Synthesis and structures of ruthenium di- and tricarbonyl complexes derived from 4,5-di­aza­fluoren-9-one

Carbon monoxide (CO) has recently been shown to impart beneficial effects in mammalian physiology and considerable research attention is now being directed toward metal-carbonyl complexes as a means of delivering CO to bio­logical targets. Two ruthenium carbonyl complexes, namely trans-di­carbonyl­dichlorido­(4,5-di­aza­fluoren-9-one-[kappa]²N,N')ruthenium(II), [RuCl₂(C₁₁H₆N₂O)(CO)₂], (1), and fac-tri­carbonyl­dichlorido­(4,5-di­aza­fluoren-9-one-[kappa]N)ruthenium(II), [RuCl₂(C₁₁H₆N₂O)(CO)₃], (2), have been isolated and structurally characterized. In the case of complex (1), the trans-directing effect of the CO ligands allows bidentate coordination of the 4,5-di­aza­fluoren-9-one (dafo) ligand despite a larger bite distance between the N-donor atoms. In complex (2), the cis disposition of two chloride ligands restricts the ability of the dafo mol­ecule to bind ruthenium in a bidentate fashion. Both complexes exhibit well defined ¹H NMR spectra confirming the diamagnetic ground state of Ru^II and display a strong absorption band around 300 nm in the UV.

S1. Introduction

Carbon monoxide (CO) has recently been shown to impart salutary effects in mammalian physiology when applied in lower concentrations (Motterlini & Otterbien, 2010). This surprising discovery has raised inetrest in metal–carbonyl complexes as potential CO donors. Although metal carbonyl complexes have been studied extensively for their photophysical and photochemical properties (Stufkens & Vlcek, 1998), considerable research attention has now been directed toward these species as means of delivering CO to biological targets under controlled conditions as opposed to its administration in the gaseous form (Bernardes & Garcia-Gallego, 2014; Romao et al., 2012). In such attempts, the photoactive CO-releasing molecules (photoCORMs) have emerged as promising therapeutics where CO release can be triggered upon illumination (Gonzalez & Mascharak, 2014; Chakraborty et al., 2014; Schatzschneider, 2015). Herein we report the syntheses, properties and X-ray structures of two ruthenium carbonyl complexes, namely trans[RuCl₂(dafo)(CO)₂], (1), and fac-[RuCl₂(CO)₃(dafo)(CO)₃], (2), where dafo is 4,5-di­aza­fluoren-9-one. The potentially bidentate ligand dafo binds the Ru^II center of (1) and (2) in a bidentate and a monodentate fashion, respectively. Both steric and electronic effects play concurrent roles in di­cta­ting the mode of binding of dafo in these two complexes.

S2. Experimental

All reagents were of commercial grade and used without further purification. The solvents were purified according to a standard procedure (Armarego & Chai, 2003). 4,5-Di­aza­fluoren-9-one (dafo) was synthesized according to a reported procedure (Eckhard & Summers, 1973). A Perkin Elmer Spectrum-One FT–IR spectrophotometer was employed to monitor the IR spectra of the compounds. UV–Vis spectra were obtained with Varian Cary 50 UV–Vis spectrophotometer. ¹H NMR spectra were recorded at 298 K on a Varian Unity Inova 500 MHz instrument. Microanalyses were carried out with a Perkin Elmer Series II Elemental Analyzer.

