Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801016166/ya6058sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801016166/ya6058Isup2.hkl |
CCDC reference: 175982
The compound was prepared by stirring hexacarbonyldicobalt[µ,η2-bis-(trimethylstannyl)]acetylene (126 mg, 0.2 mmol) with 79 mg (0.2 mmol) of bis(diphenylphosphino)methane in 10 ml of dry hexane for 5 h under reflux in an inert atmosphere. It was separated by column chromatography (silica gel, hexane/benzene) as a black solid, m.p. 446 K, yield 116 mg (60%).
Hydrogen atoms were placed in calculated positions with Uiso constrained to be 1.5 times Ueq of the carrier atom for the methyl-H and 1.2 times Ueq for the remaining H atoms. The highest peak in the final difference map is at a distance of 0.86 Å from Sn2.
Data collection: CAD-4 Software (Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97, PARST95 (Nardelli, 1995).
Fig. 1. : View of the title compound showing the labelling of all non-H atoms. Displacement ellipsoids are shown at 30% probability level. H atoms are omitted for clarity. |
C37H40Co2O4P2Sn2 | F(000) = 1912 |
Mr = 965.87 | Dx = 1.624 Mg m−3 |
Monoclinic, P21/n | Ag Kα radiation, λ = 0.56083 Å |
a = 16.012 (3) Å | Cell parameters from 25 reflections |
b = 13.761 (2) Å | θ = 10.8–12.6° |
c = 18.126 (4) Å | µ = 1.15 mm−1 |
β = 98.49 (2)° | T = 291 K |
V = 3950.1 (13) Å3 | Plate, red-brown |
Z = 4 | 0.35 × 0.35 × 0.10 mm |
CAD-4 Software (Nonius, 1989) diffractometer | 5353 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.053 |
Graphite monochromator | θmax = 21.0°, θmin = 3.0° |
ω scans | h = −20→20 |
Absorption correction: ψ scan (WinGX; Farrugia, 1999; North et al., 1968) | k = 0→17 |
Tmin = 0.819, Tmax = 1.000 | l = 0→22 |
8838 measured reflections | 3 standard reflections every 60 min |
8572 independent reflections | intensity decay: none |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.054P)2] where P = (Fo2 + 2Fc2)/3 |
8572 reflections | (Δ/σ)max = 0.002 |
430 parameters | Δρmax = 1.10 e Å−3 |
0 restraints | Δρmin = −0.56 e Å−3 |
C37H40Co2O4P2Sn2 | V = 3950.1 (13) Å3 |
Mr = 965.87 | Z = 4 |
Monoclinic, P21/n | Ag Kα radiation, λ = 0.56083 Å |
a = 16.012 (3) Å | µ = 1.15 mm−1 |
b = 13.761 (2) Å | T = 291 K |
c = 18.126 (4) Å | 0.35 × 0.35 × 0.10 mm |
β = 98.49 (2)° |
CAD-4 Software (Nonius, 1989) diffractometer | 5353 reflections with I > 2σ(I) |
Absorption correction: ψ scan (WinGX; Farrugia, 1999; North et al., 1968) | Rint = 0.053 |
Tmin = 0.819, Tmax = 1.000 | 3 standard reflections every 60 min |
8838 measured reflections | intensity decay: none |
8572 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 0.99 | Δρmax = 1.10 e Å−3 |
8572 reflections | Δρmin = −0.56 e Å−3 |
430 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 | ||
Sn1 | 0.193158 (19) | 0.18340 (3) | 0.656614 (18) | 0.05000 (10) | |
Sn2 | 0.46323 (2) | 0.15971 (3) | 0.760026 (17) | 0.05477 (11) | |
Co1 | 0.38724 (3) | 0.14064 (4) | 0.55660 (3) | 0.03985 (14) | |
Co2 | 0.38246 (3) | 0.31459 (4) | 0.59499 (3) | 0.03782 (13) | |
P1 | 0.30053 (6) | 0.15049 (8) | 0.44928 (6) | 0.0364 (2) | |
P2 | 0.31796 (6) | 0.36042 (8) | 0.48421 (6) | 0.0374 (2) | |
O1 | 0.5640 (2) | 0.1503 (4) | 0.5356 (2) | 0.0986 (16) | |
O3 | 0.3682 (3) | −0.0609 (3) | 0.5990 (2) | 0.0874 (12) | |
