Di-[mu]-benzoato-bis­[di­carbonyl­(pyri­dine)­ruthenium(I)] (new polymorph) and di-[mu]-tri­fluoro­acetato-bis­[di­carbonyl­(pyridine)­ruthenium(I)]

The syntheses and crystal structure determinations of a pair of `sawhorse' dimers are reported, viz. [Ru₂(C₆H₅CO₂)₂(C₅H₅N)₂(CO)₄] [a new polymorph, cf. Kepert, Deacon, Spiccia, Fallon, Skelton & White (2000). J. Chem. Soc. Dalton Trans. pp. 2867-2874] and [Ru₂(CF₃CO₂)₂(C₅H₅N)₂(CO)₄]. The Ru...Ru distances are 2.6724 (2) and 2.7122 (5) Å, respectively.

S1. Comment

An earlier report (Kepert et al., 2000) records the syntheses and chemical and structural characterizations of a number of binuclear ruthenium(I) `sawhorse' complexes, viz. [Ru(RCO₂)(CO)₂L]₂ (R = Me, Et, ^tBu and Ph; L is pyridine (py) or 3-methylpyridine (mpy). Despite the diversity of carboxylate substituents, the core geometry of the binuclear array proved remarkably resistant to any form of systematic substituent variation across the array. A counterpart complex with an electronically more significantly varied substituent (R = CF₃ and L = py), (II), has since been crystallized and examined structurally as an extension of the series, as reported here; also reported is the structure of a second monoclinic polymorph, (I), this time in space group P2₁/c rather than C2/c, of the previously studied complex (R = Ph and L = py). Both (I) and (II) were obtained as unsolvated crystals; a further phase of the Ph/py complex, is a toluene hemisolvate (triclinic, P1, Z=2; Li Xu and Sasaki, 1999). There are no coordinates in the CCDC deposition for this form; the limited data in that report, in particular, the Ru—Ru distance of 2.6809 (7) and <Ru—O> distance of 2.121 (4) Å, agree with the following comments.

In both phases of (I), [Ru(PhCO₂)(CO₂(py)]₂, one binuclear molecule, devoid of crystallographic symmetry, composes the asymmetric unit of the structure. The geometries of the present phase (Table 1) are generally similar to those of the other phase, insofar as bond lengths and angles are concerned. There is a significant difference, however, in respect of the dihedral angle between the pair of C₂O₂ carboxylate planes, the present value of 78.20 (7)° being more nearly comparable to the values of 67.5 (1), 71 (1)/76 (1), 73.1 (4) and 70.8 (1)° reported previously for the analogue with R/L of Me/py, Me/mpy (2 mol), Et/py and ^tBu/py, all of which are very much less than that for the C2/c Ph/py phase [84.9 (2)°]. The molecule of the present phase has quasi-mm symmetry, the pyridine ligands lying in one putative mirror plane ('upright'), the other plane containing the C—C bonds of the carboxylates and the Ru—Ru bisector; this symmetry is also compatible with the pyridine ligands lying normal to the first mirror plane (`flat'), as reported for the Me/py adduct. The previous Ph/py (P2₁/c) molecule is unusual in that the pyridine ligands have a 1 upright/1 flat combination, reducing the putative molecular symmetry to m; it seems unlikely that this conformation (rather than, for example, 'packing forces') is responsible for the considerably greater splaying of the carboxylate ligands in the less symmetrical form; the disparity in, for example, the angles about the two ruthenium atoms is less than in the present more symmetric array. The C₆/CO₂ interplanar dihedral angles of the carboxylate ligands of the C2/c form are 15.7 (2) and 10.2 (1) [cf. the present values of 4.62 (7) and 6.55 (6)°]; the Ru-atom deviations from the CCO₂ planes are 0.148 (6) and 0.131 (6) for atom Ru1, and 0.228 (6) and 0.254 (5) Å for atom Ru2.

In the trifluoroacetate/pyridine counterpart, [Ru(F₃CCO₂)(CO)₂(py)]₂, (II), again one complete binuclear neutral molecule composes the asymmetric unit of the structure, with the putative symmetry again quasi-mm, with a pair of `upright' pyridine ligands. That symmetry is broken, however, by the pair of CF<sub>3</sub> substituents, whose mutual orientations are `geared'. Again, much of the common geometry of the core of the dimer is similar to that found in the related complexes. Worthy of note as being different, however, are the Ru—O distances, with a mean value of 2.144 (8)/%A [cf. the mean value in the C2/c and P2₁/c benzoates, 2.13 (1) Å, in which these bonds are slightly lengthened, in keeping with the diminished basicity of the ligand and with the more pronounced concomitant changes in the Ru—Ru distance]. The latter is the longest observed (cf. all of the other complexes) by more than 0.03 Å. [Ru—Ru distances in all other complexes (Kepert et al., 2000; Li Xu and Sasaki, 1999) are remarkably constant, lying between 2.672 (1)–2.6780 (4) Å)]. The mean O—C—O angle is 129.9 (1)/%, [cf. the benzoates mean angle of 125.3 (1)°], and the CCO₂/CCO₂ mean interplanar dihedral angle is 68.0 (2)°; all other angles lie above 70°, except that of the complex where R is Me/py, in which it is 67.5 (1)°. Atoms Ru1 and Ru2 deviate from the CCO₂ planes by 0.325 (7) and 0.289 (7) Å (plane 11n), and 0.223 (7) and 0.256 (7) Å (plane 12n), and from the C₅N planes 10n and 20n by 0.044 (6) and 0.132 (7) Å, respectively."