S2.1. Synthesis and crystallization

S2.1.1. Synthesis of complex (1)

A slurry of [RuCl₂(CO)₃]₂ (100 mg, 0.195 mmol) in dry methanol (15 ml) was heated to reflux (338 K) while stirring for 3 h. Next, 4,5-di­aza­fluoren-9-one (dafo; 71.1 mg, 0.370 mmol) was added and the reaction mixture was allowed to reflux for an additional 3 h. The color of the solution changed from pale yellow to bright yellow during this time. Upon cooling, a yellow precipitate was observed which was then filtetred off, washed with a minimum amount of CH₂Cl₂, and dried under reduced pressure. (yield 72.8 mg, 48%). Elemental analysis (%) found: C 38.11, N 6.89, H 1.52; calculated for C₁₃H₆Cl₂N₂O₃Ru: C 38.06, N 6.83, H 1.47. IR: ν(CO) (KBr, cm-¹) 2078, 1993. ¹H NMR (CDCl₃): δ 8.96 (d, 2H), 8.24 (d, 2H), 7.73 (t, 2H).

S2.1.2. Synthesis of complex (2)

A batch of [RuCl₂(CO)₃]₂ (100 mg, 0.195 mmol) in dry methanol (20 ml) was allowed to stir at 318 K for 3 h. Next, dafo (71.2 mg, 0.370 mmol) was added and the solution was allowed to stir at 318 K for an additional 3 h. The white precipitate that formed during this time was filtered off, washed with a small amount of CH₂Cl₂, and dried under vacuum (yield: 90.9 mg, 56%). Elemental analysis (%) found: C 38.42, N 6.43, H 1.43; calculated for C₁₄H₆Cl₂N₂O₄Ru: C 38.37, N 6.39, H 1.38. IR ν (CO) (KBr, cm^-1) 2062, 1998. ¹H NMR (CDCl₃): δ 9.70 (d, 1H), 8.76 (d, 1H), 8.20 (d, 1H), 8.15 (d, 1H), 7.70 (d, 1H), 7.62 (t, 1H).

S2.1.3. Isolation of complexes (1) and (2)

Single crystals for both the complexes were obtained by layering hexanes over their CH₂Cl₂ solutions. One crystal for each complex was selected and affixed on top of MiTiGen micromounts using Paratone Oil and tranferred to the diffractometer.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The metal atoms were located by direct methods and the remaining non-H atoms emerged from successive Fourier syntheses. H atoms were included in calculated positions riding on the C atom to which they are bonded, with C—H = 0.93 Å and U_iso(H) = 1.2U_iso(C). Carbonyl atoms C1 and O1 in (2) were constrained to have equivalent atomic displacement parameters and the C6—C7 bond was restrained to emulate rigid-body motion.

S3. Results and discussion

The complexes trans-[RuCl₂(dafo)(CO)₂] (dafo is 4,5-di­aza­fluoren-9-one), (1), and fac-[RuCl₂(dafo)(CO)₃], (2), were isolated from the reaction of [RuCl₂(CO)₃]₂ with 2 equivalents of dafo in methanol. Complex (1) was isolated from the methano­lic reaction mixture under refluxing conditions. Quite in contrast, stirring of the reaction mixture in methanol at 318 K resulted in (2). In accordance with our previous report on cis- and trans-[RuCl₂(azpy)(CO)₂] [where azpy is 2-(phenyl­diazenyl)pyridine] complexes (Carrington et al., 2013), warming of [RuCl₂(CO)₃]₂ at 318 K presumably resulted in the inter­mediate solvento species fac-[RuCl₂(MeOH)(CO)₃]. Addition of dafo displaced the solvent molecule to furnish complex (2), where the dafo ligand binds the Ru^II center in a monodentate fashion. This finding is unusual compared to that observed for other analogous carbonyl complexes derived from rigid heterocycles like bi­pyridine (bpy), where, under similar conditions, the complex isolated is of formula cis-[RuCl₂(bpy)(CO)₂] (Haukka et al., 1995). In the case of complex (2), the relatively larger bite distance between the two N atoms of the dafo ligand (compared to bpy) most likely restricts bidentate coordination to the metal center (Pal et al., 2014). In the case of (1), the inter­mediate species fac-[RuCl₂(MeOH)(CO)₃] undergoes a facial → meridional isomerization upon refluxing (338 K). In this meridional inter­mediate, trans disposition of the two CO ligands across each other facilitates removal of one CO. This vacancy finally allows binding of the dafo ligand in a bidenate fashion in (1).