O5 | 0.5627 (2) | 0.3603 (3) | 0.6211 (2) | 0.0827 (12) | |
O6 | 0.3101 (3) | 0.4638 (3) | 0.6794 (2) | 0.0910 (13) | |
C1 | 0.4941 (3) | 0.1439 (4) | 0.5415 (3) | 0.0628 (14) | |
C2 | 0.2429 (2) | 0.2670 (3) | 0.4460 (2) | 0.0373 (9) | |
H2A | 0.2195 | 0.2827 | 0.3949 | 0.045* | |
H2B | 0.1970 | 0.2627 | 0.4752 | 0.045* | |
C3 | 0.3755 (3) | 0.0177 (4) | 0.5801 (3) | 0.0578 (12) | |
C5 | 0.4920 (3) | 0.3454 (3) | 0.6079 (3) | 0.0509 (11) | |
C6 | 0.3394 (3) | 0.4056 (4) | 0.6465 (2) | 0.0521 (11) | |
C7 | 0.3116 (2) | 0.2040 (3) | 0.6199 (2) | 0.0382 (9) | |
C8 | 0.3898 (3) | 0.1960 (3) | 0.6570 (2) | 0.0421 (9) | |
C9 | 0.2067 (4) | 0.2284 (5) | 0.7704 (3) | 0.0851 (18) | |
H9A | 0.2468 | 0.1872 | 0.8000 | 0.128* | |
H9B | 0.1531 | 0.2238 | 0.7879 | 0.128* | |
H9C | 0.2261 | 0.2944 | 0.7744 | 0.128* | |
C10 | 0.1627 (3) | 0.0327 (4) | 0.6441 (3) | 0.0687 (14) | |
H10A | 0.1482 | 0.0176 | 0.5921 | 0.103* | |
H10B | 0.1157 | 0.0182 | 0.6695 | 0.103* | |
H10C | 0.2105 | −0.0055 | 0.6651 | 0.103* | |
C11 | 0.0955 (3) | 0.2727 (4) | 0.5976 (3) | 0.0711 (15) | |
H11A | 0.1171 | 0.3369 | 0.5919 | 0.107* | |
H11B | 0.0488 | 0.2760 | 0.6252 | 0.107* | |
H11C | 0.0769 | 0.2452 | 0.5493 | 0.107* | |
C12 | 0.5897 (3) | 0.1339 (5) | 0.7425 (4) | 0.092 (2) | |
H12A | 0.5897 | 0.1043 | 0.6945 | 0.138* | |
H12B | 0.6168 | 0.0913 | 0.7806 | 0.138* | |
H12C | 0.6198 | 0.1944 | 0.7444 | 0.138* | |
C13 | 0.4582 (5) | 0.2781 (5) | 0.8348 (4) | 0.112 (3) | |
H13A | 0.4759 | 0.3365 | 0.8127 | 0.169* | |
H13B | 0.4950 | 0.2652 | 0.8806 | 0.169* | |
H13C | 0.4014 | 0.2859 | 0.8450 | 0.169* | |
C14 | 0.4105 (4) | 0.0339 (4) | 0.8038 (3) | 0.0823 (17) | |
H14A | 0.3641 | 0.0526 | 0.8287 | 0.123* | |
H14B | 0.4529 | 0.0023 | 0.8387 | 0.123* | |
H14C | 0.3908 | −0.0100 | 0.7638 | 0.123* | |
C21 | 0.2178 (3) | 0.0580 (3) | 0.4361 (2) | 0.0439 (10) | |
C22 | 0.2428 (3) | −0.0368 (3) | 0.4276 (3) | 0.0616 (13) | |
H22 | 0.2996 | −0.0508 | 0.4276 | 0.074* | |
C23 | 0.1845 (4) | −0.1108 (4) | 0.4191 (3) | 0.0832 (19) | |
H23 | 0.2020 | −0.1743 | 0.4129 | 0.100* | |
C24 | 0.1009 (4) | −0.0913 (5) | 0.4199 (3) | 0.0837 (19) | |
H24 | 0.0616 | −0.1414 | 0.4137 | 0.100* | |
C25 | 0.0755 (3) | 0.0004 (5) | 0.4296 (3) | 0.0789 (17) | |
H25 | 0.0188 | 0.0133 | 0.4312 | 0.095* | |
C26 | 0.1338 (3) | 0.0760 (4) | 0.4372 (3) | 0.0568 (12) | |
H26 | 0.1157 | 0.1394 | 0.4431 | 0.068* | |
C31 | 0.3353 (3) | 0.1461 (3) | 0.3574 (2) | 0.0418 (9) | |
C32 | 0.2758 (3) | 0.1456 (4) | 0.2926 (2) | 0.0566 (12) | |
H32 | 0.2184 | 0.1456 | 0.2961 | 0.068* | |
C33 | 0.3023 (4) | 0.1452 (4) | 0.2237 (3) | 0.0710 (15) | |
H33 | 0.2627 | 0.1443 | 0.1806 | 0.085* | |
C34 | 0.3865 (4) | 0.1461 (4) | 0.2186 (3) | 0.0753 (16) | |
H34 | 0.4042 | 0.1459 | 0.1719 | 0.090* | |
C35 | 0.4441 (4) | 0.1473 (4) | 0.2806 (3) | 0.0750 (16) | |
H35 | 0.5013 | 0.1494 | 0.2767 | 0.090* | |
C36 | 0.4188 (3) | 0.1456 (4) | 0.3501 (3) | 0.0575 (12) | |
H36 | 0.4592 | 0.1441 | 0.3925 | 0.069* | |
C41 | 0.3772 (3) | 0.3863 (3) | 0.4080 (2) | 0.0421 (9) | |
C42 | 0.3366 (3) | 0.4164 (4) | 0.3387 (2) | 0.0546 (11) | |
H42 | 0.2783 | 0.4251 | 0.3313 | 0.066* | |
C43 | 0.3817 (4) | 0.4336 (4) | 0.2808 (3) | 0.0704 (15) | |
H43 | 0.3538 | 0.4545 | 0.2349 | 0.084* | |
C44 | 0.4675 (4) | 0.4201 (4) | 0.2904 (3) | 0.0706 (15) | |
