μ-Pyrazine-2,5-dicarboxyl­ato-bis­[chlorido(η6-p-cymene)ruthenium(II)] tert-butanol disolvate

Sanchez Ballester, N.M.; Elsegood, M.R.J.; Smith, M.B.

doi:10.1107/S1600536808000202

μ-Pyrazine-2,5-dicarboxylato-bis[chlorido(η⁶-p-cymene)ruthenium(II)] tert-butanol disolvate

N. M. Sanchez Ballester, M. R. J. Elsegood and M. B. Smith

A new tert-butanol solvate of [{(ⁱPrC₆H₄Me)RuCl}₂{μ-2,5-pyz(COO)₂}] (pyz = pyrazine) has been crystallized and structurally characterized. The solvate, [Ru₂(C₁₀H₁₄)₂(C₆H₂N₂O₄)Cl₂]·2C₄H₁₀O, contains one half-molecule of the ruthenium(II) complex and one molecule of tert-butanol in the asymmetric unit. The complex molecule lies on an inversion centre with the two chlorides trans. In contrast, the previously reported structure was solvent-free. Similar metric parameters are found between the butanol solvate and the solvent-free form and an intermolecular O—H

O hydrogen bond exists between μ-pyrazine-2,5-dicarboxylato-bis[chlorido(η⁶-p-cymene)ruthenium(II)] and the tert-butanol molecule.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808000202/bv2088sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536808000202/bv2088Isup2.hkl Contains datablock I

CCDC reference: 677800

checkCIF report

Key indicators

Single-crystal X-ray study
T = 120 K
Mean (C-C) = 0.007 Å
R factor = 0.049
wR factor = 0.115
Data-to-parameter ratio = 19.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT221_ALERT_4_B Large Solvent/Anion  C     Ueq(max)/Ueq(min) ...       4.48 Ratio

Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.68
PLAT223_ALERT_4_C Large Solvent/Anion  H     Ueq(max)/Ueq(min) ...       4.00 Ratio
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C14
PLAT360_ALERT_2_C Short  C(sp3)-C(sp3) Bond  C14    -   C15    ...       1.42 Ang.
PLAT415_ALERT_2_C Short Inter D-H..H-X       H3     ..  H12     ..       2.10 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C4 H10 O

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

There has been considerable interest in the chemistry of areneruthenium(II) complexes for a variety of purposes. These range from their interesting and varied coordination chemistry (Cadierno et al., 2002; Drommi et al., 1995) including DNA binding studies (Dorcier et al., 2005) to applications in areas including supramolecular chemistry, as highly selective receptors and catalysis (Dann et al., 2006; Ganter, 2003; Grote et al., 2004; Ion et al., 2006). These organometallic ruthenium(II) fragments have also been used in the synthesis of chiral half-sandwich compounds (Ganter, 2003; Pinto et al., 2004). Pyrazine polycarboxylic acids are excellent ligands for metal coordination (Konar et al., 2004; Ma et al., 2004). Complexes of ruthenium(II) with pyrazine carboxylic acids are known and their redox behaviour has been studied by voltammetric methods (Govindaswamy et al., 2007). We report here the molecular structure of a new tert-butanol solvate of the ruthenium(II) complex [{(η⁶-p-ⁱPrC₆H₄Me)RuCl}₂{µ-2,5-pyz(COO)₂}]\. ^tBuOH 1. The solvent free structure, 2, which contains one molecule with a trans configuration of the two chloro ligands and a second molecule with twofold symmetry that has two chloro ligands disposed in a cis configuration, has recently been reported (Govindaswamy et al., 2007).

The molecular structure of 1 is shown in Figure 1 and shows a typical piano-stool geometry at each ruthenium(II) centre with each metal bonded to an η⁶-p-ⁱPrC₆H₄Me arene [Ru—C_centroid 1.6689 (16) Å], a terminal chloride and a dianionic N,O-chelating pyrazine ligand. The Ru—Cl bond length in 1 [2.3975 (11) Å] is slightly shorter than that in the trans isomer [2.408 (5) Å] of 2 yet similar to the cis isomer [2.388 (3) Å, 2.399 (3) Å]. The Ru—O and Ru—N bond distances in 1 [2.099 (3) Å and 2.097 (3) Å respectively] are similar to those in the cis isomer of 2 [2.083 (10)/2.109 (9) Å and 2.102 (7)/2.074 (7) Å respectively] and with those of other related three-legged piano-stool ruthenium(II) complexes (Carter et al., 1993; Gemel et al., 2000; Lahuerta et al., 1988). The N(1)—Ru(1)—O(2) bite angle in 1 [77.29 (12)°] is broadly as expected for this type of five-membered chelating ligand. The η⁶-p-ⁱPrC₆H₄Me arene ring is essentially planar with C—C bond lengths in the range 1.392 (6)–1.435 (6) Å. The Ru complex is hydrogen-bonded to a ^tBuOH molecule through a strong intermolecular O—H···O interaction.