The coordination geometry of Ru^II in both complexes is distorted o­cta­hedral (Tables 2 and 3). The two CO ligands are cis to each other in complex (1) (Fig. 1), while in complex (2) (Fig. 2), the three CO ligands are arranged in a facial disposition. The two Cl^- ligands are in trans and cis dispositions in (1) and (2), respectively. In complex (1), the chelate ring composed of atoms Ru1, N1, C7, C9, and N2 is almost planar, with a mean deviation of 0.007 (3) Å. The equatorial plane of (1) is comprised of the bidentate dafo ligand and two CO ligands (atoms C1, C2, N2, and N1), with a mean deviation of 0.040 (3) Å and the Ru^II atom is displaced by 0.010 (3) Å towards the Cl2 atom. The coordinated dafo ligand is planar [mean deviation = 0.020 (3) Å] in complex (1). In the case of complex (2), the equatorial plane is comprised of one N atom of the monodentate dafo ligand, one chloride and two CO ligands (atoms N1, Cl2, C1, and C3), with a mean deviation of 0.034 (4) Å. The Ru^II atom is displaced by 0.059 (4) Å towards the carbonyl C2 atom. In this case, the dafo ligand frame is also fairly planar, with a mean deviation of 0.028 (3) Å. The monodentate dafo ligand in (2) forms a dihedral angle of 52.16 (8)° with the equatorial plane constitued by atoms C1, C3, N1, and Cl2. The crystal packing (Dolomanov et al., 2009; Spek, 2009) for the complexes reveal no significant stacking or other nonbonded inter­actions (Figs. 3 and 4). The distance between the two N atoms (N1 and N2) of dafo in (1) and (2) are 2.833 (4) and 3.146 (5) Å, respectively, due to different modes of binding. The bidenate coordination of dafo in (1) apprears to promote pronounced competition in π back-bonding between the dafo and CO ligands for the same metal orbitals compared to complex (2). This is corroborated by the apparent CO release rate (k_CO) values of these complexes. In CH₂Cl₂ solution under 305 nm UV illumination, complex (1) exhibits a much higher k_CO value (15.34±0.02 min^-1, conc. 2.4 × 10^-4 M) compared to complex (2) (6.08±0.02 min^-1, conc. 2.4 × 10^-4 M).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Bruker 2008) and OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. A perspective view of complex (1), showing the atom-labeling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A perspective view of complex (2), showing the atom-labeling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. The crystal packing of complex (1), showing a view along the b axis.
	Fig. 4. The crystal packing of complex (2), showing a view along the b axis.

(1) trans-Dicarbonyldichlorido(4,5-diazafluoren-9-one-κ²N,N')ruthenium(II)

