Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803006597/cf6246sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803006597/cf6246Isup2.hkl |
CCDC reference: 209903
A mixture of [Ru3(CO)9(µ3,η2-C≡CSiMe3)(µ-SC≡CSiMe3)] (0.1 g, 0.13 mmol) and Co2(CO)8 (0.088 g, 0.26 mmol) in THF (15 ml) was stirred for 8 h at room temperature. The volatiles were removed under vacuum and n-hexane (2 × 15 ml) was added. When the solvent was partially removed, Co4(CO)12 precipitated. The resulting solution was dried under vacuum to afforded the title compound as a deep-red solid (0.12 g, 0.11 mmol, 86%). Crystals suitable for X-ray study were obtained from CH2Cl2/MeOH (1:1) at 253 K. Analysis calculated for C25H18Co2O15Ru3SSi2 (found): C 28.14 (27.77), H 1.76 (1.90)%. IR (hexane, cm-1): ν(CO): 2097 (w), 2082 (m), 2070 (s), 2058 (s), 2050 (m), 2033 (m), 2015 (s), 1994 (w), 1986 (w). 1H NMR (CDCl3): δ 0.56 (s, 9H, SiMe3), 0.30 (s, 9H, SiMe3). FAB+ (m/z): 1011 (M+–2CO), 929, 901, 875, 845, 817 (M+-nCO, n = 5–9), 785 [M+-5CO-Co(CO)3], 757 [M+-6CO-Co(CO)3], 696 [M+-5CO-Co2(CO)6].
H atoms were located by difference Fourier maps, but were then introduced in idealized positions, with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C); riding-model constraints included the torsion angle as a free variable. A final difference synthesis indicated some residual electron densities which might be due to disordered solvent molecules. Attempts to model these densities using CH2Cl2 molecules failed. Owing to the diffuse features of the electron density, we used the BYPASS/SQUEEZE procedure (van der Sluis & Spek, 1990) to mask the disordered solvent region.
Octacarbonyldicobalt has been used as protecting group for C≡C bonds. Adams et al. (1993) have prepared clusters [{M3(CO)11}{µ-PPh2[C2Co2(CO)6]C2PPh2}] (M = Ru, Os), in which the Co2(CO)6 moiety is linked to the C≡C bond present in the bridging ligand PPh2(C≡C)2. On the other hand, the compound S(C≡CPh)2 reacts with one or two equivalents of Co2(CO)8 to afford the mono- or dicoordinated compounds (PhC≡C)S[η2-(C≡ CPh)Co2(CO)6] and S[(η2-C≡CPh)2Co2(CO)6]2, respectively (Herres et al., 1994). We have studied the addition of the Co2(CO)6 fragment to the cluster [Ru3(CO)9(µ3,η2-C≡CSiMe3)(µ-SC≡ CSiMe3)], in order to increase its nuclearity. We report herein the synthesis and crystal structure of the new compound [Ru3(CO)9(µ3,η2-C≡CSiMe3)(µ-SC≡CSiMe3)Co2(CO)6], (I). The 1H NMR data are similar to those reported for the compound [Ru3(CO)9(µ3,η2-C≡CSiMe3)(µ-SC≡CSiMe3)] (Alcalde et al., 2001). The presence of the coordinated Co2(CO)6 group, as well as the ν(CO) pattern of the Ru3(CO)9 framework, are observed in the IR spectrum. The positive FAB mass spectrum exhibits the M+–2CO, M+–Co2(CO)6 and several other peaks corresponding to the sequential loss of CO ligands. Suitable crystals for X-ray diffraction studies of compound (I) were obtained from CH2Cl2/MeOH at 253 K.
The structure of (I) consists of an open triangular Ru3 framework with the alkynethiolate ligand bridging the two Ru atoms of the open edge, and the acetylide ligand σ-bonded to one Ru atom and π-bonded to the other two Ru atoms (Fig. 1). The Ru—Ru bond distances [2.8231 (5) and 2.8344 (4) Å] are similar to those found in {[Ru3(CO)9(µ-SC2H5)(µ-η2-C≡CR)], with R = CH3 [2.843 (1) and (2.847 (1) Å], R = Ph [2.8391 (8) and 2.8524 (8) Å] (Jeannin et al., 1994), and to those found in [Ru3(CO)9(µ3,η2-C≡CSiMe3)(µ-SC≡CSiMe3)] [2.8397 (5) and 2.8204 (5) Å; Alcalde et al., 2001]. In addition, the Ru—S distances [2.4331 (7) and 2.4276 (8) Å] are comparable to those found in the starting compound [Ru3(CO)9(µ3,η2-C≡CSiMe3)(µ-SC≡CSiMe3)] [2.4353 (7) and 2.4373 (7) Å; Alcalde et al., 2001]. As a consequence of the addition of the Co2(CO)6 fragment to the SC≡CSiMe3 ligand giving a dimetallatetrahedrane structure, it may be noted that the C3—C4 distance [1.356 (4) Å] is greater than in [Ru3(CO)9(µ-SC≡ CSiMe3)(µ3,η2-C≡CSiMe3)] [1.201 (4) Å; Alcalde et al., 2001]. Additionally, the Co1—Co2 bond length of 2.4751 (6) Å, as well as the distances from the Co atoms to the C3—C4 bond [1.958 (2), 1.917 (2), 1.970 (2) and 1.973 (2) Å], are in the ranges expected for this type of coordination (Low et al., 1999; Wadepohl et al., 1996; Herres et al., 1994). Finally, a strong deviation from linearity is observed in the angles S—C3—C4 [125.16 (18)°] and C3—C4—Si [140.26 (18)°], compared with those found in the starting compound [175.7 (2) and 178.3 (2)°, respectively].