H44 | 0.4974 | 0.4304 | 0.2509 | 0.085* | |
C45 | 0.5090 (3) | 0.3911 (4) | 0.3589 (3) | 0.0660 (14) | |
H45 | 0.5674 | 0.3832 | 0.3660 | 0.079* | |
C46 | 0.4640 (3) | 0.3738 (4) | 0.4173 (3) | 0.0524 (11) | |
H46 | 0.4923 | 0.3536 | 0.4632 | 0.063* | |
C51 | 0.2527 (3) | 0.4695 (3) | 0.4834 (2) | 0.0431 (9) | |
C52 | 0.2942 (3) | 0.5569 (3) | 0.4991 (3) | 0.0636 (13) | |
H52 | 0.3529 | 0.5583 | 0.5048 | 0.076* | |
C53 | 0.2507 (5) | 0.6419 (4) | 0.5063 (3) | 0.0796 (18) | |
H53 | 0.2796 | 0.7002 | 0.5160 | 0.096* | |
C54 | 0.1644 (5) | 0.6393 (4) | 0.4991 (3) | 0.0780 (17) | |
H54 | 0.1348 | 0.6957 | 0.5068 | 0.094* | |
C55 | 0.1214 (4) | 0.5552 (4) | 0.4808 (3) | 0.0712 (15) | |
H55 | 0.0626 | 0.5550 | 0.4733 | 0.085* | |
C56 | 0.1655 (3) | 0.4702 (4) | 0.4733 (3) | 0.0571 (12) | |
H56 | 0.1360 | 0.4127 | 0.4614 | 0.068* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.04056 (16) | 0.0610 (2) | 0.05002 (18) | −0.00602 (14) | 0.01182 (13) | 0.00162 (15) |
Sn2 | 0.0606 (2) | 0.0592 (2) | 0.03853 (17) | −0.00040 (16) | −0.01251 (14) | 0.00117 (14) |
Co1 | 0.0348 (3) | 0.0470 (3) | 0.0357 (3) | 0.0069 (2) | −0.0018 (2) | −0.0045 (2) |
Co2 | 0.0352 (3) | 0.0430 (3) | 0.0341 (3) | −0.0035 (2) | 0.0015 (2) | −0.0011 (2) |
P1 | 0.0318 (5) | 0.0405 (6) | 0.0355 (5) | −0.0001 (4) | −0.0001 (4) | −0.0022 (4) |
P2 | 0.0357 (5) | 0.0406 (6) | 0.0349 (5) | −0.0008 (4) | 0.0023 (4) | 0.0013 (4) |
O1 | 0.0362 (19) | 0.170 (5) | 0.089 (3) | 0.020 (2) | 0.0071 (18) | −0.036 (3) |
O3 | 0.129 (4) | 0.053 (2) | 0.080 (3) | 0.013 (2) | 0.016 (2) | 0.008 (2) |
O5 | 0.0404 (19) | 0.097 (3) | 0.107 (3) | −0.0188 (19) | −0.0006 (19) | −0.006 (2) |
O6 | 0.122 (4) | 0.089 (3) | 0.066 (2) | 0.020 (3) | 0.026 (2) | −0.025 (2) |
C1 | 0.044 (3) | 0.089 (4) | 0.053 (3) | 0.010 (3) | −0.001 (2) | −0.018 (3) |
C2 | 0.0307 (19) | 0.043 (2) | 0.036 (2) | 0.0025 (16) | −0.0009 (15) | 0.0007 (17) |
C3 | 0.067 (3) | 0.061 (3) | 0.043 (2) | 0.016 (3) | 0.000 (2) | −0.005 (2) |
C5 | 0.050 (3) | 0.054 (3) | 0.047 (2) | −0.003 (2) | 0.000 (2) | 0.001 (2) |
C6 | 0.060 (3) | 0.058 (3) | 0.038 (2) | −0.002 (2) | 0.005 (2) | −0.001 (2) |
C7 | 0.039 (2) | 0.041 (2) | 0.035 (2) | −0.0033 (17) | 0.0087 (16) | −0.0052 (17) |
C8 | 0.041 (2) | 0.050 (2) | 0.033 (2) | −0.0010 (18) | −0.0013 (16) | −0.0020 (18) |
C9 | 0.091 (4) | 0.110 (5) | 0.061 (3) | −0.014 (4) | 0.032 (3) | −0.020 (3) |
C10 | 0.063 (3) | 0.070 (3) | 0.072 (3) | −0.022 (3) | 0.006 (3) | 0.011 (3) |
C11 | 0.048 (3) | 0.078 (4) | 0.089 (4) | 0.011 (3) | 0.014 (3) | 0.000 (3) |
C12 | 0.055 (3) | 0.104 (5) | 0.107 (5) | 0.001 (3) | −0.019 (3) | 0.016 (4) |
C13 | 0.133 (6) | 0.108 (6) | 0.084 (5) | −0.001 (5) | −0.025 (4) | −0.043 (4) |
C14 | 0.099 (4) | 0.075 (4) | 0.075 (4) | 0.004 (3) | 0.018 (3) | 0.026 (3) |
C21 | 0.040 (2) | 0.050 (3) | 0.037 (2) | −0.0080 (19) | −0.0067 (17) | 0.0059 (18) |
C22 | 0.060 (3) | 0.050 (3) | 0.069 (3) | −0.004 (2) | −0.007 (2) | 0.003 (2) |
C23 | 0.101 (5) | 0.047 (3) | 0.093 (4) | −0.018 (3) | −0.016 (4) | 0.010 (3) |
C24 | 0.087 (5) | 0.082 (5) | 0.077 (4) | −0.047 (4) | −0.007 (3) | 0.013 (3) |
C25 | 0.049 (3) | 0.111 (5) | 0.073 (4) | −0.032 (3) | −0.002 (2) | 0.008 (4) |
C26 | 0.041 (2) | 0.067 (3) | 0.060 (3) | −0.008 (2) | −0.002 (2) | −0.005 (2) |
C31 | 0.046 (2) | 0.042 (2) | 0.037 (2) | −0.0007 (18) | 0.0024 (17) | −0.0054 (17) |