Crystal data

[RuCl2(C11H6N2O)(CO)2]	F(000) = 800
Mr = 410.17	Dx = 1.958 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.5589 (2) Å	Cell parameters from 9050 reflections
b = 16.9199 (6) Å	θ = 2.4–26.3°
c = 12.7585 (5) Å	µ = 1.52 mm^−1
β = 100.69°	T = 296 K
V = 1391.30 (8) Å^3	Block, colorless
Z = 4	0.20 × 0.15 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer	2840 independent reflections
Radiation source: fine-focus sealed tube	2598 reflections with I > 2σ(I)
Detector resolution: 8.33 pixels mm^-1	Rint = 0.055
ω scans	θmax = 26.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −8→8
Tmin = 0.668, Tmax = 0.745	k = −21→21
13644 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.076	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0393P)^2 + 1.2351P] where P = (Fo^2 + 2Fc^2)/3
2840 reflections	(Δ/σ)max = 0.001
190 parameters	Δρmax = 1.02 e Å^−3
0 restraints	Δρmin = −0.42 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ru1	0.70714 (3)	0.37385 (2)	0.63595 (2)	0.03500 (10)
Cl1	0.94807 (12)	0.34857 (5)	0.79811 (6)	0.05222 (19)
Cl2	0.49226 (13)	0.38504 (5)	0.46405 (7)	0.0547 (2)
O3	0.7415 (4)	0.01600 (13)	0.5327 (3)	0.0766 (8)
O2	0.9657 (4)	0.51454 (14)	0.6069 (2)	0.0628 (6)
O1	0.4360 (5)	0.47572 (18)	0.7402 (2)	0.0803 (8)
N1	0.5457 (3)	0.26370 (14)	0.66326 (18)	0.0392 (5)
N2	0.8830 (3)	0.29170 (13)	0.55820 (17)	0.0352 (5)
C3	0.3910 (4)	0.2398 (2)	0.7137 (2)	0.0481 (7)
H3	0.3207	0.2775	0.7465	0.058*
C4	0.3349 (5)	0.1611 (2)	0.7178 (2)	0.0564 (8)
H4	0.2307	0.1473	0.7548	0.068*
C5	0.4305 (5)	0.1020 (2)	0.6679 (3)	0.0590 (9)
H5	0.3912	0.0493	0.6699	0.071*
C6	0.5859 (5)	0.12555 (16)	0.6158 (3)	0.0489 (7)
C7	0.6332 (4)	0.20550 (16)	0.6183 (2)	0.0401 (6)
C9	0.8043 (4)	0.21970 (15)	0.5641 (2)	0.0373 (6)
C13	1.0409 (4)	0.29571 (17)	0.5048 (2)	0.0396 (6)
H13	1.1021	0.3445	0.4978	0.048*
C12	1.1159 (4)	0.23020 (18)	0.4600 (2)	0.0446 (6)
H12	1.2257	0.2360	0.4239	0.054*
C11	1.0311 (5)	0.15600 (19)	0.4678 (2)	0.0474 (7)
H11	1.0814	0.1117	0.4378	0.057*
C10	0.8679 (4)	0.15088 (17)	0.5223 (2)	0.0434 (6)
C8	0.7321 (5)	0.08520 (17)	0.5532 (3)	0.0531 (8)
C2	0.8658 (5)	0.46283 (17)	0.6145 (2)	0.0431 (6)
C1	0.5301 (5)	0.43934 (19)	0.7038 (3)	0.0514 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.03214 (14)	0.03422 (14)	0.04105 (15)	0.00096 (7)	0.01306 (10)	−0.00192 (8)
Cl1	0.0427 (4)	0.0715 (5)	0.0438 (4)	−0.0011 (3)	0.0117 (3)	0.0017 (3)
Cl2	0.0477 (4)	0.0553 (4)	0.0600 (5)	−0.0021 (3)	0.0075 (4)	0.0063 (3)
O3	0.0714 (17)	0.0331 (12)	0.120 (2)	0.0023 (11)	0.0029 (16)	−0.0037 (13)
O2	0.0662 (15)	0.0503 (13)	0.0734 (16)	−0.0131 (12)	0.0170 (13)	−0.0006 (11)
O1	0.0791 (19)	0.090 (2)	0.0798 (19)	0.0227 (16)	0.0357 (16)	0.0011 (16)
N1	0.0333 (11)	0.0471 (13)	0.0383 (11)	−0.0028 (9)	0.0099 (9)	0.0030 (10)
N2	0.0339 (11)	0.0349 (11)	0.0381 (11)	0.0020 (9)	0.0102 (9)	−0.0008 (9)
C3	0.0355 (14)	0.071 (2)	0.0372 (14)	−0.0094 (13)	0.0063 (12)	0.0048 (14)
C4	0.0457 (17)	0.078 (2)	0.0445 (16)	−0.0208 (16)	0.0050 (14)	0.0157 (16)
C5	0.0563 (19)	0.0563 (19)	0.0586 (19)	−0.0226 (16)	−0.0041 (16)	0.0186 (16)
C6	0.0472 (17)	0.0401 (16)	0.0555 (18)	−0.0052 (12)	−0.0009 (14)	0.0106 (12)
C7	0.0366 (13)	0.0383 (14)	0.0447 (15)	−0.0038 (11)	0.0058 (11)	0.0052 (11)
C9	0.0342 (13)	0.0361 (13)	0.0411 (14)	0.0025 (10)	0.0058 (11)	0.0006 (11)
C13	0.0369 (14)	0.0436 (14)	0.0395 (14)	0.0010 (11)	0.0101 (11)	0.0032 (11)
C12	0.0421 (15)	0.0553 (17)	0.0376 (14)	0.0100 (13)	0.0104 (12)	−0.0025 (12)
C11	0.0463 (16)	0.0481 (16)	0.0447 (15)	0.0156 (13)	0.0004 (13)	−0.0103 (13)
C10	0.0416 (15)	0.0366 (13)	0.0480 (16)	0.0055 (12)	−0.0023 (12)	−0.0023 (12)
C8	0.0511 (17)	0.0360 (15)	0.065 (2)	0.0023 (13)	−0.0069 (15)	0.0035 (14)
C2	0.0473 (16)	0.0381 (14)	0.0453 (15)	0.0033 (12)	0.0122 (13)	−0.0059 (12)
C1	0.0531 (18)	0.0444 (17)	0.0552 (18)	0.0069 (14)	0.0063 (15)	0.0029 (14)

