Acta Cryst.(2002). E58, m679±m680DOI: 10.1107/S1600536802019153Andrea Berenbaumet al. [Co(C5H5)2]2[RuCl3(C12H10ClSi)(CO)2]
m679
metal-organic papers
Acta Crystallographica Section E
Structure Reports Online
ISSN 1600-5368
Bis[di-
g
5-cyclopentadienylcobalt(I)]
dicarbonyl-trichloro(chlorodiphenylsilyl)ruthenium(II)
Andrea Berenbaum, Alan J. Lough* and Ian Manners
Department of Chemistry, University of Toronto, Toronto, Ontario, Canada M5S 3H6
Correspondence e-mail: alough@chem.utoronto.ca
Key indicators
Single-crystal X-ray study
T= 150 K
Mean(C±C) = 0.018 AÊ
Rfactor = 0.064
wRfactor = 0.127
Data-to-parameter ratio = 14.2
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved
The asymmetric unit of the title compound, [Co(C5H5)2]2
-[RuCl3(C12H10ClSi)(CO)2], consists of a discrete ClPh2
Si-Ru(CO)2Cl3 dianion and two (-C5H5)2Co cations. The
dianion has octahedral coordination geometry, with the three Cl atoms incispositions. In addition, two carbonyl groups (cis) and a Ph2ClSi group (bonded through Si) complete the
coordination. The RuÐSi bond length is 2.362 (3) AÊ and the longest RuÐCl bond [2.566 (2) AÊ] istransto the Si atom. In one cobaltocene cation, the cyclopentadienyl (Cp) rings are staggered, while in the other, theCprings are almost eclipsed.
Comment
Metal complexes with functional groups are of potential interest as precursors to metallopolymers. As part of our work in this area (Nguyenet al., 1999), we report the characteriza-tion of an unexpected product, (I).
Experimental
The reaction between two equivalents of (-C5H5)2Co and
[ClPh2SiRu(CO)4]2 was carried out at 298 K in tetrahydrofuran
under an atmosphere of N2. Afterca16 h, the solvent was removed
under high vacuum and CD2Cl2was added to the residue. A vigorous
reaction was observed with evolution of gas. Red±orange crystals of (I) were obtained upon slow room-temperature concentration of the resultant product mixture under an N2atmosphere.
Crystal data
[Co(C5H5)2]2
-[RuCl3(C12H10ClSi)(CO)2]
Mr= 859.40
Orthorhombic,P212121
a= 9.7462 (5) AÊ b= 10.2277 (6) AÊ c= 34.099 (2) AÊ V= 3399.0 (3) AÊ3
Z= 4
Dx= 1.679 Mg mÿ3
MoKradiation Cell parameters from 3060
re¯ections = 2.6±25.0
= 1.78 mmÿ1
T= 150 (1) K Plate, dark orange 0.200.200.02 mm
Data collection
Nonius KappaCCD diffractometer 'scans and!scans withoffsets Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)
Tmin= 0.717,Tmax= 0.965
12 795 measured re¯ections
5652 independent re¯ections 3558 re¯ections withI> 2(I) Rint= 0.109
max= 25.0
h=ÿ11!11 k=ÿ12!12 l=ÿ37!36
Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.064
wR(F2) = 0.128
S= 1.01 5652 re¯ections 397 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0371P)2]
whereP= (Fo2+ 2Fc2)/3
(/)max= 0.001 max= 0.84 e AÊÿ3 min=ÿ0.54 e AÊÿ3
Absolute structure: (Flack, 1983), 2319 Friedel pairs
Flack parameter = 0.03 (3)
Table 1
Selected geometric parameters (AÊ,).
Ru1ÐSi1 2.362 (3)
Ru1ÐCl2 2.456 (3)
Ru1ÐCl3 2.462 (3)
Ru1ÐCl1 2.566 (2)
Cl4ÐSi1 2.134 (4)
Si1ÐRu1ÐCl1 173.57 (10) Cl4ÐSi1ÐRu1 111.99 (15)
C1ÐRu1ÐSi1ÐCl4 ÿ11.3 (4)
All H atoms were included in calculated positions with distances of 0.95 AÊ for phenyl CÐH and 1.00 AÊ for cyclopentadienyl CÐH. In the re®nement, H atoms were included in a riding-motion approx-imation, withUiso= 1.2Ueqof the carrier atom.
Data collection:COLLECT(Nonius, 1997±2001); cell re®nement:
DENZO-SMN (Otwinowski & Minor, 1997); data reduction:
DENZO-SMN; program(s) used to solve structure: SHELXTL
(Sheldrick, 2001); program(s) used to re®ne structure:SHELXTL; molecular graphics:SHELXTL; software used to prepare material for publication:SHELXTL.