Data collection: IPDS Software (Stoe & Cie, 1996); cell refinement: IPDS Software; data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SIR92 (Altomare et al., 1992); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999).
[Ru3Co2(C5H9Si)(C5H9SSi)(CO)15] | Z = 2 |
Mr = 1067.7 | F(000) = 1036 |
Triclinic, P1 | Dx = 1.863 Mg m−3 |
a = 9.2407 (10) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.0579 (13) Å | Cell parameters from 8000 reflections |
c = 18.841 (2) Å | θ = 2.3–26.1° |
α = 75.882 (13)° | µ = 2.19 mm−1 |
β = 87.813 (14)° | T = 180 K |
γ = 69.403 (12)° | Parallelepiped, red |
V = 1903.2 (4) Å3 | 0.25 × 0.25 × 0.13 mm |
Stoe IPDS diffractometer | 6294 reflections with I > 2σ(I) |
φ scans | Rint = 0.031 |
Absorption correction: multi-scan (Blessing, 1995) | θmax = 26.2°, θmin = 2.8° |
Tmin = 0.624, Tmax = 0.752 | h = −10→10 |
18747 measured reflections | k = −14→14 |
6954 independent reflections | l = −23→23 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.032 | w = 1/[σ2(Fo2) + (0.0562P)2 + 2.2163P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.094 | (Δ/σ)max = 0.001 |
S = 1.11 | Δρmax = 0.76 e Å−3 |
6954 reflections | Δρmin = −0.77 e Å−3 |
439 parameters |
[Ru3Co2(C5H9Si)(C5H9SSi)(CO)15] | γ = 69.403 (12)° |
Mr = 1067.7 | V = 1903.2 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.2407 (10) Å | Mo Kα radiation |
b = 12.0579 (13) Å | µ = 2.19 mm−1 |
c = 18.841 (2) Å | T = 180 K |
α = 75.882 (13)° | 0.25 × 0.25 × 0.13 mm |
β = 87.813 (14)° |
Stoe IPDS diffractometer | 6954 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 6294 reflections with I > 2σ(I) |
Tmin = 0.624, Tmax = 0.752 | Rint = 0.031 |
18747 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.76 e Å−3 |
6954 reflections | Δρmin = −0.77 e Å−3 |
439 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ru1 | 0.86154 (3) | 0.20466 (2) | 0.168254 (15) | 0.02310 (9) | |
Ru2 | 0.66182 (3) | 0.39186 (2) | 0.228804 (15) | 0.02382 (9) | |
Ru3 | 0.49638 (3) | 0.23916 (2) | 0.215147 (15) | 0.02284 (9) | |
Co1 | 0.94896 (6) | −0.20957 (4) | 0.25695 (3) | 0.02632 (12) | |
Co2 | 0.68082 (6) | −0.18316 (4) | 0.29303 (3) | 0.02461 (12) | |
S1 | 0.74823 (10) | 0.09391 (7) | 0.26617 (5) | 0.02240 (18) | |
Si1 | 0.57662 (14) | 0.24099 (10) | 0.01678 (6) | 0.0302 (2) | |
Si2 | 0.90015 (14) | −0.16718 (9) | 0.43707 (6) | 0.0321 (2) | |
O1A | 0.9724 (5) | 0.3833 (3) | 0.0582 (2) | 0.0559 (9) | |
O2A | 0.3829 (4) | 0.6005 (3) | 0.2557 (2) | 0.0610 (10) | |
O3A | 0.3951 (5) | 0.2268 (3) | 0.37128 (18) | 0.0563 (9) | |
O4A | 0.9094 (4) | −0.2085 (3) | 0.10244 (18) | 0.0487 (8) | |