S2. Experimental

For the preparation of (I), di-µ-benzoatotetracarbonylbis(pyridine)diruthenium(I), [Ru(PhCO₂)(CO)₂(py)]₂. [Ru(CO)₂Cl₂]_n (231 mg, 1.01 mmol) was reacted with NaO₂CPh (1.4 g, 9.7 mmol) and pyridine (0.1 ml, 1.29 mmol) in methanol (30 ml) according to preparation method for [Ru(PhCO₂) (CO)₂(py)]₂ described by Kepert et al. (2000). Yellow crystals of the new polymorph of [Ru(PhCO₂)(CO)₂(py)]₂ were obtained (30 mg, 8% yield). (N·B. It is not clear what the determinant of the new, cf. the previous phase is, as yet). Analysis found: C 47.3, H 2.6, N 3.9%; calculated for C₂₈H₂₀N₂O₈Ru₂: C 47.1, H 2.8, N 3.9%. For he preparation of (II), tetracarbonylbis-µ-trifluoroacetatobis(pyridine)diruthenium(I), [Ru(CF₃CO₂)(CO)₂(py)]₂·[Ru(MeCO₂)(CO)₂(py)]₂ (109 mg, 0.185 mmol) was added to degassed trifluoroacetic acid (20 ml) and refluxed for 3 h. The reaction mixture was then stored at 4° overnight and filtered, and the filtrate was evaporated to give a yellow residue, which was recrystallized from methanol yielding yellow crystals of [Ru(CF₃CO₂)(CO)₂(py)]₂ (16 mg, 12% yield). Analysis found: C 32.0, H 1.5, N 3.9%; calculated for C₁₈H₁₀F₆N₂O₈Ru₂: C 31.0, H 1.5, N 4.0%. In another preparation, trifluoroacetic acid (0.5 ml) was added at room temperature to [Ru(MeCO₂)(CO)₂(py)]₂ (56 mg, 0.091 mmol) in methanol (5 ml) to yield a yellow precipitate of the product in much higher yield (51 mg, 80%). IR and NMR data for both compounds have been recorded in the cif.

S3. Refinement

H atoms were located from difference Fourier maps and placed at idealized positions [C—H = 0.95 Å, U_iso(H) = 1.25U_eq(C) for CH and CH₂ H atoms, and U_iso(H) = 1.5U_eq(C) for CH₃ H atoms].

Computing details

For both compounds, data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: Xtal (Hall et al., 1995); program(s) used to solve structure: Xtal; program(s) used to refine structure: CRYLSQ in Xtal; molecular graphics: Xtal; software used to prepare material for publication: BONDLA and CIFIO in Xtal.

Figures

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme and displacement ellipsoids at the 50% probability level. H atoms are represented as small circles with arbitrary radii.
	Fig. 2. The molecular structure of (II), with the atom-numbering scheme and displacement ellipsoids at the 50% probability level. H atoms are represented as small circles with arbitrary radii.

(I) Di-µ-benzoato-bis[dicarbonyl(pyridine)ruthenium(I)]

Crystal data

[Ru2(C7H5O2)2(C5H5N)2(CO)4]	F(000) = 1416
Mr = 714.61	Dx = 1.755 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ybc	Cell parameters from 7794 reflections
a = 8.6623 (3) Å	θ = 1.8–28.2°
b = 18.6501 (7) Å	µ = 1.17 mm^−1
c = 16.7546 (6) Å	T = 150 K
β = 92.680 (1)°	Prism, pale yellow
V = 2703.79 (17) Å^3	0.35 × 0.15 × 0.12 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	10364 independent reflections
Radiation source: sealed tube	9057 reflections with I > 2σ (I )
Graphite monochromator	Rint = 0.027
ω scans	θmax = 33.8°, θmin = 1.6°
Absorption correction: multi-scan SADABS; Sheldrick, 1996	h = −13→13
Tmin = 0.64, Tmax = 0.79	k = −29→29
44142 measured reflections	l = −25→25

Refinement

Refinement on F	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)] = 0.026	Hydrogen site location: difference Fourier map
wR(F^2) = 0.039	H-atom parameters not refined
S = 1.11	w = 1/(σ^2(F) + .02F + 0.0003F^2)
9057 reflections	(Δ/σ)max = 0.007
361 parameters	Δρmax = 0.86 e Å^−3
0 restraints	Δρmin = −0.48 e Å^−3
0 constraints

