Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003439/cv6003sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003439/cv6003Isup2.hkl |
CCDC reference: 159869
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.063
- wR factor = 0.146
- Data-to-parameter ratio = 14.8
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_420 Alert C D-H Without Acceptor Si(2) - H(1) ?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound, (I), was prepared using the stereoselective hydrosilylation of triphenylsilylacetylene with diphenylsilane catalyzed by rhodium metal in the presence of carbon monoxide at atmospheric pressure. The details of the synthesis will be reported elsewhere. Colorless crystals (I) (m.p. 413.2 K) were obtained by slow evaporation from a solution in n-hexane–dichloromethane (3:1 v/v) at room temperature.
Three H atoms H1, H19 and H20 bound to the Si2, C19 and C20 atoms were found from a difference Fourier synthesis and refined isotropically, and the other H atoms were located in calculated positions and allowed to ride on their attached C atoms. The highest peak are 0.98 Å from H1 and 1.65 Å from C1, respectively.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. View of (I) with the atom-numbering scheme and displacement ellipsoids at the 35% probability level. |
C32H28Si2 | Z = 2 |
Mr = 468.72 | F(000) = 496 |
Triclinic, P1 | Dx = 1.147 Mg m−3 |
a = 11.1046 (12) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 11.4205 (11) Å | Cell parameters from 25 reflections |
c = 12.7004 (9) Å | θ = 10.0–14.3° |
α = 72.632 (7)° | µ = 0.15 mm−1 |
β = 78.905 (7)° | T = 293 K |
γ = 62.198 (11)° | Plate, colorless |
V = 1357.1 (2) Å3 | 0.40 × 0.26 × 0.13 mm |
Enraf-Nonius CAD-4 diffractometer | 2575 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 25.0°, θmin = 2.1° |
non–profiled ω/2θ scans | h = −12→13 |
Absorption correction: ψ scan (North et al., 1968) | k = −12→13 |
Tmin = 0.944, Tmax = 0.981 | l = 0→15 |
4973 measured reflections | 3 standard reflections every 300 min |
4739 independent reflections | intensity decay: 1% |
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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0497P)2 + 0.2159P] where P = (Fo2 + 2Fc2)/3 |
4739 reflections | (Δ/σ)max < 0.001 |