C32 | 0.056 (3) | 0.071 (3) | 0.041 (2) | −0.001 (2) | 0.000 (2) | −0.002 (2) |
C33 | 0.099 (4) | 0.071 (4) | 0.038 (3) | −0.008 (3) | −0.006 (3) | −0.008 (2) |
C34 | 0.101 (5) | 0.081 (4) | 0.049 (3) | −0.007 (3) | 0.031 (3) | −0.010 (3) |
C35 | 0.070 (3) | 0.099 (5) | 0.062 (3) | −0.005 (3) | 0.028 (3) | −0.019 (3) |
C36 | 0.051 (3) | 0.074 (3) | 0.048 (3) | 0.001 (2) | 0.010 (2) | −0.009 (2) |
C41 | 0.043 (2) | 0.046 (2) | 0.038 (2) | −0.0068 (18) | 0.0050 (17) | −0.0049 (18) |
C42 | 0.053 (3) | 0.064 (3) | 0.044 (2) | −0.005 (2) | 0.001 (2) | 0.009 (2) |
C43 | 0.084 (4) | 0.087 (4) | 0.040 (3) | −0.006 (3) | 0.007 (2) | 0.013 (3) |
C44 | 0.077 (4) | 0.086 (4) | 0.054 (3) | −0.010 (3) | 0.028 (3) | −0.003 (3) |
C45 | 0.055 (3) | 0.086 (4) | 0.061 (3) | −0.010 (3) | 0.023 (2) | −0.007 (3) |
C46 | 0.048 (2) | 0.065 (3) | 0.046 (3) | −0.008 (2) | 0.011 (2) | −0.003 (2) |
C51 | 0.050 (2) | 0.044 (2) | 0.035 (2) | 0.0068 (19) | 0.0050 (17) | 0.0048 (18) |
C52 | 0.069 (3) | 0.047 (3) | 0.070 (3) | −0.002 (2) | −0.005 (3) | −0.001 (2) |
C53 | 0.113 (5) | 0.043 (3) | 0.079 (4) | 0.008 (3) | 0.000 (4) | 0.002 (3) |
C54 | 0.111 (5) | 0.063 (4) | 0.066 (4) | 0.030 (4) | 0.030 (3) | 0.012 (3) |
C55 | 0.063 (3) | 0.080 (4) | 0.075 (4) | 0.021 (3) | 0.024 (3) | 0.020 (3) |
C56 | 0.053 (3) | 0.052 (3) | 0.068 (3) | 0.006 (2) | 0.017 (2) | 0.012 (2) |
Sn1—C7 | 2.119 (4) | C14—H14A | 0.9600 |
Sn1—C9 | 2.133 (5) | C14—H14B | 0.9600 |
Sn1—C10 | 2.135 (5) | C14—H14C | 0.9600 |
Sn1—C11 | 2.146 (5) | C21—C26 | 1.371 (6) |
Sn2—C8 | 2.115 (4) | C21—C22 | 1.380 (6) |
Sn2—C12 | 2.126 (6) | C22—C23 | 1.374 (7) |
Sn2—C13 | 2.129 (6) | C22—H22 | 0.9300 |
Sn2—C14 | 2.131 (5) | C23—C24 | 1.367 (9) |
Co1—C3 | 1.761 (6) | C23—H23 | 0.9300 |
Co1—C1 | 1.772 (5) | C24—C25 | 1.345 (9) |
Co1—C8 | 1.968 (4) | C24—H24 | 0.9300 |
Co1—C7 | 1.989 (4) | C25—C26 | 1.391 (7) |
Co1—P1 | 2.2208 (12) | C25—H25 | 0.9300 |
Co1—Co2 | 2.4972 (8) | C26—H26 | 0.9300 |
Co2—C6 | 1.762 (5) | C31—C36 | 1.362 (6) |
Co2—C5 | 1.786 (5) | C31—C32 | 1.400 (6) |
Co2—C8 | 1.975 (4) | C32—C33 | 1.377 (7) |
Co2—C7 | 1.990 (4) | C32—H32 | 0.9300 |
Co2—P2 | 2.2100 (12) | C33—C34 | 1.366 (8) |
P1—C21 | 1.827 (4) | C33—H33 | 0.9300 |
P1—C31 | 1.833 (4) | C34—C35 | 1.345 (8) |
P1—C2 | 1.846 (4) | C34—H34 | 0.9300 |
P2—C41 | 1.823 (4) | C35—C36 | 1.379 (7) |
P2—C2 | 1.825 (4) | C35—H35 | 0.9300 |
P2—C51 | 1.827 (4) | C36—H36 | 0.9300 |
O1—C1 | 1.145 (6) | C41—C46 | 1.385 (6) |
O3—C3 | 1.146 (6) | C41—C42 | 1.389 (6) |
O5—C5 | 1.141 (5) | C42—C43 | 1.382 (7) |
O6—C6 | 1.140 (6) | C42—H42 | 0.9300 |
C2—H2A | 0.9700 | C43—C44 | 1.371 (7) |
C2—H2B | 0.9700 | C43—H43 | 0.9300 |
C7—C8 | 1.335 (5) | C44—C45 | 1.379 (7) |
C9—H9A | 0.9600 | C44—H44 | 0.9300 |
C9—H9B | 0.9600 | C45—C46 | 1.386 (6) |
C9—H9C | 0.9600 | C45—H45 | 0.9300 |
C10—H10A | 0.9600 | C46—H46 | 0.9300 |
C10—H10B | 0.9600 | C51—C56 | 1.382 (6) |
C10—H10C | 0.9600 | C51—C52 | 1.384 (6) |
C11—H11A | 0.9600 | C52—C53 | 1.377 (7) |
C11—H11B | 0.9600 | C52—H52 | 0.9300 |
C11—H11C | 0.9600 | C53—C54 | 1.369 (8) |
C12—H12A | 0.9600 | C53—H53 | 0.9300 |
C12—H12B | 0.9600 | C54—C55 | 1.363 (8) |
C12—H12C | 0.9600 | C54—H54 | 0.9300 |
C13—H13A | 0.9600 | C55—C56 | 1.384 (7) |
C13—H13B | 0.9600 | C55—H55 | 0.9300 |
C13—H13C | 0.9600 | C56—H56 | 0.9300 |