O5A | 0.5440 (4) | −0.1812 (3) | 0.15394 (18) | 0.0488 (8) | |
O1B | 1.0409 (4) | 0.0070 (3) | 0.08915 (18) | 0.0480 (8) | |
O2B | 0.8612 (4) | 0.5486 (3) | 0.1877 (2) | 0.0503 (8) | |
O3B | 0.2041 (4) | 0.4574 (3) | 0.1607 (2) | 0.0519 (9) | |
O4B | 1.2139 (4) | −0.1289 (3) | 0.2536 (2) | 0.0493 (8) | |
O5B | 0.7400 (5) | −0.4368 (3) | 0.37530 (19) | 0.0528 (9) | |
O1C | 1.1055 (4) | 0.1695 (3) | 0.28368 (19) | 0.0514 (8) | |
O2C | 0.7829 (5) | 0.2794 (3) | 0.38844 (19) | 0.0650 (11) | |
O3C | 0.3457 (4) | 0.0767 (3) | 0.16899 (19) | 0.0444 (7) | |
O4C | 1.0997 (5) | −0.4733 (3) | 0.3247 (2) | 0.0578 (10) | |
O5C | 0.4071 (4) | −0.0519 (3) | 0.3624 (2) | 0.0509 (8) | |
C1A | 0.9307 (5) | 0.3176 (4) | 0.0988 (2) | 0.0360 (9) | |
C2A | 0.4861 (5) | 0.5219 (4) | 0.2465 (2) | 0.0352 (9) | |
C3A | 0.4326 (5) | 0.2307 (4) | 0.3136 (2) | 0.0353 (9) | |
C4A | 0.9252 (5) | −0.2069 (3) | 0.1609 (2) | 0.0332 (9) | |
C5A | 0.5951 (5) | −0.1777 (3) | 0.2065 (2) | 0.0331 (9) | |
C1B | 0.9709 (5) | 0.0757 (3) | 0.1200 (2) | 0.0337 (9) | |
C2B | 0.7886 (5) | 0.4898 (4) | 0.2038 (2) | 0.0349 (9) | |
C3B | 0.3124 (5) | 0.3767 (4) | 0.1799 (2) | 0.0347 (9) | |
C4B | 1.1125 (5) | −0.1615 (3) | 0.2546 (2) | 0.0346 (9) | |
C5B | 0.7154 (5) | −0.3394 (4) | 0.3442 (2) | 0.0349 (9) | |
C1C | 1.0153 (5) | 0.1825 (3) | 0.2402 (2) | 0.0336 (9) | |
C2C | 0.7365 (6) | 0.3244 (3) | 0.3305 (2) | 0.0384 (10) | |
C3C | 0.4076 (5) | 0.1308 (3) | 0.1876 (2) | 0.0317 (8) | |
C4C | 1.0428 (5) | −0.3727 (4) | 0.2981 (3) | 0.0380 (9) | |
C5C | 0.5110 (5) | −0.1028 (4) | 0.3354 (2) | 0.0327 (8) | |
C1 | 0.6207 (4) | 0.2692 (3) | 0.10534 (18) | 0.0239 (7) | |
C2 | 0.6235 (4) | 0.3453 (3) | 0.14135 (19) | 0.0233 (7) | |
C3 | 0.7888 (4) | −0.0652 (3) | 0.27801 (19) | 0.0230 (7) | |
C4 | 0.8432 (4) | −0.1520 (3) | 0.34072 (19) | 0.0244 (7) | |
C11 | 0.6355 (6) | 0.0747 (4) | 0.0265 (3) | 0.0454 (11) | |
H11A | 0.7465 | 0.0356 | 0.0402 | 0.068* | |
H11B | 0.6145 | 0.0596 | −0.0202 | 0.068* | |
H11C | 0.5769 | 0.0407 | 0.0646 | 0.068* | |
C12 | 0.3668 (6) | 0.3209 (5) | −0.0047 (3) | 0.0547 (13) | |
H12A | 0.34 | 0.408 | −0.0071 | 0.082* | |
H12B | 0.3094 | 0.2859 | 0.0336 | 0.082* | |
H12C | 0.3395 | 0.3113 | −0.052 | 0.082* | |
C13 | 0.6889 (7) | 0.3063 (5) | −0.0532 (3) | 0.0562 (13) | |
H13A | 0.6598 | 0.3938 | −0.0564 | 0.084* | |
H13B | 0.6669 | 0.2948 | −0.1008 | 0.084* | |
H13C | 0.7997 | 0.265 | −0.0396 | 0.084* | |
C21 | 0.9501 (7) | −0.3272 (4) | 0.4911 (3) | 0.0581 (14) | |
H21A | 1.0341 | −0.3809 | 0.4684 | 0.087* | |
H21B | 0.8591 | −0.3513 | 0.4922 | 0.087* | |
H21C | 0.9836 | −0.3341 | 0.5412 | 0.087* | |
