109.5
C1—Ru1—Cl1	94.86 (11)	C7—C8—H8C	109.5
C2—Ru1—Cl2	126.86 (11)	H8A—C8—H8C	109.5
C6—Ru1—Cl2	145.24 (12)	H8B—C8—H8C	109.5
C5—Ru1—Cl2	108.47 (12)	C7—C9—H9A	109.5
N1—Ru1—Cl2	83.19 (9)	C7—C9—H9B	109.5
C3—Ru1—Cl2	96.05 (11)	H9A—C9—H9B	109.5
C4—Ru1—Cl2	87.26 (11)	C7—C9—H9C	109.5
C1—Ru1—Cl2	164.70 (11)	H9A—C9—H9C	109.5
Cl1—Ru1—Cl2	88.72 (4)	H9B—C9—H9C	109.5
C11—N1—Ru1	120.8 (2)	C4—C10—H10A	109.5
C11—N1—H1A	107.1	C4—C10—H10B	109.5
Ru1—N1—H1A	107.1	H10A—C10—H10B	109.5
C11—N1—H1B	107.1	C4—C10—H10C	109.5
Ru1—N1—H1B	107.1	H10A—C10—H10C	109.5
H1A—N1—H1B	106.8	H10B—C10—H10C	109.5
C6—C1—C2	116.8 (4)	C12—C11—C16	119.4 (4)
C6—C1—C7	122.7 (4)	C12—C11—N1	121.0 (4)
C2—C1—C7	120.4 (4)	C16—C11—N1	119.6 (4)
C6—C1—Ru1	69.6 (2)	C13—C12—C11	121.1 (4)
C2—C1—Ru1	69.3 (2)	C13—C12—H12	119.4
C7—C1—Ru1	130.9 (3)	C11—C12—H12	119.4
C3—C2—C1	122.4 (4)	C14—C13—C12	118.1 (4)
C3—C2—Ru1	72.4 (2)	C14—C13—H13	120.9
C1—C2—Ru1	72.2 (2)	C12—C13—H13	120.9
C3—C2—H2	118.8	C13—C14—C15	122.5 (5)
C1—C2—H2	118.8	C13—C14—F1	119.3 (5)
Ru1—C2—H2	129.1	C15—C14—F1	118.2 (5)
C2—C3—C4	120.2 (4)	C14—C15—C16	119.2 (5)
C2—C3—Ru1	70.3 (2)	C14—C15—H15	120.4
C4—C3—Ru1	71.1 (2)	C16—C15—H15	120.4
C2—C3—H3	119.9	C15—C16—C11	119.6 (4)
C4—C3—H3	119.9	C15—C16—H16	120.2
Ru1—C3—H3	131.6	C11—C16—H16	120.2

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cl2i	0.90	2.39	3.225 (3)	154
C6—H6···Cl1ii	0.93	2.72	3.384 (4)	129

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯Cl2i	0.90	2.39	3.225 (3)	154
C6—H6⋯Cl1ii	0.93	2.72	3.384 (4)	129

Symmetry codes: (i) ; (ii) .