In summary, we have reported the crystal structure of a new tert-butanol solvate form of [{(η⁶-p-ⁱPrC₆H₄Me)RuCl}₂{µ-2,5-pyz(COO)₂}] 1 that displays very similar bond lengths and angles around the ruthenium(II) coordination sphere to complex 2 recently published (Govindaswamy et al., 2007).

Related literature top

The structure of the solvent-free complex has been reported previously (Govindaswamy et al., 2007) and shows two molecules in the asymmetric unit. One molecule adopts a trans configuration of the two chloro ligands while the second lies on a twofold axis giving the two chloro ligands a cis configuration.

For other related literature, see: Cadierno et al. (2002); Carter et al. (1993); Dann et al. (2006); Dorcier et al. (2005); Drommi et al. (1995); Ganter (2003); Gemel et al. (2000); Grote et al. (2004); Ion et al. (2006); Konar et al. (2004); Lahuerta et al. (1988); Ma et al. (2004); Pinto et al. (2004).

Experimental top

Crystals of compound 1 were obtained unexpectedly from the experimental procedure outlined here. Boronic acid (0.004 g, 0.007 mmol) in warm ^tBuOH (10 ml) was added dropwise to a solution of [{(η⁶-p-ⁱPrC₆H₄Me)RuCl}₂{µ-2,5-pyz(COO)₂}] (0.023 g, 0.0325 mmol) in CH₂Cl₂ (10 ml) affording an orange-red solution. The solution was stirred at room temperature for 3 h and the volume was concentrated to 2–3 ml. Suitable X-ray quality crystals of 1 were obtained by slow vapour diffusion of diethyl ether into the concentrated CH₂Cl₂/^tBuOH solution.

Computing details top

Data collection: COLLECT (Hooft, 1998) or APEX2 (Bruker, 2000)?; cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT or APEX2 (Bruker, 2000)?; data reduction: DENZO and COLLECT or APEX2 (Bruker, 2000)?; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001) and local programs.

Figures top

Fig. 1. View of 1, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. All H atoms except on O(3) have been removed for clarity. Symmetry operator: A = -x, -y, -z.

µ-Pyrazine-2,5-dicarboxylato-bis[chlorido(η⁶-p-cymene)ruthenium(II)] tert-butanol disolvate top

Crystal data top

[Ru₂(C₁₀H₁₄)₂(C₆H₂N₂O₄)Cl₂]·2(C₄H₁₀O)	F(000) = 876
M_r = 855.80	D_x = 1.550 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4336 reflections
a = 9.8483 (2) Å	θ = 2.9–27.5°
b = 11.3968 (3) Å	µ = 1.01 mm⁻¹
c = 16.3448 (3) Å	T = 120 K
β = 91.465 (2)°	Rod, brown
V = 1833.93 (7) Å³	0.18 × 0.04 × 0.03 mm
Z = 2

Data collection top

Bruker Nonius APEXII CCD camera on κ-goniostat diffractometer	4195 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	3594 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 4090x4096pixels/62x62mm pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ϕ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −14→14
T_min = 0.839, T_max = 0.970	l = −20→21
18492 measured reflections

Refinement top

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0329P)² + 10.5824P] where P = (F_o² + 2F_c²)/3
4196 reflections	(Δ/σ)_max = 0.034
215 parameters	Δρ_max = 2.78 e Å⁻³
0 restraints	Δρ_min = −1.04 e Å⁻³

Crystal data top

[Ru₂(C₁₀H₁₄)₂(C₆H₂N₂O₄)Cl₂]·2(C₄H₁₀O)	V = 1833.93 (7) Å³
M_r = 855.80	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.8483 (2) Å	µ = 1.01 mm⁻¹
b = 11.3968 (3) Å	T = 120 K
c = 16.3448 (3) Å	0.18 × 0.04 × 0.03 mm
β = 91.465 (2)°