C22 | 0.7329 (7) | −0.0629 (5) | 0.4752 (3) | 0.0528 (12) | |
H22A | 0.761 | −0.065 | 0.5253 | 0.079* | |
H22B | 0.644 | −0.0895 | 0.4758 | 0.079* | |
H22C | 0.7057 | 0.0207 | 0.4446 | 0.079* | |
C23 | 1.0701 (7) | −0.1174 (5) | 0.4342 (3) | 0.0520 (13) | |
H23A | 1.1589 | −0.1759 | 0.417 | 0.078* | |
H23B | 1.0956 | −0.1139 | 0.4834 | 0.078* | |
H23C | 1.0452 | −0.0363 | 0.4006 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.01881 (18) | 0.02175 (14) | 0.02967 (16) | −0.00807 (11) | 0.00286 (11) | −0.00690 (11) |
Ru2 | 0.02326 (18) | 0.01965 (14) | 0.02881 (16) | −0.00691 (11) | 0.00023 (11) | −0.00725 (11) |
Ru3 | 0.01911 (18) | 0.02303 (15) | 0.02677 (16) | −0.00797 (11) | 0.00294 (11) | −0.00632 (11) |
Co1 | 0.0231 (3) | 0.0209 (2) | 0.0359 (3) | −0.00783 (19) | 0.0035 (2) | −0.00884 (19) |
Co2 | 0.0246 (3) | 0.0238 (2) | 0.0292 (2) | −0.01180 (19) | 0.00237 (19) | −0.00859 (18) |
S1 | 0.0223 (5) | 0.0195 (4) | 0.0257 (4) | −0.0074 (3) | 0.0005 (3) | −0.0061 (3) |
Si1 | 0.0313 (6) | 0.0339 (5) | 0.0251 (5) | −0.0105 (4) | −0.0006 (4) | −0.0078 (4) |
Si2 | 0.0408 (7) | 0.0287 (5) | 0.0288 (5) | −0.0167 (5) | −0.0057 (4) | −0.0027 (4) |
O1A | 0.059 (3) | 0.0448 (17) | 0.066 (2) | −0.0329 (17) | 0.0210 (18) | 0.0018 (16) |
O2A | 0.040 (2) | 0.0411 (18) | 0.091 (3) | 0.0030 (15) | 0.0157 (19) | −0.0256 (18) |
O3A | 0.072 (3) | 0.066 (2) | 0.0351 (17) | −0.0287 (19) | 0.0238 (17) | −0.0179 (15) |
O4A | 0.061 (2) | 0.0526 (18) | 0.0402 (18) | −0.0257 (17) | 0.0090 (15) | −0.0181 (14) |
O5A | 0.055 (2) | 0.0582 (19) | 0.0403 (17) | −0.0201 (16) | −0.0076 (15) | −0.0222 (15) |
O1B | 0.054 (2) | 0.0391 (16) | 0.0540 (19) | −0.0132 (14) | 0.0245 (16) | −0.0243 (15) |
O2B | 0.045 (2) | 0.0424 (16) | 0.079 (2) | −0.0294 (16) | 0.0133 (17) | −0.0236 (16) |
O3B | 0.0197 (19) | 0.0450 (18) | 0.072 (2) | 0.0053 (14) | −0.0071 (15) | −0.0045 (16) |
O4B | 0.027 (2) | 0.0452 (17) | 0.079 (2) | −0.0173 (14) | 0.0012 (15) | −0.0153 (16) |
O5B | 0.073 (3) | 0.0315 (16) | 0.056 (2) | −0.0262 (16) | 0.0034 (17) | −0.0028 (14) |
O1C | 0.032 (2) | 0.069 (2) | 0.055 (2) | −0.0151 (15) | −0.0122 (15) | −0.0197 (17) |
O2C | 0.098 (3) | 0.0508 (19) | 0.0385 (19) | −0.020 (2) | −0.0217 (19) | −0.0035 (15) |
O3C | 0.036 (2) | 0.0463 (17) | 0.063 (2) | −0.0240 (14) | −0.0008 (14) | −0.0209 (15) |
O4C | 0.057 (3) | 0.0251 (15) | 0.077 (3) | −0.0045 (14) | 0.0018 (19) | −0.0019 (15) |
O5C | 0.036 (2) | 0.061 (2) | 0.059 (2) | −0.0143 (15) | 0.0149 (16) | −0.0280 (17) |
C1A | 0.029 (2) | 0.0306 (19) | 0.049 (2) | −0.0093 (16) | 0.0036 (18) | −0.0117 (17) |
C2A | 0.028 (2) | 0.0331 (19) | 0.043 (2) | −0.0098 (17) | 0.0037 (17) | −0.0086 (16) |