321 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C32H28Si2 | γ = 62.198 (11)° |
Mr = 468.72 | V = 1357.1 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.1046 (12) Å | Mo Kα radiation |
b = 11.4205 (11) Å | µ = 0.15 mm−1 |
c = 12.7004 (9) Å | T = 293 K |
α = 72.632 (7)° | 0.40 × 0.26 × 0.13 mm |
β = 78.905 (7)° |
Enraf-Nonius CAD-4 diffractometer | 2575 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.024 |
Tmin = 0.944, Tmax = 0.981 | 3 standard reflections every 300 min |
4973 measured reflections | intensity decay: 1% |
4739 independent reflections |
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.23 e Å−3 |
4739 reflections | Δρmin = −0.18 e Å−3 |
321 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 | ||
Si1 | 0.34449 (10) | 0.32786 (10) | 0.55899 (8) | 0.0513 (3) | |
Si2 | 0.34458 (12) | 0.46792 (12) | 0.17876 (8) | 0.0666 (4) | |
H1 | 0.424 (3) | 0.530 (3) | 0.169 (2) | 0.048 (8)* | |
C1 | 0.5137 (3) | 0.2244 (3) | 0.6203 (3) | 0.0495 (8) | |
C2 | 0.6126 (4) | 0.2719 (4) | 0.5972 (3) | 0.0689 (11) | |
H2 | 0.5945 | 0.3565 | 0.5485 | 0.083* | |
C3 | 0.7365 (4) | 0.1984 (5) | 0.6438 (4) | 0.0867 (14) | |
H3 | 0.8001 | 0.2338 | 0.6274 | 0.104* | |
C4 | 0.7661 (4) | 0.0731 (5) | 0.7144 (4) | 0.0809 (12) | |
H4 | 0.8495 | 0.0235 | 0.7467 | 0.097* | |
C5 | 0.6733 (4) | 0.0208 (4) | 0.7375 (3) | 0.0745 (11) | |
H5 | 0.6940 | −0.0652 | 0.7844 | 0.089* | |
C6 | 0.5485 (4) | 0.0954 (4) | 0.6912 (3) | 0.0592 (10) | |
H6 | 0.4860 | 0.0587 | 0.7077 | 0.071* | |
C7 | 0.2424 (3) | 0.4776 (3) | 0.6223 (3) | 0.0501 (9) | |
C8 | 0.2855 (4) | 0.4962 (4) | 0.7088 (3) | 0.0683 (11) | |
H8 | 0.3701 | 0.4341 | 0.7362 | 0.082* | |
C9 | 0.2038 (5) | 0.6067 (4) | 0.7549 (4) | 0.0915 (14) | |
H9 | 0.2338 | 0.6167 | 0.8138 | 0.110* | |
C10 | 0.0804 (5) | 0.7005 (4) | 0.7152 (4) | 0.0914 (14) | |
H10 | 0.0264 | 0.7741 | 0.7468 | 0.110* | |
C11 | 0.0366 (4) | 0.6858 (4) | 0.6290 (4) | 0.0853 (13) | |
H11 | −0.0477 | 0.7495 | 0.6016 | 0.102* | |
C12 | 0.1167 (4) | 0.5768 (4) | 0.5822 (3) | 0.0716 (11) | |
H12 | 0.0863 | 0.5693 | 0.5223 | 0.086* | |
C13 | 0.2532 (3) | 0.2185 (3) | 0.5873 (3) | 0.0481 (8) | |
C14 | 0.1422 (3) | 0.2334 (4) | 0.6644 (3) | 0.0574 (9) | |
H14 | 0.1072 | 0.3051 | 0.6990 | 0.069* | |
C15 | 0.0833 (4) | 0.1449 (4) | 0.6908 (3) | 0.0695 (11) | |
H15 | 0.0096 | 0.1568 | 0.7427 | 0.083* | |