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

	x	y	z	Uiso*/Ueq
Ru1	0.168578 (15)	0.471227 (7)	0.832245 (8)	0.02097 (6)
Ru2	0.397052 (15)	0.566856 (7)	0.824047 (7)	0.02077 (6)
C11	0.2502 (2)	0.41815 (10)	0.91719 (10)	0.0264 (7)
O11	0.3009 (2)	0.38220 (9)	0.96769 (9)	0.0390 (8)
C12	0.0641 (2)	0.52854 (10)	0.90082 (11)	0.0272 (8)
O12	−0.0011 (2)	0.56636 (8)	0.94210 (10)	0.0376 (8)
C21	0.5258 (2)	0.51351 (10)	0.89121 (10)	0.0251 (7)
O21	0.60700 (18)	0.47969 (8)	0.93153 (9)	0.0358 (7)
C22	0.3418 (2)	0.62039 (9)	0.91041 (11)	0.0265 (7)
O22	0.30591 (19)	0.65432 (8)	0.96410 (9)	0.0366 (7)
O111	0.08353 (15)	0.52503 (7)	0.72855 (8)	0.0264 (6)
O112	0.24226 (15)	0.62015 (7)	0.73996 (8)	0.0263 (6)
C111	0.1344 (2)	0.58436 (9)	0.70495 (10)	0.0234 (7)
C112	0.0613 (2)	0.61406 (9)	0.62938 (10)	0.0246 (7)
C113	0.1040 (2)	0.68148 (10)	0.60325 (11)	0.0277 (8)
C114	0.0361 (2)	0.71026 (12)	0.53322 (12)	0.0350 (9)
C115	−0.0734 (3)	0.67092 (14)	0.49004 (13)	0.0407 (11)
C116	−0.1169 (3)	0.60341 (15)	0.51562 (15)	0.0475 (12)
C117	−0.0498 (3)	0.57501 (12)	0.58592 (13)	0.0363 (10)
O121	0.29702 (15)	0.41257 (7)	0.74853 (7)	0.0257 (6)
O122	0.44993 (15)	0.50615 (7)	0.72214 (8)	0.0263 (6)
C121	0.3968 (2)	0.44424 (9)	0.70807 (10)	0.0228 (7)
C122	0.4559 (2)	0.40497 (9)	0.63797 (10)	0.0228 (7)
C123	0.5545 (2)	0.43869 (10)	0.58640 (12)	0.0303 (8)
C124	0.6106 (3)	0.40043 (12)	0.52256 (12)	0.0367 (10)
C125	0.5687 (2)	0.32957 (12)	0.51018 (11)	0.0337 (9)
C126	0.4702 (2)	0.29608 (11)	0.56125 (11)	0.0302 (8)
C127	0.4137 (2)	0.33381 (10)	0.62517 (10)	0.0255 (7)
N101	−0.02628 (18)	0.39869 (8)	0.79835 (9)	0.0249 (6)
C102	−0.1376 (2)	0.38314 (10)	0.84887 (12)	0.0304 (8)
C103	−0.2650 (2)	0.34128 (12)	0.82691 (14)	0.0373 (10)
C104	−0.2774 (2)	0.31289 (11)	0.75082 (14)	0.0371 (10)
C105	−0.1640 (3)	0.32942 (12)	0.69824 (13)	0.0374 (10)
C106	−0.0415 (2)	0.37275 (11)	0.72344 (11)	0.0311 (8)
N201	0.58009 (18)	0.63847 (8)	0.77872 (9)	0.0255 (6)
C202	0.5640 (2)	0.66806 (12)	0.70592 (12)	0.0340 (9)
C203	0.6753 (3)	0.71196 (13)	0.67433 (12)	0.0388 (10)
C204	0.8110 (3)	0.72441 (11)	0.71810 (13)	0.0364 (10)
C205	0.8318 (2)	0.69199 (12)	0.79223 (14)	0.0363 (10)
C206	0.7142 (2)	0.65017 (11)	0.82052 (11)	0.0295 (8)
H113	0.17988	0.70828	0.63318	0.03400*
H114	0.06549	0.75648	0.51554	0.05100*
H115	−0.11979	0.69016	0.44229	0.05300*
H116	−0.19207	0.57658	0.48516	0.07200*
H117	−0.08007	0.52894	0.60387	0.03800*
H123	0.58331	0.48722	0.59484	0.03200*
H124	0.67788	0.42320	0.48709	0.04700*
H125	0.60751	0.30379	0.46654	0.03400*
H126	0.44162	0.24744	0.55261	0.03400*
H127	0.34594	0.31087	0.66017	0.02600*
H102	−0.12857	0.40133	0.90175	0.04000*
H103	−0.34272	0.33239	0.86377	0.03800*
H104	−0.36134	0.28286	0.73499	0.05100*
H105	−0.17057	0.31145	0.64506	0.06800*
H106	0.03448	0.38440	0.68661	0.03100*
H202	0.47198	0.65863	0.67450	0.04800*
H203	0.65833	0.73297	0.62317	0.05700*
H204	0.88845	0.75459	0.69813	0.03300*
H205	0.92535	0.69840	0.82314	0.04000*