C3A | 0.033 (3) | 0.0321 (19) | 0.041 (2) | −0.0110 (16) | 0.0061 (17) | −0.0092 (16) |
C4A | 0.032 (2) | 0.0276 (18) | 0.045 (2) | −0.0131 (16) | 0.0097 (17) | −0.0140 (16) |
C5A | 0.030 (2) | 0.0287 (18) | 0.045 (2) | −0.0125 (16) | 0.0069 (17) | −0.0140 (16) |
C1B | 0.032 (2) | 0.0321 (19) | 0.039 (2) | −0.0155 (17) | 0.0067 (17) | −0.0070 (16) |
C2B | 0.032 (2) | 0.0320 (19) | 0.042 (2) | −0.0088 (17) | 0.0020 (17) | −0.0144 (16) |
C3B | 0.029 (3) | 0.038 (2) | 0.039 (2) | −0.0156 (18) | 0.0069 (17) | −0.0081 (17) |
C4B | 0.027 (2) | 0.0249 (17) | 0.047 (2) | −0.0034 (16) | 0.0029 (17) | −0.0092 (16) |
C5B | 0.038 (3) | 0.036 (2) | 0.038 (2) | −0.0212 (18) | 0.0052 (17) | −0.0111 (17) |
C1C | 0.028 (2) | 0.0311 (18) | 0.043 (2) | −0.0124 (16) | 0.0039 (17) | −0.0102 (16) |
C2C | 0.050 (3) | 0.0271 (18) | 0.041 (2) | −0.0129 (17) | −0.0006 (19) | −0.0135 (17) |
C3C | 0.029 (2) | 0.0300 (18) | 0.034 (2) | −0.0101 (16) | 0.0048 (15) | −0.0045 (15) |
C4C | 0.028 (3) | 0.032 (2) | 0.055 (3) | −0.0109 (17) | 0.0059 (18) | −0.0122 (18) |
C5C | 0.027 (2) | 0.037 (2) | 0.037 (2) | −0.0156 (17) | 0.0003 (16) | −0.0092 (16) |
C1 | 0.022 (2) | 0.0280 (16) | 0.0205 (16) | −0.0101 (14) | 0.0017 (13) | −0.0029 (13) |
C2 | 0.018 (2) | 0.0212 (15) | 0.0264 (17) | −0.0064 (13) | −0.0010 (13) | 0.0011 (13) |
C3 | 0.018 (2) | 0.0250 (16) | 0.0294 (17) | −0.0094 (13) | 0.0024 (13) | −0.0095 (13) |
C4 | 0.024 (2) | 0.0239 (16) | 0.0291 (18) | −0.0120 (14) | 0.0014 (14) | −0.0074 (13) |
C11 | 0.055 (3) | 0.040 (2) | 0.045 (2) | −0.018 (2) | −0.006 (2) | −0.0138 (19) |
C12 | 0.043 (3) | 0.076 (3) | 0.042 (3) | −0.010 (2) | −0.011 (2) | −0.023 (2) |
C13 | 0.068 (4) | 0.069 (3) | 0.038 (2) | −0.035 (3) | 0.013 (2) | −0.010 (2) |
C21 | 0.078 (4) | 0.046 (3) | 0.047 (3) | −0.027 (3) | −0.020 (3) | 0.005 (2) |
C22 | 0.060 (4) | 0.062 (3) | 0.040 (2) | −0.020 (3) | 0.005 (2) | −0.020 (2) |
C23 | 0.054 (4) | 0.064 (3) | 0.046 (3) | −0.035 (3) | −0.016 (2) | −0.004 (2) |
Ru1—C1C | 1.906 (4) | Co2—C3 | 1.970 (3) |
Ru1—C1A | 1.912 (4) | S1—C3 | 1.778 (3) |
Ru1—C1B | 1.944 (4) | Si1—C13 | 1.844 (5) |
Ru1—C2 | 2.239 (4) | Si1—C12 | 1.846 (5) |
Ru1—C1 | 2.344 (4) | Si1—C11 | 1.846 (4) |
Ru1—S1 | 2.4327 (9) | Si1—C1 | 1.869 (4) |
Ru1—Ru2 | 2.8227 (6) | Si2—C21 | 1.850 (5) |
Ru2—C2A | 1.905 (4) | Si2—C4 | 1.857 (4) |
Ru2—C2B | 1.910 (4) | Si2—C23 | 1.862 (5) |
Ru2—C2C | 1.937 (4) | Si2—C22 | 1.864 (5) |
Ru2—C2 | 1.947 (4) | O1A—C1A | 1.121 (5) |
Ru2—Ru3 | 2.8346 (5) | O2A—C2A | 1.127 (5) |
Ru3—C3B | 1.909 (4) | O3A—C3A | 1.122 (5) |
Ru3—C3A | 1.915 (4) | O4A—C4A | 1.123 (5) |
Ru3—C3C | 1.941 (4) | O5A—C5A | 1.130 (5) |