Data collection top

Bruker Nonius APEXII CCD camera on κ-goniostat diffractometer	4195 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	3594 reflections with I > 2σ(I)
T_min = 0.839, T_max = 0.970	R_int = 0.046
18492 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0329P)² + 10.5824P] where P = (F_o² + 2F_c²)/3
4196 reflections	Δρ_max = 2.78 e Å⁻³
215 parameters	Δρ_min = −1.04 e Å⁻³

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
Ru1	0.09960 (3)	0.28799 (3)	0.037062 (19)	0.01586 (11)
Cl1	0.13823 (11)	0.29072 (9)	−0.10715 (6)	0.0245 (2)
C1	0.0607 (4)	0.3713 (4)	0.1547 (2)	0.0199 (8)
C2	0.1442 (4)	0.2730 (4)	0.1682 (2)	0.0206 (8)
H2	0.1190	0.2153	0.2069	0.025*
C3	0.2668 (4)	0.2590 (4)	0.1243 (3)	0.0231 (9)
H3A	0.3213	0.1912	0.1335	0.028*
C4	0.3085 (4)	0.3447 (4)	0.0673 (3)	0.0236 (9)
C5	0.2248 (4)	0.4460 (4)	0.0561 (3)	0.0217 (8)
H5	0.2516	0.5056	0.0193	0.026*
C6	0.1045 (4)	0.4591 (4)	0.0982 (3)	0.0216 (8)
H6	0.0506	0.5272	0.0893	0.026*
C7	−0.0741 (5)	0.3876 (4)	0.1953 (3)	0.0281 (10)
H7	−0.1365	0.4297	0.1560	0.034*
C8	−0.0512 (6)	0.4661 (5)	0.2700 (3)	0.0360 (11)
H8A	0.0074	0.4256	0.3103	0.054*
H8B	−0.1387	0.4839	0.2944	0.054*
H8C	−0.0076	0.5393	0.2533	0.054*
C9	−0.1430 (5)	0.2730 (5)	0.2199 (3)	0.0382 (12)
H9A	−0.1494	0.2205	0.1725	0.057*
H9B	−0.2344	0.2899	0.2392	0.057*
H9C	−0.0894	0.2352	0.2638	0.057*
C10	0.4356 (5)	0.3291 (5)	0.0202 (3)	0.0363 (12)
H10A	0.5109	0.3694	0.0487	0.054*
H10B	0.4225	0.3623	−0.0347	0.054*
H10C	0.4565	0.2453	0.0159	0.054*
N1	0.0476 (3)	0.1115 (3)	0.01791 (19)	0.0155 (6)
C11	−0.0800 (4)	0.0943 (3)	−0.0104 (2)	0.0161 (7)
C12	0.1276 (4)	0.0178 (3)	0.0281 (2)	0.0177 (8)
H12	0.2185	0.0280	0.0478	0.021*
C13	−0.1656 (4)	0.2038 (3)	−0.0213 (2)	0.0171 (8)
O1	−0.2818 (3)	0.1959 (3)	−0.0502 (2)	0.0293 (7)
O2	−0.1073 (3)	0.2977 (2)	0.00366 (18)	0.0205 (6)
C14	−0.5253 (5)	0.0313 (5)	−0.1783 (3)	0.0391 (12)
C16	−0.5410 (7)	0.1587 (6)	−0.2005 (5)	0.0596 (18)
H16A	−0.4918	0.1749	−0.2506	0.089*
H16B	−0.5041	0.2073	−0.1558	0.089*
H16C	−0.6375	0.1768	−0.2095	0.089*
C17	−0.6231 (8)	0.0080 (8)	−0.1086 (5)	0.081 (2)