C7—Sn1—C9 | 107.26 (19) | H11A—C11—H11C | 109.5 |
C7—Sn1—C10 | 107.31 (18) | H11B—C11—H11C | 109.5 |
C9—Sn1—C10 | 111.9 (2) | Sn2—C12—H12A | 109.5 |
C7—Sn1—C11 | 112.76 (19) | Sn2—C12—H12B | 109.5 |
C9—Sn1—C11 | 106.1 (2) | H12A—C12—H12B | 109.5 |
C10—Sn1—C11 | 111.4 (2) | Sn2—C12—H12C | 109.5 |
C8—Sn2—C12 | 109.0 (2) | H12A—C12—H12C | 109.5 |
C8—Sn2—C13 | 108.3 (2) | H12B—C12—H12C | 109.5 |
C12—Sn2—C13 | 110.5 (3) | Sn2—C13—H13A | 109.5 |
C8—Sn2—C14 | 108.8 (2) | Sn2—C13—H13B | 109.5 |
C12—Sn2—C14 | 111.0 (2) | H13A—C13—H13B | 109.5 |
C13—Sn2—C14 | 109.3 (3) | Sn2—C13—H13C | 109.5 |
C3—Co1—C1 | 101.6 (2) | H13A—C13—H13C | 109.5 |
C3—Co1—C8 | 97.87 (19) | H13B—C13—H13C | 109.5 |
C1—Co1—C8 | 104.2 (2) | Sn2—C14—H14A | 109.5 |
C3—Co1—C7 | 100.7 (2) | Sn2—C14—H14B | 109.5 |
C1—Co1—C7 | 139.65 (19) | H14A—C14—H14B | 109.5 |
C8—Co1—C7 | 39.43 (16) | Sn2—C14—H14C | 109.5 |
C3—Co1—P1 | 101.25 (15) | H14A—C14—H14C | 109.5 |
C1—Co1—P1 | 110.84 (16) | H14B—C14—H14C | 109.5 |
C8—Co1—P1 | 135.34 (12) | C26—C21—C22 | 118.2 (4) |
C7—Co1—P1 | 97.10 (12) | C26—C21—P1 | 124.5 (4) |
C3—Co1—Co2 | 147.64 (15) | C22—C21—P1 | 117.2 (3) |
C1—Co1—Co2 | 95.10 (18) | C23—C22—C21 | 120.7 (5) |
C8—Co1—Co2 | 50.83 (12) | C23—C22—H22 | 119.7 |
C7—Co1—Co2 | 51.14 (11) | C21—C22—H22 | 119.7 |
P1—Co1—Co2 | 98.31 (4) | C24—C23—C22 | 120.2 (6) |
C6—Co2—C5 | 102.4 (2) | C24—C23—H23 | 119.9 |
C6—Co2—C8 | 106.28 (19) | C22—C23—H23 | 119.9 |
C5—Co2—C8 | 98.47 (19) | C25—C24—C23 | 120.1 (5) |
C6—Co2—C7 | 98.15 (19) | C25—C24—H24 | 120.0 |
C5—Co2—C7 | 137.22 (19) | C23—C24—H24 | 120.0 |
C8—Co2—C7 | 39.35 (16) | C24—C25—C26 | 120.2 (6) |
C6—Co2—P2 | 96.42 (15) | C24—C25—H25 | 119.9 |
C5—Co2—P2 | 111.67 (15) | C26—C25—H25 | 119.9 |
C8—Co2—P2 | 137.17 (12) | C21—C26—C25 | 120.6 (5) |
C7—Co2—P2 | 102.66 (12) | C21—C26—H26 | 119.7 |
C6—Co2—Co1 | 149.22 (16) | C25—C26—H26 | 119.7 |
C5—Co2—Co1 | 101.22 (15) | C36—C31—C32 | 118.3 (4) |
C8—Co2—Co1 | 50.58 (12) | C36—C31—P1 | 121.5 (3) |
C7—Co2—Co1 | 51.12 (11) | C32—C31—P1 | 120.1 (3) |
P2—Co2—Co1 | 92.85 (4) | C33—C32—C31 | 119.9 (5) |
C21—P1—C31 | 99.74 (19) | C33—C32—H32 | 120.1 |
C21—P1—C2 | 104.58 (19) | C31—C32—H32 | 120.1 |
C31—P1—C2 | 102.51 (18) | C34—C33—C32 | 120.1 (5) |
C21—P1—Co1 | 114.82 (13) | C34—C33—H33 | 120.0 |
C31—P1—Co1 | 123.99 (14) | C32—C33—H33 | 120.0 |
C2—P1—Co1 | 109.05 (12) | C35—C34—C33 | 120.3 (5) |
C41—P2—C2 | 103.70 (18) | C35—C34—H34 | 119.8 |
C41—P2—C51 | 101.19 (19) | C33—C34—H34 | 119.8 |
C2—P2—C51 | 103.40 (18) | C34—C35—C36 | 120.4 (5) |
C41—P2—Co2 | 121.26 (14) | C34—C35—H35 | 119.8 |
C2—P2—Co2 | 109.71 (13) | C36—C35—H35 | 119.8 |
C51—P2—Co2 | 115.59 (13) | C31—C36—C35 | 121.0 (5) |
O1—C1—Co1 | 175.4 (4) | C31—C36—H36 | 119.5 |
P2—C2—P1 | 107.55 (18) | C35—C36—H36 | 119.5 |
P2—C2—H2A | 110.2 | C46—C41—C42 | 118.4 (4) |
P1—C2—H2A | 110.2 | C46—C41—P2 | 120.5 (3) |
P2—C2—H2B | 110.2 | C42—C41—P2 | 121.1 (3) |
P1—C2—H2B | 110.2 | C43—C42—C41 | 120.7 (5) |
H2A—C2—H2B | 108.5 | C43—C42—H42 | 119.7 |
O3—C3—Co1 | 176.5 (4) | C41—C42—H42 | 119.7 |
O5—C5—Co2 | 174.4 (4) | C44—C43—C42 | 120.5 (5) |
O6—C6—Co2 | 178.8 (5) | C44—C43—H43 | 119.8 |
C8—C7—Co1 | 69.4 (2) | C42—C43—H43 | 119.8 |
C8—C7—Co2 | 69.7 (2) | C43—C44—C45 | 119.7 (5) |
Co1—C7—Co2 | 77.74 (14) | C43—C44—H44 | 120.2 |
C8—C7—Sn1 | 130.3 (3) | C45—C44—H44 | 120.2 |