The authors acknowledge NSERC Canada and the University of Toronto for ®nancial support.
References
Flack, H. D. (1983).Acta Cryst.A39, 876±881.
Nonius (1997±2001).COLLECT. Nonius BV, Delft, The Netherlands. Nguyen, P., GoÂmez-Elipe, P. & Manners, I. (1999).Chem. Rev.99, 1515±1548. Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr and R. M. Sweet, pp. 307±326. New York: Academic Press.
Sheldrick, G. M. (2001).SHELXTL/PC. Version 5.1 for Windows NT. Bruker AXS Inc., Madison, Wisconsin, USA.
Figure 1
supporting information
sup-1 Acta Cryst. (2002). E58, m679–m680
supporting information
Acta Cryst. (2002). E58, m679–m680 [https://doi.org/10.1107/S1600536802019153]
Bis[di-
η
5-cyclopentadienylcobalt(I)]
dicarbonyltrichloro(chlorodiphenyl-silyl)ruthenium(II)
Andrea Berenbaum, Alan J. Lough and Ian Manners
dicarbonyltrichloro(chlorodiphenylsilyl)ruthenium(II) bis[di-η5-cyclopentadienylcobalt(I)]
Crystal data
[Co(C5H5)2]2[RuCl3(C12H10ClSi)(CO)2]
Mr = 859.40
Orthorhombic, P212121
Hall symbol: P 2ac 2ab
a = 9.7462 (5) Å
b = 10.2277 (6) Å
c = 34.099 (2) Å
V = 3399.0 (3) Å3
Z = 4
F(000) = 1720
Dx = 1.679 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3060 reflections
θ = 2.6–25.0°
µ = 1.78 mm−1
T = 150 K Plate, dark orange 0.20 × 0.20 × 0.02 mm
Data collection
Nonius KappaCCD diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
Detector resolution: 9 pixels mm-1
φ scans and ω scans with κ offsets Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
Tmin = 0.717, Tmax = 0.965
12795 measured reflections 5652 independent reflections 3558 reflections with I > 2σ(I)
Rint = 0.109
θmax = 25.0°, θmin = 2.7°
h = −11→11
k = −12→12
l = −37→36
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.064
wR(F2) = 0.128
S = 1.01 5652 reflections 397 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(F
o2) + (0.0371P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.84 e Å−3
Δρmin = −0.54 e Å−3
Absolute structure: (Flack, 1983), 2319 Friedel pairs
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.
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)
x y z Uiso*/Ueq
Ru1 0.76741 (8) 0.48626 (7) 0.34656 (2) 0.0406 (2) Cl1 0.7378 (3) 0.4406 (2) 0.27306 (6) 0.0507 (7) Cl2 0.9653 (3) 0.6236 (2) 0.32940 (7) 0.0482 (7) Cl3 0.6065 (3) 0.6703 (2) 0.33936 (8) 0.0490 (7) Cl4 0.6548 (3) 0.4860 (3) 0.45106 (7) 0.0643 (8) Si1 0.8154 (3) 0.5437 (3) 0.41222 (8) 0.0445 (8) O1 0.5304 (8) 0.3205 (8) 0.3724 (2) 0.067 (3) O2 0.9436 (8) 0.2481 (7) 0.3578 (2) 0.065 (2) C1 0.6202 (13) 0.3830 (12) 0.3629 (3) 0.053 (3) C2 0.8796 (11) 0.3401 (11) 0.3527 (3) 0.045 (3) C3 0.9706 (12) 0.4584 (10) 0.4331 (3) 0.053 (3) C4 0.9636 (15) 0.3622 (11) 0.4626 (3) 0.071 (4)