H17A	−0.7153	0.0310	−0.1260	0.122*
H17B	−0.5948	0.0538	−0.0604	0.122*
H17C	−0.6218	−0.0757	−0.0949	0.122*
C15	−0.5355 (14)	−0.0404 (12)	−0.2492 (7)	0.176 (8)
H15A	−0.4682	−0.0151	−0.2887	0.264*
H15B	−0.6268	−0.0333	−0.2739	0.264*
H15C	−0.5184	−0.1224	−0.2340	0.264*
O3	−0.3929 (4)	0.0100 (3)	−0.1422 (3)	0.0438 (10)
H3	−0.3711	0.0663	−0.1114	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.01907 (17)	0.01018 (16)	0.01823 (17)	0.00040 (12)	−0.00136 (11)	−0.00046 (12)
Cl1	0.0329 (5)	0.0211 (5)	0.0194 (5)	0.0014 (4)	0.0014 (4)	−0.0001 (4)
C1	0.0221 (19)	0.0154 (19)	0.022 (2)	−0.0005 (15)	−0.0016 (16)	−0.0046 (16)
C2	0.028 (2)	0.017 (2)	0.0160 (19)	−0.0009 (16)	−0.0094 (16)	−0.0006 (15)
C3	0.023 (2)	0.019 (2)	0.027 (2)	0.0026 (16)	−0.0100 (17)	−0.0034 (17)
C4	0.023 (2)	0.023 (2)	0.025 (2)	−0.0061 (17)	−0.0033 (16)	−0.0053 (17)
C5	0.029 (2)	0.0116 (18)	0.025 (2)	−0.0073 (16)	−0.0016 (17)	−0.0005 (16)
C6	0.031 (2)	0.0112 (19)	0.022 (2)	−0.0005 (16)	−0.0028 (17)	−0.0057 (16)
C7	0.030 (2)	0.028 (2)	0.027 (2)	0.0027 (19)	0.0020 (18)	−0.0011 (19)
C8	0.049 (3)	0.031 (3)	0.029 (2)	0.003 (2)	0.010 (2)	−0.006 (2)
C9	0.032 (3)	0.039 (3)	0.044 (3)	−0.004 (2)	0.012 (2)	−0.005 (2)
C10	0.025 (2)	0.040 (3)	0.044 (3)	−0.005 (2)	0.004 (2)	−0.012 (2)
N1	0.0189 (15)	0.0120 (15)	0.0155 (15)	0.0026 (12)	0.0002 (12)	0.0012 (12)
C11	0.0156 (17)	0.0163 (18)	0.0163 (18)	0.0013 (14)	−0.0009 (14)	0.0015 (15)
C12	0.0193 (18)	0.0127 (18)	0.021 (2)	0.0029 (14)	−0.0025 (15)	0.0024 (15)
C13	0.0175 (18)	0.0118 (18)	0.022 (2)	0.0012 (14)	−0.0015 (15)	0.0016 (15)
O1	0.0230 (15)	0.0192 (16)	0.045 (2)	0.0034 (12)	−0.0097 (14)	−0.0013 (14)
O2	0.0194 (14)	0.0138 (14)	0.0280 (16)	0.0032 (11)	−0.0038 (11)	−0.0024 (12)
C14	0.033 (3)	0.045 (3)	0.039 (3)	−0.004 (2)	−0.014 (2)	0.010 (2)
C16	0.048 (4)	0.052 (4)	0.077 (5)	0.013 (3)	−0.018 (3)	0.006 (3)
C17	0.073 (5)	0.079 (6)	0.092 (6)	−0.014 (4)	0.014 (5)	0.027 (5)
C15	0.225 (14)	0.180 (13)	0.117 (9)	0.140 (12)	−0.123 (10)	−0.100 (9)
O3	0.0337 (19)	0.0284 (19)	0.068 (3)	0.0077 (15)	−0.0194 (18)	−0.0112 (18)