Geometric parameters (Å, º)

Ru1—C2	1.879 (3)	C4—C5	1.395 (5)
Ru1—C1	1.923 (3)	C4—H4	0.9300
Ru1—N2	2.161 (2)	C5—C6	1.375 (5)
Ru1—N1	2.203 (2)	C5—H5	0.9300
Ru1—Cl2	2.3844 (9)	C6—C7	1.387 (4)
Ru1—Cl1	2.3974 (8)	C6—C8	1.519 (5)
O3—C8	1.204 (4)	C7—C9	1.443 (4)
O2—C2	1.108 (4)	C9—C10	1.377 (4)
O1—C1	1.040 (4)	C13—C12	1.379 (4)
N1—C7	1.323 (4)	C13—H13	0.9300
N1—C3	1.360 (3)	C12—C11	1.384 (4)
N2—C9	1.330 (3)	C12—H12	0.9300
N2—C13	1.343 (3)	C11—C10	1.383 (4)
C3—C4	1.385 (5)	C11—H11	0.9300
C3—H3	0.9300	C10—C8	1.521 (4)
C2—Ru1—C1	90.05 (13)	C6—C5—H5	121.6
C2—Ru1—N2	95.24 (10)	C4—C5—H5	121.6
C1—Ru1—N2	174.48 (11)	C5—C6—C7	117.0 (3)
C2—Ru1—N1	175.16 (10)	C5—C6—C8	136.2 (3)
C1—Ru1—N1	93.90 (11)	C7—C6—C8	106.8 (3)
N2—Ru1—N1	80.89 (8)	N1—C7—C6	128.5 (3)
C2—Ru1—Cl2	92.93 (9)	N1—C7—C9	121.5 (2)
C1—Ru1—Cl2	93.72 (10)	C6—C7—C9	110.0 (3)
N2—Ru1—Cl2	84.47 (6)	N2—C9—C10	127.1 (3)
N1—Ru1—Cl2	89.61 (6)	N2—C9—C7	121.6 (2)
C2—Ru1—Cl1	88.54 (9)	C10—C9—C7	111.3 (2)
C1—Ru1—Cl1	94.06 (10)	N2—C13—C12	122.5 (3)
N2—Ru1—Cl1	87.65 (6)	N2—C13—H13	118.7
N1—Ru1—Cl1	88.39 (6)	C12—C13—H13	118.7
Cl2—Ru1—Cl1	172.08 (3)	C13—C12—C11	121.4 (3)
C7—N1—C3	114.0 (3)	C13—C12—H12	119.3
C7—N1—Ru1	107.51 (17)	C11—C12—H12	119.3
C3—N1—Ru1	138.5 (2)	C12—C11—C10	116.8 (3)
C9—N2—C13	114.8 (2)	C12—C11—H11	121.6
C9—N2—Ru1	108.51 (16)	C10—C11—H11	121.6
C13—N2—Ru1	136.70 (18)	C9—C10—C11	117.4 (3)
N1—C3—C4	122.0 (3)	C9—C10—C8	106.5 (3)
N1—C3—H3	119.0	C11—C10—C8	136.1 (3)
C4—C3—H3	119.0	O3—C8—C6	127.9 (3)
C3—C4—C5	121.8 (3)	O3—C8—C10	126.8 (3)
C3—C4—H4	119.1	C6—C8—C10	105.4 (2)
C5—C4—H4	119.1	O2—C2—Ru1	176.3 (3)
C6—C5—C4	116.7 (3)	O1—C1—Ru1	178.9 (3)