Ru3—C2 | 2.240 (3) | O1B—C1B | 1.128 (5) |
Ru3—C1 | 2.341 (3) | O2B—C2B | 1.122 (5) |
Ru3—S1 | 2.4268 (10) | O3B—C3B | 1.119 (5) |
Co1—C4B | 1.795 (4) | O4B—C4B | 1.134 (5) |
Co1—C4A | 1.822 (4) | O5B—C5B | 1.123 (5) |
Co1—C4C | 1.825 (4) | O1C—C1C | 1.135 (5) |
Co1—C3 | 1.964 (3) | O2C—C2C | 1.120 (5) |
Co1—C4 | 1.967 (4) | O3C—C3C | 1.125 (5) |
Co1—Co2 | 2.4748 (8) | O4C—C4C | 1.128 (5) |
Co2—C5C | 1.803 (4) | O5C—C5C | 1.121 (5) |
Co2—C5B | 1.815 (4) | C1—C2 | 1.275 (5) |
Co2—C5A | 1.816 (4) | C3—C4 | 1.348 (5) |
Co2—C4 | 1.966 (4) | ||
C1C—Ru1—C1A | 91.75 (18) | C4—Co1—Co2 | 50.99 (11) |
C1C—Ru1—C1B | 100.98 (18) | C5C—Co2—C5B | 100.49 (19) |
C1A—Ru1—C1B | 90.37 (16) | C5C—Co2—C5A | 100.59 (18) |
C1C—Ru1—C2 | 130.28 (15) | C5B—Co2—C5A | 102.26 (17) |
C1A—Ru1—C2 | 86.21 (16) | C5C—Co2—C4 | 101.21 (16) |
C1B—Ru1—C2 | 128.68 (16) | C5B—Co2—C4 | 99.26 (17) |
C1C—Ru1—C1 | 160.99 (15) | C5A—Co2—C4 | 145.83 (17) |
C1A—Ru1—C1 | 93.35 (16) | C5C—Co2—C3 | 99.72 (16) |
C1B—Ru1—C1 | 97.29 (15) | C5B—Co2—C3 | 137.55 (17) |
C2—Ru1—C1 | 32.20 (13) | C5A—Co2—C3 | 110.15 (16) |
C1C—Ru1—S1 | 86.48 (13) | C4—Co2—C3 | 40.04 (15) |
C1A—Ru1—S1 | 169.17 (12) | C5C—Co2—Co1 | 148.99 (12) |
C1B—Ru1—S1 | 100.45 (11) | C5B—Co2—Co1 | 97.95 (14) |
C2—Ru1—S1 | 86.79 (9) | C5A—Co2—Co1 | 99.57 (14) |
C1—Ru1—S1 | 85.08 (9) | C4—Co2—Co1 | 51.02 (11) |
C1C—Ru1—Ru2 | 87.22 (12) | C3—Co2—Co1 | 50.92 (10) |
C1A—Ru1—Ru2 | 92.10 (12) | C3—S1—Ru3 | 119.63 (12) |
C1B—Ru1—Ru2 | 171.36 (13) | C3—S1—Ru1 | 120.46 (12) |
C2—Ru1—Ru2 | 43.36 (9) | Ru3—S1—Ru1 | 87.56 (3) |
C1—Ru1—Ru2 | 74.31 (8) | C13—Si1—C12 | 110.8 (3) |
S1—Ru1—Ru2 | 77.15 (2) | C13—Si1—C11 | 110.2 (3) |
C2A—Ru2—C2B | 94.32 (18) | C12—Si1—C11 | 112.3 (3) |
C2A—Ru2—C2C | 95.52 (18) | C13—Si1—C1 | 107.1 (2) |
C2B—Ru2—C2C | 95.92 (19) | C12—Si1—C1 | 106.9 (2) |
C2A—Ru2—C2 | 110.64 (17) | C11—Si1—C1 | 109.31 (18) |
C2B—Ru2—C2 | 108.14 (16) | C21—Si2—C4 | 110.6 (2) |
C2C—Ru2—C2 | 142.31 (14) | C21—Si2—C23 | 110.8 (3) |
C2A—Ru2—Ru1 | 162.75 (13) | C4—Si2—C23 | 106.9 (2) |
C2B—Ru2—Ru1 | 93.03 (12) | C21—Si2—C22 | 110.9 (3) |
C2C—Ru2—Ru1 | 99.22 (12) | C4—Si2—C22 | 107.2 (2) |
C2—Ru2—Ru1 | 52.14 (10) | C23—Si2—C22 | 110.4 (3) |
C2A—Ru2—Ru3 | 95.69 (13) | O1A—C1A—Ru1 | 179.5 (5) |
C2B—Ru2—Ru3 | 159.92 (12) | O2A—C2A—Ru2 | 178.5 (4) |
C2C—Ru2—Ru3 | 100.38 (13) | O3A—C3A—Ru3 | 179.4 (4) |
C2—Ru2—Ru3 | 51.92 (10) | O4A—C4A—Co1 | 177.8 (4) |
Ru1—Ru2—Ru3 | 72.925 (13) | O5A—C5A—Co2 | 176.1 (3) |
C3B—Ru3—C3A | 90.32 (18) | O1B—C1B—Ru1 | 174.2 (4) |
C3B—Ru3—C3C | 91.05 (17) | O2B—C2B—Ru2 | 178.4 (4) |
C3A—Ru3—C3C | 100.39 (17) | O3B—C3B—Ru3 | 178.6 (4) |