Geometric parameters (Å, º) top

Ru1—N1	2.097 (3)	C9—H9B	0.9800
Ru1—O2	2.099 (3)	C9—H9C	0.9800
Ru1—C3	2.176 (4)	C10—H10A	0.9800
Ru1—C2	2.184 (4)	C10—H10B	0.9800
Ru1—C1	2.187 (4)	C10—H10C	0.9800
Ru1—C6	2.191 (4)	N1—C12	1.335 (5)
Ru1—C5	2.200 (4)	N1—C11	1.343 (5)
Ru1—C4	2.201 (4)	C11—C12ⁱ	1.389 (5)
Ru1—Cl1	2.3975 (11)	C11—C13	1.514 (5)
C1—C2	1.404 (6)	C12—C11ⁱ	1.389 (5)
C1—C6	1.435 (6)	C12—H12	0.9500
C1—C7	1.511 (6)	C13—O1	1.231 (5)
C2—C3	1.429 (6)	C13—O2	1.277 (5)
C2—H2	0.9500	C14—C15	1.419 (10)
C3—C4	1.417 (6)	C14—O3	1.438 (6)
C3—H3A	0.9500	C14—C16	1.503 (8)
C4—C5	1.428 (6)	C14—C17	1.534 (9)
C4—C10	1.496 (7)	C16—H16A	0.9800
C5—C6	1.392 (6)	C16—H16B	0.9800
C5—H5	0.9500	C16—H16C	0.9800
C6—H6	0.9500	C17—H17A	0.9800
C7—C8	1.525 (6)	C17—H17B	0.9800
C7—C9	1.530 (7)	C17—H17C	0.9800
C7—H7	1.0000	C15—H15A	0.9800
C8—H8A	0.9800	C15—H15B	0.9800
C8—H8B	0.9800	C15—H15C	0.9800
C8—H8C	0.9800	O3—H3	0.8400
C9—H9A	0.9800

N1—Ru1—O2	77.29 (12)	C5—C6—Ru1	71.9 (2)
N1—Ru1—C3	97.48 (14)	C1—C6—Ru1	70.7 (2)
O2—Ru1—C3	153.12 (15)	C5—C6—H6	119.5
N1—Ru1—C2	96.53 (14)	C1—C6—H6	119.5
O2—Ru1—C2	115.40 (14)	Ru1—C6—H6	130.7
C3—Ru1—C2	38.27 (17)	C1—C7—C8	108.1 (4)
N1—Ru1—C1	120.00 (14)	C1—C7—C9	114.3 (4)
O2—Ru1—C1	90.86 (13)	C8—C7—C9	110.4 (4)
C3—Ru1—C1	68.67 (16)	C1—C7—H7	108.0
C2—Ru1—C1	37.47 (15)	C8—C7—H7	108.0
N1—Ru1—C6	157.55 (15)	C9—C7—H7	108.0
O2—Ru1—C6	94.69 (14)	C7—C8—H8A	109.5
C3—Ru1—C6	80.13 (16)	C7—C8—H8B	109.5
C2—Ru1—C6	67.69 (15)	H8A—C8—H8B	109.5
C1—Ru1—C6	38.28 (15)	C7—C8—H8C	109.5
N1—Ru1—C5	160.06 (15)	H8A—C8—H8C	109.5
O2—Ru1—C5	122.04 (14)	H8B—C8—H8C	109.5
C3—Ru1—C5	67.62 (16)	C7—C9—H9A	109.5
C2—Ru1—C5	80.04 (16)	C7—C9—H9B	109.5
C1—Ru1—C5	68.30 (16)	H9A—C9—H9B	109.5
C6—Ru1—C5	36.97 (16)	C7—C9—H9C	109.5
N1—Ru1—C4	122.58 (15)	H9A—C9—H9C	109.5