Co1—C7—Sn1 | 140.5 (2) | C44—C45—C46 | 120.0 (5) |
Co2—C7—Sn1 | 137.8 (2) | C44—C45—H45 | 120.0 |
C7—C8—Co1 | 71.1 (2) | C46—C45—H45 | 120.0 |
C7—C8—Co2 | 70.9 (2) | C41—C46—C45 | 120.8 (4) |
Co1—C8—Co2 | 78.59 (15) | C41—C46—H46 | 119.6 |
C7—C8—Sn2 | 145.3 (3) | C45—C46—H46 | 119.6 |
Co1—C8—Sn2 | 131.2 (2) | C56—C51—C52 | 117.8 (4) |
Co2—C8—Sn2 | 132.6 (2) | C56—C51—P2 | 124.9 (3) |
Sn1—C9—H9A | 109.5 | C52—C51—P2 | 117.1 (3) |
Sn1—C9—H9B | 109.5 | C53—C52—C51 | 121.6 (5) |
H9A—C9—H9B | 109.5 | C53—C52—H52 | 119.2 |
Sn1—C9—H9C | 109.5 | C51—C52—H52 | 119.2 |
H9A—C9—H9C | 109.5 | C54—C53—C52 | 119.1 (6) |
H9B—C9—H9C | 109.5 | C54—C53—H53 | 120.4 |
Sn1—C10—H10A | 109.5 | C52—C53—H53 | 120.4 |
Sn1—C10—H10B | 109.5 | C55—C54—C53 | 120.8 (5) |
H10A—C10—H10B | 109.5 | C55—C54—H54 | 119.6 |
Sn1—C10—H10C | 109.5 | C53—C54—H54 | 119.6 |
H10A—C10—H10C | 109.5 | C54—C55—C56 | 119.7 (5) |
H10B—C10—H10C | 109.5 | C54—C55—H55 | 120.2 |
Sn1—C11—H11A | 109.5 | C56—C55—H55 | 120.2 |
Sn1—C11—H11B | 109.5 | C51—C56—C55 | 120.9 (5) |
H11A—C11—H11B | 109.5 | C51—C56—H56 | 119.5 |
Sn1—C11—H11C | 109.5 | C55—C56—H56 | 119.5 |
C3—Co1—Co2—C6 | −30.7 (4) | Co1—C7—C8—Co2 | 84.09 (12) |
C1—Co1—Co2—C6 | −152.0 (3) | Sn1—C7—C8—Co2 | −136.2 (3) |
C8—Co1—Co2—C6 | −47.8 (3) | Co1—C7—C8—Sn2 | −136.7 (5) |
C7—Co1—Co2—C6 | 3.6 (3) | Co2—C7—C8—Sn2 | 139.2 (5) |
P1—Co1—Co2—C6 | 96.1 (3) | Sn1—C7—C8—Sn2 | 3.0 (8) |
C3—Co1—Co2—C5 | 108.9 (3) | C3—Co1—C8—C7 | −97.3 (3) |
C1—Co1—Co2—C5 | −12.3 (2) | C1—Co1—C8—C7 | 158.5 (3) |
C8—Co1—Co2—C5 | 91.8 (2) | P1—Co1—C8—C7 | 17.5 (3) |
C7—Co1—Co2—C5 | 143.3 (2) | Co2—Co1—C8—C7 | 73.5 (2) |
P1—Co1—Co2—C5 | −124.30 (15) | C3—Co1—C8—Co2 | −170.85 (18) |
C3—Co1—Co2—C8 | 17.1 (3) | C1—Co1—C8—Co2 | 85.0 (2) |
C1—Co1—Co2—C8 | −104.1 (2) | C7—Co1—C8—Co2 | −73.5 (2) |
C7—Co1—Co2—C8 | 51.5 (2) | P1—Co1—C8—Co2 | −56.0 (2) |
P1—Co1—Co2—C8 | 143.91 (16) | C3—Co1—C8—Sn2 | 51.4 (3) |
C3—Co1—Co2—C7 | −34.4 (3) | C1—Co1—C8—Sn2 | −52.7 (3) |
C1—Co1—Co2—C7 | −155.6 (2) | C7—Co1—C8—Sn2 | 148.7 (4) |
C8—Co1—Co2—C7 | −51.5 (2) | P1—Co1—C8—Sn2 | 166.25 (15) |
P1—Co1—Co2—C7 | 92.44 (15) | Co2—Co1—C8—Sn2 | −137.7 (3) |
C3—Co1—Co2—P2 | −138.3 (3) | C6—Co2—C8—C7 | 82.9 (3) |
C1—Co1—Co2—P2 | 100.43 (17) | C5—Co2—C8—C7 | −171.4 (3) |
C8—Co1—Co2—P2 | −155.45 (16) | P2—Co2—C8—C7 | −36.2 (3) |
C7—Co1—Co2—P2 | −103.98 (15) | Co1—Co2—C8—C7 | −73.8 (2) |
P1—Co1—Co2—P2 | −11.54 (5) | C6—Co2—C8—Co1 | 156.72 (17) |
C3—Co1—P1—C21 | 22.8 (2) | C5—Co2—C8—Co1 | −97.60 (18) |
C1—Co1—P1—C21 | 130.0 (2) | C7—Co2—C8—Co1 | 73.8 (2) |
C8—Co1—P1—C21 | −90.7 (2) | P2—Co2—C8—Co1 | 37.6 (2) |
C7—Co1—P1—C21 | −79.6 (2) | C6—Co2—C8—Sn2 | −66.7 (3) |
Co2—Co1—P1—C21 | −131.26 (17) | C5—Co2—C8—Sn2 | 39.0 (3) |
C3—Co1—P1—C31 | −99.6 (2) | C7—Co2—C8—Sn2 | −149.6 (4) |
C1—Co1—P1—C31 | 7.6 (3) | P2—Co2—C8—Sn2 | 174.19 (14) |
C8—Co1—P1—C31 | 146.8 (2) | Co1—Co2—C8—Sn2 | 136.6 (3) |
C7—Co1—P1—C31 | 157.9 (2) | C12—Sn2—C8—C7 | 162.7 (6) |
Co2—Co1—P1—C31 | 106.29 (16) | C13—Sn2—C8—C7 | −77.1 (6) |
C3—Co1—P1—C2 | 139.8 (2) | C14—Sn2—C8—C7 | 41.6 (6) |
C1—Co1—P1—C2 | −113.1 (2) | C12—Sn2—C8—Co1 | 42.2 (3) |
C8—Co1—P1—C2 | 26.2 (2) | C13—Sn2—C8—Co1 | 162.4 (3) |
C7—Co1—P1—C2 | 37.31 (18) | C14—Sn2—C8—Co1 | −78.9 (3) |
Co2—Co1—P1—C2 | −14.32 (14) | C12—Sn2—C8—Co2 | −74.2 (3) |
C6—Co2—P2—C41 | 125.5 (2) | C13—Sn2—C8—Co2 | 46.0 (4) |