H206	0.72880	0.62875	0.87171	0.03400*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.02119 (7)	0.02290 (7)	0.01910 (6)	0.00016 (4)	0.00397 (4)	−0.00015 (4)
Ru2	0.02103 (7)	0.02276 (6)	0.01857 (6)	−0.00002 (4)	0.00148 (4)	−0.00109 (4)
C11	0.0294 (8)	0.0267 (8)	0.0235 (7)	−0.0004 (6)	0.0046 (6)	−0.0009 (6)
O11	0.0458 (9)	0.0388 (8)	0.0321 (7)	0.0054 (7)	−0.0005 (6)	0.0088 (6)
C12	0.0270 (8)	0.0289 (8)	0.0261 (8)	−0.0009 (6)	0.0062 (6)	−0.0000 (6)
O12	0.0398 (8)	0.0374 (8)	0.0367 (8)	0.0057 (6)	0.0131 (6)	−0.0033 (6)
C21	0.0255 (8)	0.0267 (7)	0.0233 (7)	0.0014 (6)	0.0031 (6)	−0.0040 (6)
O21	0.0350 (7)	0.0397 (8)	0.0324 (7)	0.0098 (6)	−0.0006 (6)	0.0029 (6)
C22	0.0279 (8)	0.0249 (7)	0.0268 (8)	−0.0004 (6)	0.0036 (6)	−0.0000 (6)
O22	0.0450 (8)	0.0322 (7)	0.0336 (7)	−0.0001 (6)	0.0105 (6)	−0.0080 (6)
O111	0.0252 (6)	0.0280 (6)	0.0258 (6)	−0.0024 (5)	−0.0016 (5)	0.0034 (5)
O112	0.0257 (6)	0.0261 (6)	0.0268 (6)	−0.0002 (5)	−0.0024 (5)	0.0010 (5)
C111	0.0214 (7)	0.0264 (7)	0.0226 (7)	0.0024 (6)	0.0025 (6)	−0.0007 (6)
C112	0.0221 (7)	0.0286 (8)	0.0231 (7)	0.0012 (6)	0.0012 (6)	−0.0001 (6)
C113	0.0281 (8)	0.0313 (8)	0.0240 (7)	−0.0000 (7)	0.0023 (6)	0.0028 (6)
C114	0.0337 (10)	0.0412 (10)	0.0302 (9)	−0.0010 (8)	0.0031 (7)	0.0116 (8)
C115	0.0362 (10)	0.0534 (13)	0.0318 (9)	−0.0027 (9)	−0.0069 (8)	0.0128 (9)
C116	0.0457 (13)	0.0537 (14)	0.0412 (12)	−0.0124 (11)	−0.0197 (10)	0.0089 (10)
C117	0.0357 (10)	0.0358 (10)	0.0364 (10)	−0.0059 (8)	−0.0093 (8)	0.0059 (8)
O121	0.0267 (6)	0.0269 (6)	0.0241 (5)	0.0004 (5)	0.0072 (5)	−0.0018 (5)
O122	0.0283 (6)	0.0274 (6)	0.0237 (5)	−0.0019 (5)	0.0059 (5)	−0.0033 (5)
C121	0.0226 (7)	0.0265 (7)	0.0193 (6)	0.0027 (6)	0.0010 (5)	0.0000 (6)
C122	0.0223 (7)	0.0269 (7)	0.0194 (6)	0.0027 (6)	0.0028 (5)	−0.0012 (5)
C123	0.0328 (9)	0.0306 (8)	0.0284 (8)	0.0014 (7)	0.0098 (7)	0.0009 (7)
C124	0.0399 (11)	0.0415 (11)	0.0298 (9)	0.0045 (8)	0.0136 (8)	0.0016 (8)
C125	0.0352 (10)	0.0415 (10)	0.0250 (8)	0.0091 (8)	0.0080 (7)	−0.0056 (7)
C126	0.0322 (9)	0.0320 (9)	0.0265 (8)	0.0032 (7)	0.0015 (7)	−0.0073 (7)
C127	0.0264 (8)	0.0282 (8)	0.0220 (7)	0.0005 (6)	0.0020 (6)	−0.0028 (6)
N101	0.0252 (7)	0.0237 (6)	0.0259 (7)	0.0001 (5)	0.0022 (5)	0.0029 (5)
C102	0.0306 (9)	0.0272 (8)	0.0341 (9)	−0.0023 (7)	0.0088 (7)	0.0006 (7)
C103	0.0291 (9)	0.0323 (9)	0.0509 (12)	−0.0040 (7)	0.0073 (8)	0.0058 (9)
C104	0.0321 (10)	0.0314 (9)	0.0466 (11)	−0.0055 (7)	−0.0116 (8)	0.0111 (8)
C105	0.0385 (11)	0.0382 (10)	0.0344 (10)	−0.0033 (8)	−0.0104 (8)	0.0036 (8)
C106	0.0311 (9)	0.0353 (9)	0.0265 (8)	−0.0017 (7)	−0.0008 (7)	0.0008 (7)
N201	0.0260 (7)	0.0266 (7)	0.0239 (6)	−0.0019 (5)	0.0018 (5)	−0.0035 (5)
C202	0.0344 (10)	0.0416 (10)	0.0259 (8)	−0.0065 (8)	0.0018 (7)	0.0039 (7)
C203	0.0425 (11)	0.0438 (11)	0.0308 (9)	−0.0087 (9)	0.0105 (8)	0.0036 (8)
C204	0.0369 (10)	0.0337 (9)	0.0400 (10)	−0.0083 (8)	0.0174 (8)	−0.0099 (8)
C205	0.0274 (9)	0.0382 (10)	0.0437 (11)	−0.0057 (8)	0.0052 (8)	−0.0067 (8)
C206	0.0269 (8)	0.0313 (9)	0.0303 (8)	−0.0016 (7)	0.0006 (7)	−0.0027 (7)