O2—Ru1—C4	159.86 (14)	H9B—C9—H9C	109.5
C3—Ru1—C4	37.78 (17)	C4—C10—H10A	109.5
C2—Ru1—C4	68.83 (16)	C4—C10—H10B	109.5
C1—Ru1—C4	81.87 (16)	H10A—C10—H10B	109.5
C6—Ru1—C4	68.07 (16)	C4—C10—H10C	109.5
C5—Ru1—C4	37.87 (16)	H10A—C10—H10C	109.5
N1—Ru1—Cl1	84.84 (9)	H10B—C10—H10C	109.5
O2—Ru1—Cl1	85.47 (9)	C12—N1—C11	118.1 (3)
C3—Ru1—Cl1	120.66 (13)	C12—N1—Ru1	127.4 (3)
C2—Ru1—Cl1	158.93 (12)	C11—N1—Ru1	114.5 (3)
C1—Ru1—Cl1	153.45 (11)	N1—C11—C12ⁱ	121.0 (4)
C6—Ru1—Cl1	115.75 (12)	N1—C11—C13	115.7 (3)
C5—Ru1—Cl1	91.50 (12)	C12ⁱ—C11—C13	123.3 (3)
C4—Ru1—Cl1	92.66 (12)	N1—C12—C11ⁱ	121.0 (4)
C2—C1—C6	118.2 (4)	N1—C12—H12	119.5
C2—C1—C7	123.1 (4)	C11ⁱ—C12—H12	119.5
C6—C1—C7	118.6 (4)	O1—C13—O2	126.2 (4)
C2—C1—Ru1	71.2 (2)	O1—C13—C11	119.6 (3)
C6—C1—Ru1	71.0 (2)	O2—C13—C11	114.2 (3)
C7—C1—Ru1	128.0 (3)	C13—O2—Ru1	117.7 (2)
C1—C2—C3	120.6 (4)	C15—C14—O3	106.4 (6)
C1—C2—Ru1	71.4 (2)	C15—C14—C16	110.8 (7)
C3—C2—Ru1	70.6 (2)	O3—C14—C16	110.4 (5)
C1—C2—H2	119.7	C15—C14—C17	118.3 (9)
C3—C2—H2	119.7	O3—C14—C17	104.3 (5)
Ru1—C2—H2	131.2	C16—C14—C17	106.4 (6)
C4—C3—C2	121.1 (4)	C14—C16—H16A	109.5
C4—C3—Ru1	72.1 (2)	C14—C16—H16B	109.5
C2—C3—Ru1	71.2 (2)	H16A—C16—H16B	109.5
C4—C3—H3A	119.5	C14—C16—H16C	109.5
C2—C3—H3A	119.5	H16A—C16—H16C	109.5
Ru1—C3—H3A	129.9	H16B—C16—H16C	109.5
C3—C4—C5	117.7 (4)	C14—C17—H17A	109.5
C3—C4—C10	121.1 (4)	C14—C17—H17B	109.5
C5—C4—C10	121.2 (4)	H17A—C17—H17B	109.5
C3—C4—Ru1	70.2 (2)	C14—C17—H17C	109.5
C5—C4—Ru1	71.0 (2)	H17A—C17—H17C	109.5
C10—C4—Ru1	129.7 (3)	H17B—C17—H17C	109.5
C6—C5—C4	121.3 (4)	C14—C15—H15A	109.5
C6—C5—Ru1	71.2 (2)	C14—C15—H15B	109.5
C4—C5—Ru1	71.1 (2)	H15A—C15—H15B	109.5
C6—C5—H5	119.4	C14—C15—H15C	109.5
C4—C5—H5	119.4	H15A—C15—H15C	109.5
Ru1—C5—H5	131.3	H15B—C15—H15C	109.5
C5—C6—C1	121.1 (4)	C14—O3—H3	109.5