C5—Co2—P2—C41 | 19.3 (2) | C14—Sn2—C8—Co2 | 164.6 (3) |
C8—Co2—P2—C41 | −112.1 (2) | C31—P1—C21—C26 | −115.8 (4) |
C7—Co2—P2—C41 | −134.7 (2) | C2—P1—C21—C26 | −10.1 (4) |
Co1—Co2—P2—C41 | −83.92 (16) | Co1—P1—C21—C26 | 109.4 (4) |
C6—Co2—P2—C2 | −113.7 (2) | C31—P1—C21—C22 | 67.0 (4) |
C5—Co2—P2—C2 | 140.1 (2) | C2—P1—C21—C22 | 172.8 (4) |
C8—Co2—P2—C2 | 8.7 (2) | Co1—P1—C21—C22 | −67.7 (4) |
C7—Co2—P2—C2 | −13.87 (18) | C26—C21—C22—C23 | 1.2 (7) |
Co1—Co2—P2—C2 | 36.86 (14) | P1—C21—C22—C23 | 178.5 (4) |
C6—Co2—P2—C51 | 2.6 (2) | C21—C22—C23—C24 | −0.7 (9) |
C5—Co2—P2—C51 | −103.5 (2) | C22—C23—C24—C25 | −0.6 (9) |
C8—Co2—P2—C51 | 125.1 (2) | C23—C24—C25—C26 | 1.4 (9) |
C7—Co2—P2—C51 | 102.5 (2) | C22—C21—C26—C25 | −0.3 (7) |
Co1—Co2—P2—C51 | 153.24 (16) | P1—C21—C26—C25 | −177.4 (4) |
C41—P2—C2—P1 | 78.1 (2) | C24—C25—C26—C21 | −1.0 (8) |
C51—P2—C2—P1 | −176.58 (19) | C21—P1—C31—C36 | −135.4 (4) |
Co2—P2—C2—P1 | −52.7 (2) | C2—P1—C31—C36 | 117.2 (4) |
C21—P1—C2—P2 | 164.34 (19) | Co1—P1—C31—C36 | −6.4 (5) |
C31—P1—C2—P2 | −92.0 (2) | C21—P1—C31—C32 | 46.3 (4) |
Co1—P1—C2—P2 | 41.1 (2) | C2—P1—C31—C32 | −61.2 (4) |
C3—Co1—C7—C8 | 89.4 (3) | Co1—P1—C31—C32 | 175.3 (3) |
C1—Co1—C7—C8 | −33.2 (4) | C36—C31—C32—C33 | −0.3 (7) |
P1—Co1—C7—C8 | −167.7 (2) | P1—C31—C32—C33 | 178.1 (4) |
Co2—Co1—C7—C8 | −72.7 (2) | C31—C32—C33—C34 | −0.6 (8) |
C3—Co1—C7—Co2 | 162.10 (16) | C32—C33—C34—C35 | 0.1 (9) |
C1—Co1—C7—Co2 | 39.5 (4) | C33—C34—C35—C36 | 1.4 (9) |
C8—Co1—C7—Co2 | 72.7 (2) | C32—C31—C36—C35 | 1.7 (7) |
P1—Co1—C7—Co2 | −94.98 (9) | P1—C31—C36—C35 | −176.6 (4) |
C3—Co1—C7—Sn1 | −39.8 (4) | C34—C35—C36—C31 | −2.3 (9) |
C1—Co1—C7—Sn1 | −162.4 (3) | C2—P2—C41—C46 | −120.9 (4) |
C8—Co1—C7—Sn1 | −129.2 (5) | C51—P2—C41—C46 | 132.1 (4) |
P1—Co1—C7—Sn1 | 63.1 (3) | Co2—P2—C41—C46 | 2.7 (4) |
Co2—Co1—C7—Sn1 | 158.1 (4) | C2—P2—C41—C42 | 57.3 (4) |
C6—Co2—C7—C8 | −105.8 (3) | C51—P2—C41—C42 | −49.7 (4) |
C5—Co2—C7—C8 | 12.6 (4) | Co2—P2—C41—C42 | −179.1 (3) |
P2—Co2—C7—C8 | 155.7 (2) | C46—C41—C42—C43 | −0.2 (7) |
Co1—Co2—C7—C8 | 72.4 (2) | P2—C41—C42—C43 | −178.4 (4) |
C6—Co2—C7—Co1 | −178.13 (16) | C41—C42—C43—C44 | 0.8 (8) |
C5—Co2—C7—Co1 | −59.8 (3) | C42—C43—C44—C45 | −1.4 (9) |
C8—Co2—C7—Co1 | −72.4 (2) | C43—C44—C45—C46 | 1.4 (9) |
P2—Co2—C7—Co1 | 83.37 (10) | C42—C41—C46—C45 | 0.2 (7) |
C6—Co2—C7—Sn1 | 22.5 (3) | P2—C41—C46—C45 | 178.4 (4) |
C5—Co2—C7—Sn1 | 140.9 (3) | C44—C45—C46—C41 | −0.8 (8) |
C8—Co2—C7—Sn1 | 128.3 (4) | C41—P2—C51—C56 | 121.2 (4) |
P2—Co2—C7—Sn1 | −76.0 (3) | C2—P2—C51—C56 | 14.0 (4) |
Co1—Co2—C7—Sn1 | −159.4 (4) | Co2—P2—C51—C56 | −105.9 (4) |
C9—Sn1—C7—C8 | 33.3 (5) | C41—P2—C51—C52 | −63.4 (4) |
C10—Sn1—C7—C8 | −87.1 (4) | C2—P2—C51—C52 | −170.6 (4) |
C11—Sn1—C7—C8 | 149.8 (4) | Co2—P2—C51—C52 | 69.5 (4) |
C9—Sn1—C7—Co1 | 141.1 (3) | C56—C51—C52—C53 | 1.5 (7) |
C10—Sn1—C7—Co1 | 20.7 (4) | P2—C51—C52—C53 | −174.2 (4) |
C11—Sn1—C7—Co1 | −102.4 (4) | C51—C52—C53—C54 | 1.1 (9) |
C9—Sn1—C7—Co2 | −71.7 (3) | C52—C53—C54—C55 | −3.8 (9) |
C10—Sn1—C7—Co2 | 167.9 (3) | C53—C54—C55—C56 | 3.6 (9) |
C11—Sn1—C7—Co2 | 44.8 (3) | C52—C51—C56—C55 | −1.7 (7) |
Co2—C7—C8—Co1 | −84.09 (12) | P2—C51—C56—C55 | 173.6 (4) |
Sn1—C7—C8—Co1 | 139.7 (3) | C54—C55—C56—C51 | −0.8 (8) |
Experimental details
Crystal data | |