C16 | 0.1333 (4) | 0.0394 (4) | 0.6405 (4) | 0.0750 (12) | |
H16 | 0.0936 | −0.0205 | 0.6583 | 0.090* | |
C17 | 0.2423 (4) | 0.0215 (4) | 0.5635 (3) | 0.0717 (11) | |
H17 | 0.2767 | −0.0505 | 0.5294 | 0.086* | |
C18 | 0.2994 (3) | 0.1108 (4) | 0.5378 (3) | 0.0605 (10) | |
H18 | 0.3722 | 0.0987 | 0.4849 | 0.073* | |
C19 | 0.3716 (5) | 0.3919 (4) | 0.4085 (3) | 0.0660 (11) | |
H19 | 0.435 (4) | 0.420 (4) | 0.379 (3) | 0.109 (17)* | |
C20 | 0.3069 (5) | 0.4040 (4) | 0.3286 (3) | 0.0728 (12) | |
H20 | 0.238 (4) | 0.370 (4) | 0.349 (3) | 0.102 (15)* | |
C21 | 0.1857 (4) | 0.5924 (4) | 0.1083 (3) | 0.0661 (11) | |
C22 | 0.0754 (5) | 0.5628 (5) | 0.1157 (4) | 0.0861 (13) | |
H22 | 0.0801 | 0.4790 | 0.1580 | 0.103* | |
C23 | −0.0397 (6) | 0.6562 (8) | 0.0614 (5) | 0.121 (2) | |
H23 | −0.1124 | 0.6351 | 0.0667 | 0.145* | |
C24 | −0.0486 (7) | 0.7795 (8) | −0.0003 (6) | 0.144 (3) | |
H24 | −0.1277 | 0.8429 | −0.0360 | 0.173* | |
C25 | 0.0576 (8) | 0.8102 (6) | −0.0096 (5) | 0.136 (3) | |
H25 | 0.0521 | 0.8938 | −0.0534 | 0.163* | |
C26 | 0.1732 (6) | 0.7190 (5) | 0.0449 (4) | 0.0930 (14) | |
H26 | 0.2443 | 0.7425 | 0.0393 | 0.112* | |
C27 | 0.4393 (4) | 0.3197 (4) | 0.1137 (3) | 0.0611 (10) | |
C28 | 0.4030 (4) | 0.3177 (4) | 0.0162 (3) | 0.0736 (11) | |
H28 | 0.3285 | 0.3924 | −0.0185 | 0.088* | |
C29 | 0.4750 (5) | 0.2072 (5) | −0.0307 (4) | 0.0927 (14) | |
H29 | 0.4485 | 0.2082 | −0.0962 | 0.111* | |
C30 | 0.5847 (5) | 0.0969 (5) | 0.0189 (4) | 0.0898 (14) | |
H30 | 0.6332 | 0.0228 | −0.0129 | 0.108* | |
C31 | 0.6233 (4) | 0.0952 (5) | 0.1147 (4) | 0.0866 (14) | |
H31 | 0.6983 | 0.0200 | 0.1484 | 0.104* | |
C32 | 0.5513 (4) | 0.2048 (5) | 0.1619 (3) | 0.0805 (12) | |
H32 | 0.5783 | 0.2019 | 0.2279 | 0.097* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Si1 | 0.0526 (6) | 0.0554 (6) | 0.0465 (6) | −0.0226 (5) | −0.0048 (5) | −0.0136 (5) |
Si2 | 0.0840 (8) | 0.0771 (8) | 0.0468 (6) | −0.0442 (7) | −0.0050 (6) | −0.0104 (6) |
C1 | 0.046 (2) | 0.051 (2) | 0.054 (2) | −0.0201 (18) | 0.0009 (17) | −0.0212 (18) |
C2 | 0.059 (3) | 0.054 (2) | 0.091 (3) | −0.025 (2) | −0.014 (2) | −0.007 (2) |
C3 | 0.055 (3) | 0.079 (3) | 0.128 (4) | −0.033 (2) | −0.021 (3) | −0.013 (3) |
C4 | 0.049 (2) | 0.083 (3) | 0.101 (3) | −0.016 (2) | −0.022 (2) | −0.019 (3) |