H4A 0.8769 0.3409 0.4737 0.085*
C5 1.0822 (17) 0.2964 (12) 0.4764 (4) 0.078 (4)
H5A 1.0754 0.2312 0.4962 0.093*
C6 1.2088 (18) 0.3294 (12) 0.4602 (4) 0.082 (5)
H6A 1.2897 0.2878 0.4696 0.098*
C7 1.2183 (13) 0.4227 (11) 0.4305 (3) 0.067 (3)
H7A 1.3048 0.4443 0.4195 0.080*
C8 1.0989 (12) 0.4843 (11) 0.4172 (3) 0.060 (3)
H8A 1.1058 0.5459 0.3964 0.072*
supporting information
sup-3 Acta Cryst. (2002). E58, m679–m680
C16 0.3816 (14) 0.4297 (12) 0.2907 (3) 0.065 (3) H16A 0.4530 0.4961 0.2975 0.078* C17 0.2514 (15) 0.4211 (11) 0.3070 (3) 0.062 (3) H17A 0.2126 0.4805 0.3275 0.074* C18 0.1854 (14) 0.3182 (14) 0.2901 (4) 0.074 (4) H18A 0.0892 0.2906 0.2960 0.089* C19 0.2716 (17) 0.2578 (11) 0.2630 (3) 0.065 (4) H19A 0.2494 0.1798 0.2464 0.079* C20 0.2555 (11) 0.4925 (9) 0.1914 (3) 0.049 (3) H20A 0.3223 0.4541 0.1723 0.059* C21 0.2756 (13) 0.6051 (10) 0.2143 (3) 0.054 (3) H21A 0.3604 0.6601 0.2147 0.065* C22 0.1573 (12) 0.6259 (10) 0.2372 (3) 0.049 (3) H22A 0.1433 0.6982 0.2565 0.058* C23 0.0628 (11) 0.5258 (10) 0.2282 (3) 0.049 (3) H23A −0.0307 0.5146 0.2398 0.058* C24 0.1243 (11) 0.4445 (11) 0.1999 (3) 0.053 (3) H24A 0.0816 0.3649 0.1881 0.063* Co2 0.68687 (14) 0.43589 (13) 0.11062 (4) 0.0463 (4) C25 0.639 (2) 0.2732 (14) 0.0810 (4) 0.090 (5) H25A 0.6280 0.1837 0.0925 0.108* C26 0.7599 (16) 0.3266 (14) 0.0659 (3) 0.080 (4) H26A 0.8516 0.2830 0.0645 0.096* C27 0.7272 (17) 0.4549 (14) 0.0524 (3) 0.074 (4) H27A 0.7918 0.5187 0.0401 0.088* C28 0.5907 (17) 0.4742 (15) 0.0597 (4) 0.080 (4) H28A 0.5399 0.5569 0.0539 0.096* C29 0.5339 (15) 0.3665 (19) 0.0766 (4) 0.084 (5) H29A 0.4357 0.3558 0.0845 0.101* C30 0.7802 (16) 0.3932 (13) 0.1612 (3) 0.078 (4) H30A 0.8282 0.3096 0.1677 0.094* C31 0.8419 (12) 0.5088 (15) 0.1435 (3) 0.070 (4) H31A 0.9398 0.5194 0.1353 0.083* C32 0.7377 (17) 0.6016 (12) 0.1401 (3) 0.077 (4) H32A 0.7462 0.6915 0.1288 0.092* C33 0.6194 (14) 0.5451 (14) 0.1561 (4) 0.077 (4) H33A 0.5278 0.5889 0.1571 0.093* C34 0.6436 (13) 0.4221 (14) 0.1683 (3) 0.065 (4) H34A 0.5748 0.3619 0.1804 0.078*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Si1 0.0557 (19) 0.0346 (18) 0.0432 (18) −0.0024 (16) −0.0025 (14) 0.0023 (13) O1 0.059 (6) 0.056 (6) 0.086 (6) −0.019 (5) −0.006 (5) −0.002 (4) O2 0.067 (6) 0.040 (5) 0.087 (6) 0.021 (4) 0.000 (5) 0.004 (4) C1 0.052 (8) 0.052 (8) 0.056 (8) 0.010 (7) −0.016 (6) −0.011 (6) C2 0.050 (7) 0.044 (8) 0.040 (6) −0.017 (6) 0.009 (5) −0.003 (6) C3 0.060 (8) 0.034 (7) 0.065 (8) 0.011 (6) −0.013 (6) 0.001 (6) C4 0.102 (11) 0.040 (8) 0.069 (9) 0.015 (8) −0.013 (8) 0.000 (7) C5 