N1—Ru1—C1—C2	57.5 (3)	Cl1—Ru1—C4—C10	−26.2 (4)
O2—Ru1—C1—C2	133.3 (2)	C3—C4—C5—C6	−1.5 (6)
C3—Ru1—C1—C2	−28.8 (2)	C10—C4—C5—C6	178.2 (4)
C6—Ru1—C1—C2	−130.2 (4)	Ru1—C4—C5—C6	52.6 (4)
C5—Ru1—C1—C2	−102.3 (3)	C3—C4—C5—Ru1	−54.1 (3)
C4—Ru1—C1—C2	−65.6 (3)	C10—C4—C5—Ru1	125.5 (4)
Cl1—Ru1—C1—C2	−145.2 (2)	N1—Ru1—C5—C6	−147.6 (4)
N1—Ru1—C1—C6	−172.3 (2)	O2—Ru1—C5—C6	47.9 (3)
O2—Ru1—C1—C6	−96.5 (2)	C3—Ru1—C5—C6	−103.8 (3)
C3—Ru1—C1—C6	101.4 (3)	C2—Ru1—C5—C6	−66.0 (3)
C2—Ru1—C1—C6	130.2 (4)	C1—Ru1—C5—C6	−28.8 (2)
C5—Ru1—C1—C6	27.9 (2)	C4—Ru1—C5—C6	−134.2 (4)
C4—Ru1—C1—C6	64.7 (3)	Cl1—Ru1—C5—C6	133.5 (2)
Cl1—Ru1—C1—C6	−14.9 (4)	N1—Ru1—C5—C4	−13.4 (6)
N1—Ru1—C1—C7	−60.3 (4)	O2—Ru1—C5—C4	−178.0 (2)
O2—Ru1—C1—C7	15.5 (4)	C3—Ru1—C5—C4	30.3 (3)
C3—Ru1—C1—C7	−146.6 (4)	C2—Ru1—C5—C4	68.2 (3)
C2—Ru1—C1—C7	−117.8 (5)	C1—Ru1—C5—C4	105.3 (3)
C6—Ru1—C1—C7	112.0 (5)	C6—Ru1—C5—C4	134.2 (4)
C5—Ru1—C1—C7	139.9 (4)	Cl1—Ru1—C5—C4	−92.4 (2)
C4—Ru1—C1—C7	176.6 (4)	C4—C5—C6—C1	0.3 (6)
Cl1—Ru1—C1—C7	97.1 (4)	Ru1—C5—C6—C1	52.9 (3)
C6—C1—C2—C3	−2.4 (6)	C4—C5—C6—Ru1	−52.6 (3)
C7—C1—C2—C3	176.3 (4)	C2—C1—C6—C5	1.7 (6)
Ru1—C1—C2—C3	52.6 (3)	C7—C1—C6—C5	−177.0 (4)
C6—C1—C2—Ru1	−55.0 (3)	Ru1—C1—C6—C5	−53.4 (3)
C7—C1—C2—Ru1	123.6 (4)	C2—C1—C6—Ru1	55.1 (3)
N1—Ru1—C2—C1	−132.7 (2)	C7—C1—C6—Ru1	−123.6 (4)
O2—Ru1—C2—C1	−53.7 (3)	N1—Ru1—C6—C5	151.4 (3)
C3—Ru1—C2—C1	133.5 (4)	O2—Ru1—C6—C5	−140.9 (2)
C6—Ru1—C2—C1	30.7 (2)	C3—Ru1—C6—C5	65.7 (3)
C5—Ru1—C2—C1	67.2 (3)	C2—Ru1—C6—C5	103.5 (3)
C4—Ru1—C2—C1	104.8 (3)	C1—Ru1—C6—C5	133.7 (4)
Cl1—Ru1—C2—C1	134.7 (3)	C4—Ru1—C6—C5	28.3 (2)
N1—Ru1—C2—C3	93.8 (2)	Cl1—Ru1—C6—C5	−53.7 (3)
O2—Ru1—C2—C3	172.8 (2)	N1—Ru1—C6—C1	17.7 (5)
C1—Ru1—C2—C3	−133.5 (4)	O2—Ru1—C6—C1	85.4 (2)
C6—Ru1—C2—C3	−102.8 (3)	C3—Ru1—C6—C1	−68.0 (2)
C5—Ru1—C2—C3	−66.3 (3)	C2—Ru1—C6—C1	−30.1 (2)
C4—Ru1—C2—C3	−28.7 (2)	C5—Ru1—C6—C1	−133.7 (4)
Cl1—Ru1—C2—C3	1.2 (5)	C4—Ru1—C6—C1	−105.3 (3)
C1—C2—C3—C4	1.2 (6)	Cl1—Ru1—C6—C1	172.66 (19)
Ru1—C2—C3—C4	54.2 (3)	C2—C1—C7—C8	97.1 (5)
C1—C2—C3—Ru1	−53.0 (3)	C6—C1—C7—C8	−84.3 (5)
N1—Ru1—C3—C4	135.8 (3)	Ru1—C1—C7—C8	−171.7 (3)
O2—Ru1—C3—C4	−147.6 (3)	C2—C1—C7—C9	−26.2 (6)
C2—Ru1—C3—C4	−133.1 (4)	C6—C1—C7—C9	152.5 (4)
C1—Ru1—C3—C4	−104.8 (3)	Ru1—C1—C7—C9	65.0 (5)
C6—Ru1—C3—C4	−66.8 (3)	O2—Ru1—N1—C12	−177.7 (4)
C5—Ru1—C3—C4	−30.4 (3)	C3—Ru1—N1—C12	−24.5 (4)
Cl1—Ru1—C3—C4	47.4 (3)	C2—Ru1—N1—C12	−63.0 (3)
N1—Ru1—C3—C2	−91.1 (2)	C1—Ru1—N1—C12	−94.1 (4)
O2—Ru1—C3—C2	−14.5 (4)	C6—Ru1—N1—C12	−106.7 (5)
C1—Ru1—C3—C2	28.3 (2)	C5—Ru1—N1—C12	15.7 (6)
C6—Ru1—C3—C2	66.3 (3)	C4—Ru1—N1—C12	6.0 (4)