C5 | 0.064 (3) | 0.067 (3) | 0.077 (3) | −0.019 (2) | −0.017 (2) | −0.005 (2) |
C6 | 0.057 (2) | 0.065 (3) | 0.059 (2) | −0.032 (2) | 0.0011 (19) | −0.014 (2) |
C7 | 0.058 (2) | 0.044 (2) | 0.044 (2) | −0.0206 (18) | −0.0060 (17) | −0.0064 (16) |
C8 | 0.074 (3) | 0.057 (2) | 0.067 (3) | −0.015 (2) | −0.020 (2) | −0.017 (2) |
C9 | 0.120 (4) | 0.070 (3) | 0.083 (3) | −0.026 (3) | −0.016 (3) | −0.037 (3) |
C10 | 0.098 (4) | 0.044 (3) | 0.104 (4) | −0.007 (3) | 0.001 (3) | −0.024 (3) |
C11 | 0.064 (3) | 0.058 (3) | 0.100 (4) | −0.004 (2) | −0.009 (3) | −0.009 (3) |
C12 | 0.071 (3) | 0.065 (3) | 0.068 (3) | −0.019 (2) | −0.017 (2) | −0.011 (2) |
C13 | 0.044 (2) | 0.050 (2) | 0.046 (2) | −0.0142 (17) | −0.0080 (16) | −0.0138 (17) |
C14 | 0.053 (2) | 0.061 (2) | 0.059 (2) | −0.021 (2) | −0.0054 (19) | −0.0210 (19) |
C15 | 0.054 (2) | 0.083 (3) | 0.076 (3) | −0.034 (2) | 0.004 (2) | −0.023 (2) |
C16 | 0.076 (3) | 0.073 (3) | 0.093 (3) | −0.047 (3) | −0.011 (3) | −0.016 (3) |
C17 | 0.070 (3) | 0.064 (3) | 0.087 (3) | −0.025 (2) | −0.009 (2) | −0.032 (2) |
C18 | 0.047 (2) | 0.061 (2) | 0.070 (3) | −0.019 (2) | 0.0002 (19) | −0.021 (2) |
C19 | 0.075 (3) | 0.074 (3) | 0.056 (3) | −0.037 (3) | −0.006 (2) | −0.016 (2) |
C20 | 0.079 (3) | 0.091 (3) | 0.055 (3) | −0.044 (3) | −0.001 (2) | −0.017 (2) |
C21 | 0.086 (3) | 0.064 (3) | 0.044 (2) | −0.030 (2) | 0.006 (2) | −0.017 (2) |
C22 | 0.082 (3) | 0.094 (3) | 0.075 (3) | −0.036 (3) | −0.002 (3) | −0.017 (3) |
C23 | 0.080 (4) | 0.165 (6) | 0.097 (4) | −0.024 (4) | −0.002 (3) | −0.054 (4) |
C24 | 0.108 (5) | 0.139 (7) | 0.091 (5) | 0.039 (5) | −0.020 (5) | −0.045 (5) |
C25 | 0.181 (7) | 0.070 (4) | 0.089 (4) | −0.001 (5) | −0.016 (5) | −0.014 (3) |
C26 | 0.132 (4) | 0.070 (3) | 0.070 (3) | −0.040 (3) | −0.006 (3) | −0.013 (3) |
C27 | 0.066 (3) | 0.069 (3) | 0.043 (2) | −0.034 (2) | −0.0005 (19) | −0.0018 (19) |
C28 | 0.080 (3) | 0.067 (3) | 0.061 (3) | −0.020 (2) | −0.015 (2) | −0.011 (2) |
C29 | 0.113 (4) | 0.076 (3) | 0.077 (3) | −0.021 (3) | −0.017 (3) | −0.028 (3) |
C30 | 0.087 (4) | 0.065 (3) | 0.097 (4) | −0.021 (3) | 0.006 (3) | −0.020 (3) |
C31 | 0.065 (3) | 0.075 (3) | 0.088 (4) | −0.017 (3) | −0.011 (3) | 0.005 (3) |
C32 | 0.077 (3) | 0.089 (3) | 0.064 (3) | −0.033 (3) | −0.017 (2) | −0.001 (3) |
Si1—C19 | 1.852 (4) | C14—H14 | 0.9300 |