0.115 (13) 0.050 (9) 0.068 (10) 0.007 (10) −0.007 (9) 0.019 (7) C6 0.124 (14) 0.046 (8) 0.076 (10) 0.022 (9) −0.052 (10) −0.005 (7) C7 0.057 (9) 0.061 (8) 0.082 (9) −0.001 (8) −0.016 (7) −0.004 (7) C8 0.047 (7) 0.054 (8) 0.080 (8) 0.011 (7) −0.014 (6) 0.011 (7) C9 0.048 (7) 0.036 (7) 0.040 (7) −0.006 (5) 0.008 (5) 0.001 (5) C10 0.139 (13) 0.031 (7) 0.044 (7) 0.002 (7) −0.013 (8) 0.007 (6) C11 0.166 (15) 0.037 (8) 0.051 (8) −0.023 (9) −0.014 (8) −0.006 (6) C12 0.104 (10) 0.038 (7) 0.069 (9) −0.005 (7) 0.014 (7) −0.016 (7) C13 0.076 (8) 0.036 (7) 0.056 (8) −0.002 (6) 0.007 (6) −0.012 (6) C14 0.048 (7) 0.061 (8) 0.037 (6) 0.007 (6) 0.002 (5) 0.001 (6) Co1 0.0433 (9) 0.0321 (7) 0.0498 (8) −0.0007 (8) −0.0021 (8) −0.0014 (6) C15 0.088 (11) 0.077 (10) 0.063 (9) 0.052 (9) 0.011 (8) 0.002 (8) C16 0.066 (9) 0.057 (9) 0.071 (9) 0.001 (7) −0.034 (7) −0.003 (7) C17 0.067 (9) 0.061 (8) 0.056 (7) 0.023 (9) 0.000 (7) 0.005 (6) C18 0.059 (9) 0.079 (10) 0.084 (10) −0.027 (8) −0.008 (8) 0.025 (8) C19 0.098 (12) 0.040 (7) 0.059 (8) −0.003 (9) −0.007 (8) 0.008 (6) C20 0.053 (7) 0.040 (6) 0.055 (6) 0.014 (7) 0.005 (6) −0.001 (5) C21 0.073 (9) 0.042 (7) 0.047 (7) −0.004 (7) 0.014 (7) 0.007 (5) C22 0.070 (9) 0.023 (6) 0.053 (7) 0.001 (6) 0.002 (6) 0.004 (5) C23 0.047 (7) 0.039 (7) 0.060 (7) 0.007 (6) 0.003 (5) 0.007 (6) C24 0.055 (8) 0.053 (8) 0.051 (7) 0.003 (6) −0.010 (6) −0.007 (6) Co2 0.0467 (9) 0.0427 (9) 0.0496 (9) −0.0025 (7) 0.0008 (7) 0.0001 (7) C25 0.135 (15) 0.061 (10) 0.076 (10) −0.036 (11) 0.014 (10) −0.030 (8) C26 0.085 (11) 0.067 (9) 0.087 (9) −0.001 (10) 0.024 (9) −0.022 (7) C27 0.084 (11) 0.088 (11) 0.049 (7) −0.049 (10) −0.017 (7) 0.000 (6) C28 0.084 (11) 0.084 (12) 0.071 (9) −0.016 (10) −0.044 (8) 0.010 (8) C29 0.066 (10) 0.135 (15) 0.052 (9) −0.026 (12) −0.007 (7) −0.027 (10) C30 0.105 (12) 0.063 (9) 0.068 (9) 0.028 (9) −0.023 (9) 0.008 (7) C31 0.046 (7) 0.098 (12) 0.065 (8) 0.003 (9) −0.014 (6) 0.007 (8) C32 0.109 (12) 0.048 (7) 0.074 (8) −0.021 (10) −0.005 (10) 0.005 (6) C33 0.079 (10) 0.064 (9) 0.089 (10) −0.007 (8) 0.008 (8) 0.003 (9) C34 0.069 (10) 0.059 (9) 0.066 (9) −0.023 (8) 0.007 (7) 0.010 (7)
Geometric parameters (Å, º)
Ru1—C2 1.864 (12) C16—H16A 1.0000
Ru1—C1 1.867 (14) C17—C18 1.362 (15)
Ru1—Si1 2.362 (3) C17—H17A 1.0000
Ru1—Cl2 2.456 (3) C18—C19 1.395 (16)
Ru1—Cl3 2.462 (3) C18—H18A 1.0000
supporting information
sup-5 Acta Cryst. (2002). E58, m679–m680
Cl4—Si1 2.134 (4) C20—C24 1.400 (13) Si1—C3 1.886 (11) C20—C21 1.405 (12)
Si1—C9 1.901 (10) C20—H20A 1.0000
O1—C1 1.131 (12) C21—C22 1.408 (14)
O2—C2 1.143 (11) C21—H21A 1.0000
C3—C8 1.389 (14) C22—C23 1.411 (13)