Geometric parameters (Å, º)

Ru1—Ru2	2.6724 (2)	C122—C127	1.391 (3)
Ru1—C11	1.8469 (18)	C123—C124	1.392 (3)
Ru1—C12	1.8383 (19)	C123—H123	0.948
Ru1—O111	2.1091 (13)	C124—C125	1.383 (3)
Ru1—O121	2.1326 (13)	C124—H124	0.952
Ru1—N101	2.2164 (15)	C125—C126	1.385 (3)
Ru2—C21	1.8391 (18)	C125—H125	0.950
Ru2—C22	1.8396 (18)	C126—C127	1.389 (3)
Ru2—O112	2.1433 (13)	C126—H126	0.950
Ru2—O122	2.1166 (13)	C127—H127	0.9508
Ru2—N201	2.2332 (15)	N101—C102	1.344 (3)
C11—O11	1.150 (2)	N101—C106	1.346 (2)
C12—O12	1.154 (2)	C102—C103	1.387 (3)
C21—O21	1.142 (2)	C102—H102	0.949
C22—O22	1.154 (2)	C103—C104	1.380 (3)
O111—C111	1.262 (2)	C103—H103	0.949
O112—C111	1.269 (2)	C104—C105	1.384 (3)
C111—C112	1.495 (2)	C104—H104	0.946
C112—C113	1.387 (3)	C105—C106	1.384 (3)
C112—C117	1.386 (3)	C105—H105	0.951
C113—C114	1.395 (3)	C106—H106	0.948
C113—H113	0.9497	N201—C202	1.340 (2)
C114—C115	1.377 (3)	N201—C206	1.346 (2)
C114—H114	0.950	C202—C203	1.388 (3)
C115—C116	1.388 (4)	C202—H202	0.951
C115—H115	0.949	C203—C204	1.376 (3)
C116—C117	1.394 (3)	C203—H203	0.948
C116—H116	0.950	C204—C205	1.385 (3)
C117—H117	0.951	C204—H204	0.948
O121—C121	1.269 (2)	C205—C206	1.384 (3)
O122—C121	1.261 (2)	C205—H205	0.949
C121—C122	1.495 (2)	C206—H206	0.949
C122—C123	1.393 (3)
Ru2—Ru1—C11	98.02 (6)	Ru2—O122—C121	123.34 (11)
Ru2—Ru1—C12	91.81 (6)	O121—C121—O122	125.33 (16)
Ru2—Ru1—O111	82.60 (4)	O121—C121—C122	117.29 (15)
Ru2—Ru1—O121	84.16 (4)	O122—C121—C122	117.39 (15)
Ru2—Ru1—N101	162.02 (4)	C121—C122—C123	120.57 (16)
C11—Ru1—C12	90.69 (8)	C121—C122—C127	119.45 (15)
C11—Ru1—O111	174.96 (7)	C123—C122—C127	119.97 (16)
C11—Ru1—O121	92.24 (7)	C122—C123—C124	119.43 (18)
C11—Ru1—N101	97.46 (7)	C122—C123—H123	120.2
C12—Ru1—O111	94.30 (7)	C124—C123—H123	120.4
C12—Ru1—O121	175.31 (7)	C123—C124—C125	120.4 (2)
C12—Ru1—N101	97.10 (7)	C123—C124—H124	119.8
O111—Ru1—O121	82.83 (5)	C125—C124—H124	119.8
O111—Ru1—N101	81.19 (5)	C124—C125—C126	120.20 (19)
O121—Ru1—N101	86.15 (5)	C124—C125—H125	120.0
Ru1—Ru2—C21	92.11 (6)	C126—C125—H125	119.9
Ru1—Ru2—C22	95.82 (6)	C125—C126—C127	119.81 (18)
Ru1—Ru2—O112	84.33 (3)	C125—C126—H126	120.0
Ru1—Ru2—O122	82.71 (4)	C127—C126—H126	120.2
Ru1—Ru2—N201	162.92 (4)	C122—C127—C126	120.19 (17)
C21—Ru2—C22	89.13 (8)	C122—C127—H127	119.98
C21—Ru2—O112	174.77 (7)	C126—C127—H127	119.83
C21—Ru2—O122	93.23 (7)	Ru1—N101—C102	122.04 (12)
C21—Ru2—N201	96.42 (7)	Ru1—N101—C106	119.92 (13)
C22—Ru2—O112	95.03 (7)	C102—N101—C106	117.88 (16)
C22—Ru2—O122	177.26 (7)	N101—C102—C103	122.65 (19)
C22—Ru2—N201	99.07 (7)	N101—C102—H102	118.73
O112—Ru2—O122	82.54 (5)	C103—C102—H102	118.6
O112—Ru2—N201	86.07 (5)	C102—C103—C104	119.2 (2)
O122—Ru2—N201	82.05 (5)	C102—C103—H103	120.4
Ru1—C11—O11	176.65 (17)	C104—C103—H103	120.5
Ru1—C12—O12	177.73 (17)	C103—C104—C105	118.4 (2)
Ru2—C21—O21	178.53 (17)	C103—C104—H104	120.8
Ru2—C22—O22	179.26 (16)	C105—C104—H104	120.8
Ru1—O111—C111	124.19 (11)	C104—C105—C106	119.5 (2)
Ru2—O112—C111	118.97 (11)	C104—C105—H105	120.3
O111—C111—O112	125.22 (16)	C106—C105—H105	120.2
O111—C111—C112	116.76 (15)	N101—C106—C105	122.34 (19)
O112—C111—C112	118.03 (15)	N101—C106—H106	118.91
C111—C112—C113	119.63 (15)	C105—C106—H106	118.8
C111—C112—C117	120.41 (17)	Ru2—N201—C202	120.69 (13)
C113—C112—C117	119.96 (17)	Ru2—N201—C206	121.95 (12)
C112—C113—C114	120.38 (17)	C202—N201—C206	117.23 (17)
C112—C113—H113	119.90	N201—C202—C203	123.03 (18)
C114—C113—H113	119.72	N201—C202—H202	118.5
C113—C114—C115	119.3 (2)	C203—C202—H202	118.5
C113—C114—H114	120.2	C202—C203—C204	119.2 (2)
C115—C114—H114	120.5	C202—C203—H203	120.5
C114—C115—C116	120.8 (2)	C204—C203—H203	120.3
C114—C115—H115	119.7	C203—C204—C205	118.4 (2)
C116—C115—H115	119.5	C203—C204—H204	120.8
C115—C116—C117	119.8 (2)	C205—C204—H204	120.7
C115—C116—H116	120.1	C204—C205—C206	119.1 (2)
C117—C116—H116	120.1	C204—C205—H205	120.4
C112—C117—C116	119.8 (2)	C206—C205—H205	120.5
C112—C117—H117	120.2	N201—C206—C205	122.97 (18)
C116—C117—H117	120.0	N201—C206—H206	118.53
Ru1—O121—C121	120.12 (11)	C205—C206—H206	118.50

(II) Di-µ-trifluoroacetato-bis[dicarbonyl(pyridine)ruthenium(I)]

Crystal data

[Ru2(C2F3O2)2(C5H5N)2(CO)4]	Z = 2
Mr = 698.41	F(000) = 676
Triclinic, P1	Dx = 2.022 Mg m^−3
Hall symbol: -p 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.211 (2) Å	Cell parameters from 7874 reflections
b = 9.292 (2) Å	θ = 2.9–28.3°
c = 15.266 (4) Å	µ = 1.41 mm^−1
α = 105.280 (6)°	T = 150 K
β = 94.669 (6)°	Prism, pale yellow
γ = 111.726 (6)°	0.3 × 0.12 × 0.1 mm
V = 1147.3 (5) Å^3

Data collection

Bruker SMART CCD diffractometer	5738 independent reflections
Radiation source: sealed tube	5127 reflections with I > 2.00 σ(I)
Graphite monochromator	Rint = 0.023
ω scans	θmax = 28.9°, θmin = 1.4°
Absorption correction: multi-scan SADABS; Sheldrick, 1996	h = −12→12
Tmin = 0.66, Tmax = 0.79	k = −12→12
13924 measured reflections	l = −20→20