C3B—Ru3—C2 | 86.53 (15) | O4B—C4B—Co1 | 178.5 (4) |
C3A—Ru3—C2 | 134.03 (15) | O5B—C5B—Co2 | 178.5 (4) |
C3C—Ru3—C2 | 125.49 (15) | O1C—C1C—Ru1 | 179.1 (4) |
C3B—Ru3—C1 | 94.05 (15) | O2C—C2C—Ru2 | 176.2 (4) |
C3A—Ru3—C1 | 164.83 (16) | O3C—C3C—Ru3 | 174.1 (4) |
C3C—Ru3—C1 | 94.05 (14) | O4C—C4C—Co1 | 178.7 (4) |
C2—Ru3—C1 | 32.23 (13) | O5C—C5C—Co2 | 178.7 (4) |
C3B—Ru3—S1 | 168.62 (12) | C2—C1—Si1 | 148.5 (3) |
C3A—Ru3—S1 | 87.58 (13) | C2—C1—Ru3 | 69.5 (2) |
C3C—Ru3—S1 | 100.33 (12) | Si1—C1—Ru3 | 127.36 (18) |
C2—Ru3—S1 | 86.91 (9) | C2—C1—Ru1 | 69.4 (2) |
C1—Ru3—S1 | 85.29 (9) | Si1—C1—Ru1 | 128.32 (18) |
C3B—Ru3—Ru2 | 91.87 (12) | Ru3—C1—Ru1 | 91.73 (12) |
C3A—Ru3—Ru2 | 91.24 (13) | C1—C2—Ru2 | 154.2 (3) |
C3C—Ru3—Ru2 | 167.99 (12) | C1—C2—Ru1 | 78.4 (2) |
C2—Ru3—Ru2 | 43.16 (9) | Ru2—C2—Ru1 | 84.50 (13) |
C1—Ru3—Ru2 | 74.12 (9) | C1—C2—Ru3 | 78.2 (2) |
S1—Ru3—Ru2 | 77.01 (2) | Ru2—C2—Ru3 | 84.92 (13) |
C4B—Co1—C4A | 100.96 (19) | Ru1—C2—Ru3 | 97.29 (12) |
C4B—Co1—C4C | 99.82 (19) | C4—C3—S1 | 125.6 (3) |
C4A—Co1—C4C | 101.90 (19) | C4—C3—Co1 | 70.1 (2) |
C4B—Co1—C3 | 99.11 (15) | S1—C3—Co1 | 140.0 (2) |
C4A—Co1—C3 | 108.82 (16) | C4—C3—Co2 | 69.8 (2) |
C4C—Co1—C3 | 139.81 (18) | S1—C3—Co2 | 140.2 (2) |
C4B—Co1—C4 | 100.87 (17) | Co1—C3—Co2 | 77.96 (12) |
C4A—Co1—C4 | 144.66 (17) | C3—C4—Si2 | 140.0 (3) |
C4C—Co1—C4 | 101.35 (17) | C3—C4—Co2 | 70.1 (2) |
C3—Co1—C4 | 40.09 (15) | Si2—C4—Co2 | 134.8 (2) |
C4B—Co1—Co2 | 148.57 (12) | C3—C4—Co1 | 69.9 (2) |
C4A—Co1—Co2 | 98.90 (14) | Si2—C4—Co1 | 135.7 (2) |
C4C—Co1—Co2 | 99.62 (14) | Co2—C4—Co1 | 77.99 (13) |
C3—Co1—Co2 | 51.12 (10) |
Experimental details
Crystal data | |
Chemical formula | [Ru3Co2(C5H9Si)(C5H9SSi)(CO)15] |
Mr | 1067.7 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 180 |
a, b, c (Å) | 9.2407 (10), 12.0579 (13), 18.841 (2) |
α, β, γ (°) | 75.882 (13), 87.813 (14), 69.403 (12) |
V (Å3) | 1903.2 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.19 |
Crystal size (mm) | 0.25 × 0.25 × 0.13 |
Data collection | |
Diffractometer | Stoe IPDS |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.624, 0.752 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18747, 6954, 6294 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.622 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.094, 1.11 |
No. of reflections | 6954 |
No. of parameters | 439 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.76, −0.77 |
Computer programs: IPDS Software (Stoe & Cie, 1996), IPDS Software, X-RED (Stoe & Cie, 1996), SIR92 (Altomare et al., 1992), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 and WinGX (Farrugia, 1999).