(2) fac-Tricarbonyldichlorido(4,5-diazafluoren-9-one-κN)ruthenium(II)

Crystal data

[RuCl2(C11H6N2O)(CO)3]	Z = 2
Mr = 438.18	F(000) = 428
Triclinic, P1	Dx = 1.853 Mg m^−3
a = 7.458 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.701 (2) Å	Cell parameters from 2934 reflections
c = 11.594 (9) Å	θ = 2.7–26.0°
α = 90.43 (3)°	µ = 1.36 mm^−1
β = 108.60 (4)°	T = 296 K
γ = 98.41 (2)°	Block, colorless
V = 785.1 (7) Å^3	0.15 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer	2934 independent reflections
Radiation source: fine-focus sealed tube	2141 reflections with I > 2σ(I)
Detector resolution: 8.33 pixels mm^-1	Rint = 0.049
ω scans	θmax = 25.7°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→9
Tmin = 0.682, Tmax = 0.745	k = −11→11
7433 measured reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.060	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2)] where P = (Fo^2 + 2Fc^2)/3
2934 reflections	(Δ/σ)max = 0.001
202 parameters	Δρmax = 0.74 e Å^−3
1 restraint	Δρmin = −0.60 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ru1	0.34512 (5)	0.19385 (3)	0.80951 (3)	0.05637 (13)
Cl1	0.31437 (16)	−0.05628 (10)	0.78187 (11)	0.0812 (4)
Cl2	0.01300 (14)	0.19209 (12)	0.69578 (13)	0.0944 (4)
O1	0.2193 (5)	0.1340 (3)	1.0283 (3)	0.0996 (9)
O2	0.3520 (4)	0.5013 (3)	0.8646 (2)	0.0701 (8)
O4	0.7583 (4)	0.4634 (3)	0.4104 (3)	0.0928 (10)
O3	0.7628 (4)	0.1844 (3)	0.9465 (3)	0.0816 (9)
N1	0.4091 (4)	0.2135 (3)	0.6401 (3)	0.0517 (8)
N2	0.7099 (4)	0.4535 (3)	0.8075 (3)	0.0539 (8)
C1	0.2690 (8)	0.1590 (5)	0.9463 (5)	0.0996 (9)
C2	0.3567 (5)	0.3899 (4)	0.8389 (3)	0.0543 (10)
C14	0.5432 (5)	0.3041 (4)	0.6140 (3)	0.0472 (9)
C13	0.6820 (5)	0.4209 (4)	0.6922 (4)	0.0460 (9)
C9	0.7831 (5)	0.4932 (4)	0.6231 (4)	0.0558 (10)
C8	0.7136 (6)	0.4259 (5)	0.4978 (4)	0.0647 (12)
C7	0.5671 (6)	0.3054 (4)	0.5003 (4)	0.0552 (10)
C6	0.4577 (7)	0.2099 (5)	0.4087 (4)	0.0749 (13)
H6	0.4751	0.2088	0.3328	0.090*
C5	0.3210 (7)	0.1158 (5)	0.4337 (4)	0.0775 (14)