Refinement

Refinement on F	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)] = 0.033	Hydrogen site location: difference Fourier map
wR(F^2) = 0.06	H-atom parameters not refined
S = 1.07	w = 1/(σ^2(F) + .04F + 0.002F^2)
5127 reflections	(Δ/σ)max = 0.011
325 parameters	Δρmax = 0.92 e Å^−3
0 restraints	Δρmin = −0.94 e Å^−3
0 constraints

Special details

Experimental. I. Di-µ-benzoatotetracarbonylbis(pyridine)diruthenium(I), [Ru(PhCO₂)(CO)₂(py)]₂. IR (KBr disc), cm⁻¹: 3070w, 2019 s, 1968m, 1944 s, 1912m(sh) ν(CO); 1600m, 1557m ν_as(CO₂); 1446w, 1415 ms ν_sym(CO₂); 1216w, 1174vw, 1066w, 1026vw, 1010vw, 851w, 755w, 716m, 694m, 669w, 628vw, 573vw, 526vw, 486vw. {(Nujol) cm⁻¹: 2019 s, 1968m, 1944 s, 1911w(sh) ν(CO)} ¹H NMR (CDCl₃): 7.27 (4H, bm, PhCO₂—H3,5), 7.39 (2H, tt, ³J_H3,H4 7.3 Hz,⁴J_H2,H4 1.5 Hz, PhCO₂—H4), 7.53 (4H, td, ³J_H2,H3 4.9 Hz, ³J_H3,H4 7.5 Hz, py-H3,5), 7.85 (4H, dt, ³J_H2,H3 8.4 Hz, ⁴J_H2,H4 1.2 Hz, PhCO₂—H2,6),7.94 (2H, tt, ³J_H3,H4 7.5 Hz, ⁴J_H2,H4 1.5 Hz, py-H4), 8.93 (4H, dt, ³J_H2,H3 4.7 Hz, ⁴J_H2,H4 1.6 Hz, py-H2,6).

II. Tetracarbonylbis-µ-trifluoroacetatobis(pyridine)diruthenium(I), [Ru(CF₃CO₂)(CO)₂(py)]₂. IR (KBr disc), cm⁻¹: 2925w ν(CH); 2039vs, 1984 s(sh), 1958vs ν(CO); 1669vs ν_as(CO₂); 1602m, 1467m ν_s(CO₂); 1450m, 1401w, 1207vs, 1151 s ν(CF₃); 1068m, 1010w, 862m, 789w, 753m, 736m, 690m, 631w, 577m, 522w. ¹H NMR (CDCl₃): 7.49 (4H, dt, ³J_H2,H3 5 Hz, ⁴J_H1,H3 1.2 Hz, H3,5), 7.90 (2H, t, ³J_H3,H4 8.4 Hz, H4), 8.64 (4H, dt, ³J_H2,H3 4.8 Hz, ⁴J_H2,H4 1.5 Hz.