Ru1—C2 | 2.239 (4) | Ru3—C1 | 2.341 (3) |
Ru1—C1 | 2.344 (4) | Ru3—S1 | 2.4268 (10) |
Ru1—S1 | 2.4327 (9) | Co1—Co2 | 2.4748 (8) |
Ru1—Ru2 | 2.8227 (6) | S1—C3 | 1.778 (3) |
Ru2—Ru3 | 2.8346 (5) | C1—C2 | 1.275 (5) |
Ru3—C2 | 2.240 (3) | C3—C4 | 1.348 (5) |
Ru1—Ru2—Ru3 | 72.925 (13) | C4—C3—S1 | 125.6 (3) |
Ru3—S1—Ru1 | 87.56 (3) | C3—C4—Si2 | 140.0 (3) |
Octacarbonyldicobalt has been used as protecting group for C≡C bonds. Adams et al. (1993) have prepared clusters [{M3(CO)11}{µ-PPh2[C2Co2(CO)6]C2PPh2}] (M = Ru, Os), in which the Co2(CO)6 moiety is linked to the C≡C bond present in the bridging ligand PPh2(C≡C)2. On the other hand, the compound S(C≡CPh)2 reacts with one or two equivalents of Co2(CO)8 to afford the mono- or dicoordinated compounds (PhC≡C)S[η2-(C≡ CPh)Co2(CO)6] and S[(η2-C≡CPh)2Co2(CO)6]2, respectively (Herres et al., 1994). We have studied the addition of the Co2(CO)6 fragment to the cluster [Ru3(CO)9(µ3,η2-C≡CSiMe3)(µ-SC≡ CSiMe3)], in order to increase its nuclearity. We report herein the synthesis and crystal structure of the new compound [Ru3(CO)9(µ3,η2-C≡CSiMe3)(µ-SC≡CSiMe3)Co2(CO)6], (I). The 1H NMR data are similar to those reported for the compound [Ru3(CO)9(µ3,η2-C≡CSiMe3)(µ-SC≡CSiMe3)] (Alcalde et al., 2001). The presence of the coordinated Co2(CO)6 group, as well as the ν(CO) pattern of the Ru3(CO)9 framework, are observed in the IR spectrum. The positive FAB mass spectrum exhibits the M+–2CO, M+–Co2(CO)6 and several other peaks corresponding to the sequential loss of CO ligands. Suitable crystals for X-ray diffraction studies of compound (I) were obtained from CH2Cl2/MeOH at 253 K.
The structure of (I) consists of an open triangular Ru3 framework with the alkynethiolate ligand bridging the two Ru atoms of the open edge, and the acetylide ligand σ-bonded to one Ru atom and π-bonded to the other two Ru atoms (Fig. 1). The Ru—Ru bond distances [2.8231 (5) and 2.8344 (4) Å] are similar to those found in {[Ru3(CO)9(µ-SC2H5)(µ-η2-C≡CR)], with R = CH3 [2.843 (1) and (2.847 (1) Å], R = Ph [2.8391 (8) and 2.8524 (8) Å] (Jeannin et al., 1994), and to those found in [Ru3(CO)9(µ3,η2-C≡CSiMe3)(µ-SC≡CSiMe3)] [2.8397 (5) and 2.8204 (5) Å; Alcalde et al., 2001]. In addition, the Ru—S distances [2.4331 (7) and 2.4276 (8) Å] are comparable to those found in the starting compound [Ru3(CO)9(µ3,η2-C≡CSiMe3)(µ-SC≡CSiMe3)] [2.4353 (7) and 2.4373 (7) Å; Alcalde et al., 2001]. As a consequence of the addition of the Co2(CO)6 fragment to the SC≡CSiMe3 ligand giving a dimetallatetrahedrane structure, it may be noted that the C3—C4 distance [1.356 (4) Å] is greater than in [Ru3(CO)9(µ-SC≡ CSiMe3)(µ3,η2-C≡CSiMe3)] [1.201 (4) Å; Alcalde et al., 2001]. Additionally, the Co1—Co2 bond length of 2.4751 (6) Å, as well as the distances from the Co atoms to the C3—C4 bond [1.958 (2), 1.917 (2), 1.970 (2) and 1.973 (2) Å], are in the ranges expected for this type of coordination (Low et al., 1999; Wadepohl et al., 1996; Herres et al., 1994). Finally, a strong deviation from linearity is observed in the angles S—C3—C4 [125.16 (18)°] and C3—C4—Si [140.26 (18)°], compared with those found in the starting compound [175.7 (2) and 178.3 (2)°, respectively].