Si1—C1 | 1.864 (3) | C15—C16 | 1.365 (5) |
Si1—C13 | 1.868 (3) | C15—H15 | 0.9300 |
Si1—C7 | 1.875 (3) | C16—C17 | 1.376 (5) |
Si2—C21 | 1.855 (4) | C16—H16 | 0.9300 |
Si2—C20 | 1.865 (4) | C17—C18 | 1.370 (5) |
Si2—C27 | 1.869 (4) | C17—H17 | 0.9300 |
Si2—H1 | 1.35 (3) | C18—H18 | 0.9300 |
C1—C2 | 1.388 (4) | C19—C20 | 1.292 (5) |
C1—C6 | 1.393 (4) | C19—H19 | 0.89 (4) |
C2—C3 | 1.374 (5) | C20—H20 | 0.97 (4) |
C2—H2 | 0.9300 | C21—C26 | 1.386 (5) |
C3—C4 | 1.367 (5) | C21—C22 | 1.395 (5) |
C3—H3 | 0.9300 | C22—C23 | 1.370 (6) |
C4—C5 | 1.364 (5) | C22—H22 | 0.9300 |
C4—H4 | 0.9300 | C23—C24 | 1.359 (8) |
C5—C6 | 1.380 (5) | C23—H23 | 0.9300 |
C5—H5 | 0.9300 | C24—C25 | 1.355 (8) |
C6—H6 | 0.9300 | C24—H24 | 0.9300 |
C7—C8 | 1.384 (4) | C25—C26 | 1.370 (7) |
C7—C12 | 1.395 (5) | C25—H25 | 0.9300 |
C8—C9 | 1.388 (5) | C26—H26 | 0.9300 |
C8—H8 | 0.9300 | C27—C28 | 1.383 (5) |
C9—C10 | 1.361 (6) | C27—C32 | 1.391 (5) |
C9—H9 | 0.9300 | C28—C29 | 1.382 (5) |
C10—C11 | 1.362 (6) | C28—H28 | 0.9300 |
C10—H10 | 0.9300 | C29—C30 | 1.363 (6) |
C11—C12 | 1.378 (5) | C29—H29 | 0.9300 |
C11—H11 | 0.9300 | C30—C31 | 1.358 (6) |
C12—H12 | 0.9300 | C30—H30 | 0.9300 |
C13—C18 | 1.386 (4) | C31—C32 | 1.377 (6) |
C13—C14 | 1.395 (4) | C31—H31 | 0.9300 |
C14—C15 | 1.376 (4) | C32—H32 | 0.9300 |
C19—Si1—C1 | 108.84 (18) | C16—C15—C14 | 119.8 (4) |
C19—Si1—C13 | 111.04 (18) | C16—C15—H15 | 120.1 |
C1—Si1—C13 | 108.81 (15) | C14—C15—H15 | 120.1 |
C19—Si1—C7 | 108.66 (16) | C15—C16—C17 | 120.3 (4) |
C1—Si1—C7 | 109.48 (15) | C15—C16—H16 | 119.9 |
C13—Si1—C7 | 109.98 (15) | C17—C16—H16 | 119.9 |
C21—Si2—C20 | 111.20 (19) | C18—C17—C16 | 119.2 (4) |
C21—Si2—C27 | 110.76 (17) | C18—C17—H17 | 120.4 |
C20—Si2—C27 | 109.02 (18) | C16—C17—H17 | 120.4 |
C21—Si2—H1 | 108.6 (11) | C17—C18—C13 | 122.6 (3) |
C20—Si2—H1 | 108.4 (11) | C17—C18—H18 | 118.7 |
C27—Si2—H1 | 108.8 (11) | C13—C18—H18 | 118.7 |
C2—C1—C6 | 116.2 (3) | C20—C19—Si1 | 129.0 (4) |
C2—C1—Si1 | 121.5 (3) | C20—C19—H19 | 107 (3) |
C6—C1—Si1 | 122.3 (3) | Si1—C19—H19 | 124 (3) |
C3—C2—C1 | 122.2 (4) | C19—C20—Si2 | 125.4 (4) |
C3—C2—H2 | 118.9 | C19—C20—H20 | 116 (2) |
C1—C2—H2 | 118.9 | Si2—C20—H20 | 118 (2) |
C4—C3—C2 | 119.9 (4) | C26—C21—C22 | 117.4 (4) |
C4—C3—H3 | 120.1 | C26—C21—Si2 | 120.6 (4) |
C2—C3—H3 | 120.1 | C22—C21—Si2 | 122.0 (3) |