Chemical formula | C37H40Co2O4P2Sn2 |
Mr | 965.87 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 291 |
a, b, c (Å) | 16.012 (3), 13.761 (2), 18.126 (4) |
β (°) | 98.49 (2) |
V (Å3) | 3950.1 (13) |
Z | 4 |
Radiation type | Ag Kα, λ = 0.56083 Å |
µ (mm−1) | 1.15 |
Crystal size (mm) | 0.35 × 0.35 × 0.10 |
Data collection | |
Diffractometer | CAD-4 Software (Nonius, 1989) diffractometer |
Absorption correction | ψ scan (WinGX; Farrugia, 1999; North et al., 1968) |
Tmin, Tmax | 0.819, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8838, 8572, 5353 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.105, 0.99 |
No. of reflections | 8572 |
No. of parameters | 430 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.10, −0.56 |
Computer programs: CAD-4 Software (Nonius, 1989), CAD-4 Software, XCAD4 (Harms, 1996), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1991), SHELXL97, PARST95 (Nardelli, 1995).
The transformation of bis(trimethylstannyl)ethyne into a stannyl-substituted dicobaltatetrahedrane by treating it with dicobalt octacarbonyl `protects' the carbon–carbon triple bond and thus, as expected, also stabilizes the bond between tin and the tetrahedrane moiety. Nevertheless, Stille-type palladium-catalysed carbon–carbon coupling reactions are still possible using activated organyl halides (Zavgorodnii et al., 2000). However, unactivated organyl halides require more rigorous reaction conditions, under which the dicobaltatetrahedrane decomposes.
The title compound (I) was thus prepared by displacing two molecules of carbon monoxide in hexacarbonyldicobalt[µ,η2-bis-(trimethylstannyl)]acetylene (Seyferth & White, 1971; Zachwieja et al., 2001) with bis(diphenylphosphino)methane, a procedure, which, according to literature precedent (Iwasawa & Hiroishi, 1999), should increase the thermal stability of the dicobaltatetrahedrane.
This prediction was correct, the decomposition temperature being increased by 80 K. The differences between the structures of the title compound (Fig. 1) and its carbonyl precursor are subtle: the carbon–carbon bond in the dicobaltatetrahedrane moiety increased in length from 1.309 (5) to 1.335 (5) Å, while the cobalt–cobalt bond contracted slightly from 2.5043 (9) to 2.4972 (8) Å. The cobalt–carbon bonds in the tetrahedrane moiety decreased in length quite considerably, lying between 1.968 (4) and 1.990 (4) Å compared with 2.000 to 2.007 Å in the starting material.
These bond length changes also affect the bond angles in the dicobaltatetrahedrane moiety, particularly at the C(7) atom, where the Sn(1)—C(7)—C(8) angle decreases from 144.7 to 130.3 (3)°, while the Sn(2)—C(8)—C(7) angle remains almost unchanged at 145.3 (3) °. At the same time the angle Sn(1)—C(7)—Co(2) increases from 132.3° to 137.8 (2)°, while Sn(2)—C(8)—Co(1) somewhat decreases from 133.3° to 131.2 (2)°. This asymmetry in bond angles between C(7) and C(8) is reflected in the slightly asymmetric position of the diphosphinomethane moiety, the Co—P bond lengths being 2.2208 (12) and 2.2100 (12) Å respectively.
It is also noteworthy that the bonds between the cobalt atoms and the carbonyl carbons in the title compound are considerably shortened as compared to the analogous bonds in the starting carbonyl complex (the corresonding average values are 1.770 Å and 1.798 Å).