C5—Ru1—C3—C2	102.7 (3)	Cl1—Ru1—N1—C12	95.8 (3)
C4—Ru1—C3—C2	133.1 (4)	O2—Ru1—N1—C11	4.7 (3)
Cl1—Ru1—C3—C2	−179.5 (2)	C3—Ru1—N1—C11	157.9 (3)
C2—C3—C4—C5	0.8 (6)	C2—Ru1—N1—C11	119.3 (3)
Ru1—C3—C4—C5	54.6 (3)	C1—Ru1—N1—C11	88.2 (3)
C2—C3—C4—C10	−178.9 (4)	C6—Ru1—N1—C11	75.6 (5)
Ru1—C3—C4—C10	−125.1 (4)	C5—Ru1—N1—C11	−161.9 (4)
C2—C3—C4—Ru1	−53.8 (3)	C4—Ru1—N1—C11	−171.7 (3)
N1—Ru1—C4—C3	−55.1 (3)	Cl1—Ru1—N1—C11	−81.8 (3)
O2—Ru1—C4—C3	135.3 (4)	C12—N1—C11—C12ⁱ	0.3 (6)
C2—Ru1—C4—C3	29.0 (3)	Ru1—N1—C11—C12ⁱ	178.2 (3)
C1—Ru1—C4—C3	65.4 (3)	C12—N1—C11—C13	−179.6 (3)
C6—Ru1—C4—C3	102.6 (3)	Ru1—N1—C11—C13	−1.8 (4)
C5—Ru1—C4—C3	130.3 (4)	C11—N1—C12—C11ⁱ	−0.3 (6)
Cl1—Ru1—C4—C3	−140.7 (2)	Ru1—N1—C12—C11ⁱ	−177.9 (3)
N1—Ru1—C4—C5	174.6 (2)	N1—C11—C13—O1	176.9 (4)
O2—Ru1—C4—C5	5.0 (6)	C12ⁱ—C11—C13—O1	−3.0 (6)
C3—Ru1—C4—C5	−130.3 (4)	N1—C11—C13—O2	−4.7 (5)
C2—Ru1—C4—C5	−101.3 (3)	C12ⁱ—C11—C13—O2	175.3 (4)
C1—Ru1—C4—C5	−64.9 (3)	O1—C13—O2—Ru1	−172.8 (4)
C6—Ru1—C4—C5	−27.7 (2)	C11—C13—O2—Ru1	9.0 (4)
Cl1—Ru1—C4—C5	89.0 (2)	N1—Ru1—O2—C13	−7.8 (3)
N1—Ru1—C4—C10	59.4 (5)	C3—Ru1—O2—C13	−89.2 (4)
O2—Ru1—C4—C10	−110.3 (5)	C2—Ru1—O2—C13	−99.1 (3)
C3—Ru1—C4—C10	114.5 (5)	C1—Ru1—O2—C13	−128.4 (3)
C2—Ru1—C4—C10	143.5 (5)	C6—Ru1—O2—C13	−166.6 (3)
C1—Ru1—C4—C10	179.9 (5)	C5—Ru1—O2—C13	166.9 (3)
C6—Ru1—C4—C10	−143.0 (5)	C4—Ru1—O2—C13	163.3 (4)
C5—Ru1—C4—C10	−115.2 (5)	Cl1—Ru1—O2—C13	77.9 (3)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1	0.84	1.98	2.804 (5)	168

Experimental details

Crystal data
Chemical formula	[Ru₂(C₁₀H₁₄)₂(C₆H₂N₂O₄)Cl₂]·2(C₄H₁₀O)
M_r	855.80
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	9.8483 (2), 11.3968 (3), 16.3448 (3)
β (°)	91.465 (2)
V (Å³)	1833.93 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.01
Crystal size (mm)	0.18 × 0.04 × 0.03

Data collection
Diffractometer	Bruker Nonius APEXII CCD camera on κ-goniostat diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2007)
T_min, T_max	0.839, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	18492, 4195, 3594
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.115, 1.06
No. of reflections	4196
No. of parameters	215
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0329P)² + 10.5824P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	2.78, −1.04

Computer programs: COLLECT (Hooft, 1998) or APEX2 (Bruker, 2000)?, DENZO (Otwinowski & Minor, 1997) and COLLECT or APEX2 (Bruker, 2000)?, DENZO and COLLECT or APEX2 (Bruker, 2000)?, SHELXTL (Sheldrick, 2001) and local programs.