H5	0.2432	0.0489	0.3740	0.093*
C4	0.2986 (6)	0.1201 (4)	0.5465 (4)	0.0706 (12)
H4	0.2029	0.0560	0.5602	0.085*
C10	0.9183 (6)	0.6085 (4)	0.6741 (5)	0.0684 (12)
H10	0.9866	0.6593	0.6297	0.082*
C11	0.9465 (6)	0.6442 (4)	0.7941 (5)	0.0739 (13)
H11	1.0349	0.7218	0.8331	0.089*
C12	0.8448 (6)	0.5657 (4)	0.8559 (4)	0.0644 (11)
H12	0.8703	0.5913	0.9377	0.077*
C3	0.6052 (7)	0.1911 (4)	0.8956 (4)	0.0611 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.0571 (2)	0.0437 (2)	0.0766 (3)	0.00962 (15)	0.03234 (18)	0.00607 (16)
Cl1	0.0980 (8)	0.0420 (6)	0.1220 (10)	0.0094 (6)	0.0617 (8)	0.0079 (6)
Cl2	0.0528 (7)	0.0710 (8)	0.1545 (12)	0.0099 (6)	0.0270 (7)	−0.0064 (8)
O1	0.129 (2)	0.0729 (17)	0.141 (3)	0.0402 (16)	0.094 (2)	0.0351 (17)
O2	0.089 (2)	0.0517 (19)	0.073 (2)	0.0212 (17)	0.0251 (16)	−0.0041 (16)
O4	0.099 (2)	0.131 (3)	0.074 (2)	0.044 (2)	0.0520 (19)	0.0392 (19)
O3	0.074 (2)	0.082 (2)	0.089 (2)	0.0230 (18)	0.0218 (19)	0.0225 (17)
N1	0.054 (2)	0.0403 (19)	0.058 (2)	0.0090 (16)	0.0139 (17)	−0.0020 (16)
N2	0.056 (2)	0.049 (2)	0.056 (2)	0.0045 (16)	0.0185 (18)	0.0003 (17)
C1	0.129 (2)	0.0729 (17)	0.141 (3)	0.0402 (16)	0.094 (2)	0.0351 (17)
C2	0.051 (2)	0.062 (3)	0.050 (3)	0.010 (2)	0.016 (2)	0.009 (2)
C14	0.047 (2)	0.049 (3)	0.049 (3)	0.0187 (19)	0.016 (2)	0.004 (2)
C13	0.047 (2)	0.040 (2)	0.057 (3)	0.0170 (18)	0.019 (2)	0.011 (2)
C9	0.050 (2)	0.059 (3)	0.071 (3)	0.023 (2)	0.030 (2)	0.020 (2)
C8	0.064 (3)	0.082 (3)	0.068 (3)	0.039 (2)	0.035 (3)	0.026 (3)
C7	0.057 (3)	0.062 (3)	0.050 (3)	0.027 (2)	0.014 (2)	−0.001 (2)
C6	0.085 (3)	0.088 (4)	0.059 (3)	0.042 (3)	0.021 (3)	0.005 (3)
C5	0.094 (4)	0.064 (3)	0.057 (3)	0.019 (3)	−0.003 (3)	−0.021 (2)
C4	0.067 (3)	0.053 (3)	0.079 (4)	0.006 (2)	0.008 (3)	−0.007 (3)
C10	0.052 (3)	0.055 (3)	0.108 (4)	0.010 (2)	0.039 (3)	0.024 (3)
C11	0.064 (3)	0.058 (3)	0.096 (4)	0.003 (2)	0.023 (3)	0.005 (3)
C12	0.066 (3)	0.055 (3)	0.065 (3)	0.007 (2)	0.012 (2)	−0.004 (2)
C3	0.080 (3)	0.046 (3)	0.069 (3)	0.012 (2)	0.039 (3)	0.011 (2)