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

	x	y	z	Uiso*/Ueq
Ru1	0.51956 (3)	0.72402 (3)	0.291646 (18)	0.01942 (12)
Ru2	0.24970 (3)	0.44529 (3)	0.224738 (17)	0.02000 (12)
C11	0.4593 (4)	0.8344 (4)	0.2222 (3)	0.0256 (12)
O11	0.4252 (4)	0.9079 (4)	0.1811 (2)	0.0424 (13)
C12	0.4261 (4)	0.8116 (5)	0.3803 (3)	0.0253 (12)
O12	0.3628 (3)	0.8658 (4)	0.4331 (2)	0.0347 (11)
C21	0.1627 (4)	0.5266 (5)	0.1469 (3)	0.0265 (12)
O21	0.1073 (4)	0.5758 (4)	0.0985 (2)	0.0432 (13)
C22	0.1356 (5)	0.5067 (5)	0.3087 (3)	0.0300 (13)
O22	0.0592 (4)	0.5432 (4)	0.3593 (2)	0.0480 (14)
O111	0.5908 (3)	0.5905 (3)	0.3679 (2)	0.0273 (9)
O112	0.3686 (3)	0.3571 (3)	0.31110 (18)	0.0264 (9)
C111	0.5061 (4)	0.4447 (4)	0.3567 (2)	0.0235 (11)
C112	0.5888 (5)	0.3587 (5)	0.4030 (3)	0.0318 (14)
F111	0.6640 (4)	0.4501 (4)	0.4894 (2)	0.0634 (14)
F112	0.4894 (3)	0.2153 (3)	0.4064 (2)	0.0523 (12)
F113	0.6952 (4)	0.3330 (5)	0.3564 (3)	0.0689 (18)
O121	0.6135 (3)	0.6005 (3)	0.18646 (18)	0.0291 (9)
O122	0.3868 (3)	0.3708 (3)	0.13031 (18)	0.0267 (9)
C121	0.5301 (4)	0.4578 (4)	0.1362 (2)	0.0231 (11)
C122	0.6143 (4)	0.3735 (5)	0.0712 (3)	0.0300 (13)
F121	0.7714 (3)	0.4483 (4)	0.0956 (3)	0.0681 (14)
F122	0.5726 (5)	0.3723 (5)	−0.0149 (2)	0.0639 (16)
F123	0.5717 (4)	0.2196 (4)	0.0661 (3)	0.0649 (16)
N101	0.7716 (3)	0.9004 (4)	0.3444 (2)	0.0240 (10)
C102	0.8103 (4)	1.0569 (5)	0.3902 (3)	0.0320 (14)
C103	0.9661 (5)	1.1711 (5)	0.4265 (3)	0.0403 (16)
C104	1.0886 (5)	1.1230 (6)	0.4148 (3)	0.0409 (16)
C105	1.0508 (5)	0.9624 (6)	0.3669 (4)	0.0450 (18)
C106	0.8920 (5)	0.8556 (6)	0.3338 (3)	0.0393 (16)
N201	0.0798 (4)	0.1877 (4)	0.1664 (2)	0.0273 (11)
C202	0.1309 (5)	0.0677 (5)	0.1428 (3)	0.0341 (14)
C203	0.0284 (6)	−0.0958 (5)	0.1000 (3)	0.0419 (17)
C204	−0.1328 (6)	−0.1381 (6)	0.0823 (3)	0.0461 (17)
C205	−0.1867 (6)	−0.0153 (6)	0.1072 (4)	0.0463 (18)
C206	−0.0778 (5)	0.1425 (6)	0.1489 (3)	0.0360 (15)
H102	0.72646	1.09385	0.39926	0.03900*
H103	0.98728	1.28283	0.45995	0.04900*
H104	1.19771	1.19752	0.43962	0.04800*
H105	1.13219	0.92301	0.35577	0.05700*
H106	0.86775	0.74202	0.30129	0.04900*
H202	0.24442	0.09543	0.15594	0.04200*
H203	0.07066	−0.17721	0.08249	0.05300*
H204	−0.20556	−0.24977	0.05374	0.05700*
H205	−0.29860	−0.04102	0.09565	0.05600*
H206	−0.11887	0.22469	0.16619	0.04500*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.01594 (15)	0.01732 (16)	0.02268 (15)	0.00645 (11)	0.00049 (10)	0.00414 (11)
Ru2	0.01450 (14)	0.01960 (16)	0.02268 (15)	0.00557 (11)	0.00043 (10)	0.00462 (11)
C11	0.0196 (15)	0.0207 (16)	0.0302 (17)	0.0032 (13)	0.0007 (12)	0.0065 (14)
O11	0.054 (2)	0.0450 (18)	0.0390 (16)	0.0284 (16)	0.0025 (14)	0.0198 (14)
C12	0.0225 (16)	0.0255 (17)	0.0256 (16)	0.0103 (14)	−0.0020 (12)	0.0058 (13)
O12	0.0307 (14)	0.0377 (16)	0.0317 (14)	0.0162 (13)	0.0064 (11)	0.0017 (12)
C21	0.0172 (15)	0.0258 (18)	0.0332 (18)	0.0063 (14)	0.0009 (13)	0.0091 (15)
O21	0.0298 (15)	0.047 (2)	0.0526 (18)	0.0137 (14)	−0.0063 (13)	0.0227 (15)
C22	0.0228 (16)	0.0260 (19)	0.0324 (18)	0.0034 (15)	0.0031 (14)	0.0055 (15)
O22	0.0339 (16)	0.049 (2)	0.053 (2)	0.0150 (15)	0.0212 (14)	0.0019 (15)
O111	0.0222 (12)	0.0213 (12)	0.0371 (14)	0.0077 (10)	−0.0016 (10)	0.0110 (11)
O112	0.0229 (12)	0.0218 (12)	0.0309 (13)	0.0065 (10)	−0.0020 (10)	0.0088 (10)
C111	0.0227 (15)	0.0216 (16)	0.0243 (15)	0.0082 (13)	0.0021 (12)	0.0062 (13)
C112	0.0267 (17)	0.034 (2)	0.039 (2)	0.0132 (16)	0.0010 (15)	0.0176 (16)
F111	0.077 (2)	0.0419 (17)	0.0529 (18)	0.0138 (16)	−0.0290 (16)	0.0145 (14)
F112	0.0371 (14)	0.0382 (15)	0.080 (2)	0.0071 (12)	−0.0075 (13)	0.0347 (15)
F113	0.063 (2)	0.088 (3)	0.110 (3)	0.060 (2)	0.051 (2)	0.066 (2)
O121	0.0234 (12)	0.0293 (14)	0.0294 (13)	0.0102 (11)	0.0043 (10)	0.0023 (11)
O122	0.0203 (11)	0.0234 (13)	0.0304 (13)	0.0063 (10)	0.0055 (9)	0.0024 (10)
C121	0.0214 (15)	0.0236 (17)	0.0223 (15)	0.0090 (13)	0.0011 (12)	0.0052 (13)
C122	0.0214 (16)	0.0209 (17)	0.038 (2)	0.0047 (14)	0.0062 (14)	0.0002 (14)
F121	0.0238 (13)	0.067 (2)	0.085 (2)	0.0152 (14)	0.0102 (14)	−0.0162 (17)
F122	0.088 (2)	0.098 (3)	0.0334 (14)	0.067 (2)	0.0233 (15)	0.0183 (16)
F123	0.072 (2)	0.0361 (16)	0.106 (3)	0.0333 (16)	0.048 (2)	0.0269 (17)
N101	0.0185 (13)	0.0208 (14)	0.0274 (14)	0.0044 (11)	0.0011 (10)	0.0059 (11)
C102	0.0207 (16)	0.027 (2)	0.044 (2)	0.0055 (15)	0.0053 (15)	0.0119 (17)
C103	0.030 (2)	0.0215 (19)	0.054 (3)	−0.0014 (16)	0.0040 (18)	0.0058 (18)
C104	0.0233 (18)	0.037 (2)	0.049 (2)	−0.0001 (17)	0.0045 (17)	0.011 (2)
C105	0.0223 (18)	0.046 (3)	0.064 (3)	0.0166 (19)	0.0054 (18)	0.010 (2)
C106	0.0259 (18)	0.037 (2)	0.047 (2)	0.0161 (17)	−0.0050 (16)	−0.0006 (18)
N201	0.0212 (14)	0.0251 (15)	0.0277 (14)	0.0034 (12)	−0.0006 (11)	0.0062 (12)
C202	0.0290 (18)	0.027 (2)	0.040 (2)	0.0085 (16)	−0.0036 (15)	0.0072 (16)
C203	0.045 (2)	0.026 (2)	0.047 (2)	0.0069 (18)	0.0010 (19)	0.0123 (18)
C204	0.044 (2)	0.029 (2)	0.043 (2)	−0.006 (2)	−0.004 (2)	0.0101 (18)
C205	0.029 (2)	0.039 (3)	0.051 (3)	0.000 (2)	0.0021 (18)	0.003 (2)
C206	0.0282 (19)	0.036 (2)	0.035 (2)	0.0083 (17)	0.0059 (15)	0.0036 (17)