C3—C4 1.409 (13) C22—H22A 1.0000
C4—C5 1.417 (16) C23—C24 1.408 (13)
C4—H4A 0.9500 C23—H23A 1.0000
C5—C6 1.393 (18) C24—H24A 1.0000
C5—H5A 0.9500 Co2—C30 1.997 (11)
C6—C7 1.395 (15) Co2—C25 2.002 (12)
C6—H6A 0.9500 Co2—C28 2.011 (11)
C7—C8 1.399 (14) Co2—C34 2.017 (11)
C7—H7A 0.9500 Co2—C29 2.017 (12)
C8—H8A 0.9500 Co2—C26 2.021 (11)
C9—C10 1.373 (13) Co2—C33 2.021 (13) C9—C14 1.384 (12) Co2—C31 2.024 (11) C10—C11 1.323 (14) Co2—C27 2.032 (11)
C10—H10A 0.9500 Co2—C32 2.032 (11)
C11—C12 1.403 (15) C25—C26 1.402 (18)
C11—H11A 0.9500 C25—C29 1.405 (19)
C12—C13 1.353 (13) C25—H25A 1.0000
C12—H12A 0.9500 C26—C27 1.425 (16)
C13—C14 1.413 (13) C26—H26A 1.0000
C13—H13A 0.9500 C27—C28 1.367 (18)
C14—H14A 0.9500 C27—H27A 1.0000
Co1—C16 2.001 (11) C28—C29 1.361 (17) Co1—C18 2.004 (12) C28—H28A 1.0000 Co1—C24 2.007 (10) C29—H29A 1.0000 Co1—C17 2.009 (10) C30—C34 1.386 (16) Co1—C20 2.015 (9) C30—C31 1.456 (16) Co1—C23 2.024 (10) C30—H30A 1.0000 Co1—C21 2.025 (10) C31—C32 1.395 (15) Co1—C19 2.025 (11) C31—H31A 1.0000 Co1—C22 2.031 (10) C32—C33 1.400 (16) Co1—C15 2.061 (12) C32—H32A 1.0000 C15—C16 1.409 (15) C33—C34 1.346 (16) C15—C19 1.411 (17) C33—H33A 1.0000
C15—H15A 1.0000 C34—H34A 1.0000
C16—C17 1.389 (15)
supporting information
sup-7 Acta Cryst. (2002). E58, m679–m680
C19—Co1—C15 40.4 (5) C25—C29—H29A 126.3 C22—Co1—C15 153.2 (6) Co2—C29—H29A 126.3 C16—C15—C19 107.0 (11) C34—C30—C31 107.2 (11) C16—C15—Co1 67.4 (7) C34—C30—Co2 70.6 (7) C19—C15—Co1 68.4 (7) C31—C30—Co2 69.8 (6) C16—C15—H15A 126.5 C34—C30—H30A 126.4 C19—C15—H15A 126.5 C31—C30—H30A 126.4 Co1—C15—H15A 126.5 Co2—C30—H30A 126.4 C17—C16—C15 108.2 (12) C32—C31—C30 106.6 (10) C17—C16—Co1 70.1 (6) C32—C31—Co2 70.2 (6) C15—C16—Co1 72.0 (7) C30—C31—Co2 67.8 (7) C17—C16—H16A 125.9 C32—C31—H31A 126.7 C15—C16—H16A 125.9 C30—C31—H31A 126.7 Co1—C16—H16A 125.9 Co2—C31—H31A 126.7 C18—C17—C16 108.1 (11) C31—C32—C33 106.6 (11) C18—C17—Co1 70.0 (7) C31—C32—Co2 69.6 (7) C16—C17—Co1 69.4 (6) C33—C32—Co2 69.4 (7) C18—C17—H17A 126.0 C31—C32—H32A 126.7 C16—C17—H17A 126.0 C33—C32—H32A 126.7 Co1—C17—H17A 126.0 Co2—C32—H32A 126.7 C17—C18—C19 109.8 (12) C34—C33—C32 111.2 (13) C17—C18—Co1 70.3 (7) C34—C33—Co2 70.3 (8) C19—C18—Co1 70.6 (7) C32—C33—Co2 70.2 (7) C17—C18—H18A 125.1 C34—C33—H33A 124.3 C19—C18—H18A 125.1 C32—C33—H33A 124.3 Co1—C18—H18A 125.1 Co2—C33—H33A 124.3 C18—C19—C15 106.8 (11) C33—C34—C30 108.3 (12) C18—C19—Co1 69.0 (7) C33—C34—Co2 70.7 (8) C15—C19—Co1 71.2 (7) C30—C34—Co2 69.0 (7) C18—C19—H19A 126.6 C33—C34—H34A 125.9 C15—C19—H19A 126.6 C30—C34—H34A 125.9 Co1—C19—H19A 126.6 Co2—C34—H34A 125.9 C24—C20—C21 107.4 (10)