Geometric parameters (Å, º)

Ru1—C1	1.865 (5)	C13—C9	1.394 (5)
Ru1—C3	1.882 (5)	C9—C10	1.377 (5)
Ru1—C2	1.914 (4)	C9—C8	1.488 (5)
Ru1—N1	2.168 (3)	C8—C7	1.486 (5)
Ru1—Cl2	2.4037 (16)	C7—C6	1.365 (5)
Ru1—Cl1	2.4128 (12)	C6—C5	1.370 (6)
O1—C1	1.141 (5)	C6—H6	0.9300
O2—C2	1.128 (4)	C5—C4	1.372 (5)
O4—C8	1.206 (4)	C5—H5	0.9300
O3—C3	1.146 (4)	C4—H4	0.9300
N1—C14	1.344 (4)	C10—C11	1.373 (5)
N1—C4	1.369 (4)	C10—H10	0.9300
N2—C13	1.314 (4)	C11—C12	1.362 (5)
N2—C12	1.350 (4)	C11—H11	0.9300
C14—C7	1.385 (5)	C12—H12	0.9300
C14—C13	1.490 (5)
C1—Ru1—C3	93.5 (2)	C10—C9—C8	131.2 (4)
C1—Ru1—C2	89.90 (18)	C13—C9—C8	108.6 (4)
C3—Ru1—C2	95.34 (16)	O4—C8—C7	126.6 (4)
C1—Ru1—N1	173.34 (18)	O4—C8—C9	128.1 (4)
C3—Ru1—N1	90.43 (15)	C7—C8—C9	105.2 (4)
C2—Ru1—N1	95.11 (13)	C6—C7—C14	121.1 (4)
C1—Ru1—Cl2	87.35 (18)	C6—C7—C8	129.3 (4)
C3—Ru1—Cl2	178.40 (13)	C14—C7—C8	109.5 (4)
C2—Ru1—Cl2	86.04 (12)	C7—C6—C5	117.0 (4)
N1—Ru1—Cl2	88.62 (10)	C7—C6—H6	121.5
C1—Ru1—Cl1	85.99 (15)	C5—C6—H6	121.5
C3—Ru1—Cl1	86.50 (12)	C6—C5—C4	120.2 (4)
C2—Ru1—Cl1	175.60 (11)	C6—C5—H5	119.9
N1—Ru1—Cl1	88.86 (9)	C4—C5—H5	119.9
Cl2—Ru1—Cl1	92.18 (5)	N1—C4—C5	123.6 (4)
C14—N1—C4	115.2 (3)	N1—C4—H4	118.2
C14—N1—Ru1	129.1 (3)	C5—C4—H4	118.2
C4—N1—Ru1	115.7 (3)	C11—C10—C9	116.3 (4)
C13—N2—C12	114.9 (3)	C11—C10—H10	121.9
O1—C1—Ru1	177.9 (5)	C9—C10—H10	121.9
O2—C2—Ru1	172.3 (3)	C12—C11—C10	119.8 (4)
N1—C14—C7	122.9 (4)	C12—C11—H11	120.1
N1—C14—C13	129.2 (3)	C10—C11—H11	120.1
C7—C14—C13	107.9 (4)	N2—C12—C11	125.0 (4)
N2—C13—C9	123.9 (4)	N2—C12—H12	117.5
N2—C13—C14	127.4 (3)	C11—C12—H12	117.5
C9—C13—C14	108.7 (3)	O3—C3—Ru1	177.4 (4)
C10—C9—C13	120.1 (4)