Geometric parameters (Å, º)

Ru1—Ru2	2.7122 (5)	C122—F122	1.334 (6)
Ru1—C11	1.839 (5)	C122—F123	1.314 (6)
Ru1—C12	1.834 (4)	N101—C102	1.330 (5)
Ru1—O111	2.137 (3)	N101—C106	1.329 (6)
Ru1—O121	2.153 (3)	C102—C103	1.388 (5)
Ru1—N101	2.215 (3)	C102—H102	0.960
Ru2—C21	1.842 (5)	C103—C104	1.368 (8)
Ru2—C22	1.830 (4)	C103—H103	0.965
Ru2—O112	2.147 (3)	C104—C105	1.372 (7)
Ru2—O122	2.138 (3)	C104—H104	0.958
Ru2—N201	2.202 (3)	C105—C106	1.385 (5)
C11—O11	1.146 (6)	C105—H105	0.957
C12—O12	1.150 (5)	C106—H106	0.970
C21—O21	1.142 (6)	N201—C202	1.341 (6)
C22—O22	1.155 (6)	N201—C206	1.335 (6)
O111—C111	1.244 (4)	C202—C203	1.393 (5)
O112—C111	1.244 (4)	C202—H202	0.969
C111—C112	1.543 (7)	C203—C204	1.371 (8)
C112—F111	1.328 (5)	C203—H203	0.961
C112—F112	1.326 (5)	C204—C205	1.384 (9)
C112—F113	1.312 (6)	C204—H204	0.956
O121—C121	1.245 (4)	C205—C206	1.370 (6)
O122—C121	1.248 (4)	C205—H205	0.957
C121—C122	1.538 (6)	C206—H206	0.959
C122—F121	1.322 (4)
Ru2—Ru1—C11	95.65 (9)	Ru2—O122—C121	121.8 (2)
Ru2—Ru1—C12	90.94 (10)	O121—C121—O122	129.8 (4)
Ru2—Ru1—O111	83.75 (6)	O121—C121—C122	116.1 (3)
Ru2—Ru1—O121	84.32 (6)	O122—C121—C122	114.1 (3)
Ru2—Ru1—N101	163.39 (10)	C121—C122—F121	112.6 (3)
C11—Ru1—C12	86.2 (2)	C121—C122—F122	109.5 (4)
C11—Ru1—O111	177.95 (15)	C121—C122—F123	112.5 (4)
C11—Ru1—O121	95.85 (16)	F121—C122—F122	107.8 (4)
C11—Ru1—N101	97.46 (14)	F121—C122—F123	108.4 (4)
C12—Ru1—O111	95.73 (17)	F122—C122—F123	105.7 (3)
C12—Ru1—O121	174.99 (13)	Ru1—N101—C102	121.5 (3)
C12—Ru1—N101	100.04 (13)	Ru1—N101—C106	122.1 (2)
O111—Ru1—O121	82.15 (12)	C102—N101—C106	116.4 (3)
O111—Ru1—N101	82.79 (12)	N101—C102—C103	123.7 (4)
O121—Ru1—N101	84.23 (11)	N101—C102—H102	118.8
Ru1—Ru2—C21	93.01 (10)	C103—C102—H102	117.5
Ru1—Ru2—C22	96.29 (10)	C102—C103—C104	119.2 (4)
Ru1—Ru2—O112	83.96 (6)	C102—C103—H103	120.2
Ru1—Ru2—O122	83.49 (6)	C104—C103—H103	120.6
Ru1—Ru2—N201	163.76 (10)	C103—C104—C105	117.8 (4)
C21—Ru2—C22	88.0 (2)	C103—C104—H104	121.9
C21—Ru2—O112	175.32 (14)	C105—C104—H104	120.3
C21—Ru2—O122	94.10 (16)	C104—C105—C106	119.4 (5)
C21—Ru2—N201	97.77 (14)	C104—C105—H105	121.1
C22—Ru2—O112	95.87 (18)	C106—C105—H105	119.5
C22—Ru2—O122	177.91 (18)	N101—C106—C105	123.5 (4)
C22—Ru2—N201	96.19 (14)	N101—C106—H106	118.4
O112—Ru2—O122	82.04 (12)	C105—C106—H106	118.1
O112—Ru2—N201	84.47 (12)	Ru2—N201—C202	121.1 (2)
O122—Ru2—N201	83.66 (11)	Ru2—N201—C206	122.5 (3)
Ru1—C11—O11	177.8 (3)	C202—N201—C206	116.4 (3)
Ru1—C12—O12	177.3 (4)	N201—C202—C203	123.2 (4)
Ru2—C21—O21	179.3 (3)	N201—C202—H202	118.8
Ru2—C22—O22	177.7 (3)	C203—C202—H202	118.1
Ru1—O111—C111	121.4 (3)	C202—C203—C204	119.1 (5)
Ru2—O112—C111	120.7 (3)	C202—C203—H203	120.2
O111—C111—O112	130.0 (4)	C204—C203—H203	120.7
O111—C111—C112	114.3 (3)	C203—C204—C205	118.2 (4)
O112—C111—C112	115.6 (3)	C203—C204—H204	120.6
C111—C112—F111	111.3 (4)	C205—C204—H204	121.2
C111—C112—F112	113.6 (3)	C204—C205—C206	119.0 (5)
C111—C112—F113	109.4 (4)	C204—C205—H205	120.1
F111—C112—F112	107.2 (4)	C206—C205—H205	120.9
F111—C112—F113	107.8 (4)	N201—C206—C205	124.2 (5)
F112—C112—F113	107.3 (4)	N201—C206—H206	118.7
Ru1—O121—C121	120.2 (3)	C205—C206—H206	117.1