C5—C4—C3 | 120.0 (4) | C23—C22—C21 | 120.6 (5) |
C5—C4—H4 | 120.0 | C23—C22—H22 | 119.7 |
C3—C4—H4 | 120.0 | C21—C22—H22 | 119.7 |
C4—C5—C6 | 120.0 (4) | C24—C23—C22 | 120.5 (6) |
C4—C5—H5 | 120.0 | C24—C23—H23 | 119.7 |
C6—C5—H5 | 120.0 | C22—C23—H23 | 119.7 |
C5—C6—C1 | 121.8 (3) | C25—C24—C23 | 120.0 (7) |
C5—C6—H6 | 119.1 | C25—C24—H24 | 120.0 |
C1—C6—H6 | 119.1 | C23—C24—H24 | 120.0 |
C8—C7—C12 | 116.9 (3) | C24—C25—C26 | 120.5 (7) |
C8—C7—Si1 | 123.2 (3) | C24—C25—H25 | 119.8 |
C12—C7—Si1 | 119.9 (3) | C26—C25—H25 | 119.8 |
C7—C8—C9 | 120.8 (4) | C25—C26—C21 | 121.0 (5) |
C7—C8—H8 | 119.6 | C25—C26—H26 | 119.5 |
C9—C8—H8 | 119.6 | C21—C26—H26 | 119.5 |
C10—C9—C8 | 120.9 (4) | C28—C27—C32 | 116.5 (4) |
C10—C9—H9 | 119.6 | C28—C27—Si2 | 122.5 (3) |
C8—C9—H9 | 119.6 | C32—C27—Si2 | 121.0 (3) |
C9—C10—C11 | 119.5 (4) | C29—C28—C27 | 121.5 (4) |
C9—C10—H10 | 120.2 | C29—C28—H28 | 119.2 |
C11—C10—H10 | 120.2 | C27—C28—H28 | 119.2 |
C10—C11—C12 | 120.2 (4) | C30—C29—C28 | 120.1 (4) |
C10—C11—H11 | 119.9 | C30—C29—H29 | 119.9 |
C12—C11—H11 | 119.9 | C28—C29—H29 | 119.9 |
C11—C12—C7 | 121.6 (4) | C31—C30—C29 | 120.0 (4) |
C11—C12—H12 | 119.2 | C31—C30—H30 | 120.0 |
C7—C12—H12 | 119.2 | C29—C30—H30 | 120.0 |
C18—C13—C14 | 116.3 (3) | C30—C31—C32 | 119.9 (4) |
C18—C13—Si1 | 121.0 (3) | C30—C31—H31 | 120.0 |
C14—C13—Si1 | 122.6 (3) | C32—C31—H31 | 120.0 |
C15—C14—C13 | 121.7 (3) | C31—C32—C27 | 121.9 (4) |
C15—C14—H14 | 119.1 | C31—C32—H32 | 119.1 |
C13—C14—H14 | 119.1 | C27—C32—H32 | 119.1 |
C19—Si1—C1—C2 | 48.3 (3) | C13—C14—C15—C16 | −0.3 (5) |
C13—Si1—C1—C2 | 169.5 (3) | C14—C15—C16—C17 | 0.0 (6) |
C7—Si1—C1—C2 | −70.3 (3) | C15—C16—C17—C18 | −0.3 (6) |
C19—Si1—C1—C6 | −131.4 (3) | C16—C17—C18—C13 | 0.9 (6) |
C13—Si1—C1—C6 | −10.3 (3) | C14—C13—C18—C17 | −1.2 (5) |
C7—Si1—C1—C6 | 110.0 (3) | Si1—C13—C18—C17 | 174.3 (3) |
C6—C1—C2—C3 | −1.9 (6) | C1—Si1—C19—C20 | 141.2 (4) |
Si1—C1—C2—C3 | 178.4 (3) | C13—Si1—C19—C20 | 21.5 (5) |
C1—C2—C3—C4 | 0.9 (7) | C7—Si1—C19—C20 | −99.6 (4) |
C2—C3—C4—C5 | 0.7 (7) | Si1—C19—C20—Si2 | −179.1 (2) |
C3—C4—C5—C6 | −1.2 (6) | C21—Si2—C20—C19 | −134.7 (4) |
C4—C5—C6—C1 | 0.1 (6) | C27—Si2—C20—C19 | 102.9 (4) |
C2—C1—C6—C5 | 1.4 (5) | C20—Si2—C21—C26 | 128.0 (3) |
Si1—C1—C6—C5 | −178.9 (3) | C27—Si2—C21—C26 | −110.6 (3) |
C19—Si1—C7—C8 | −124.5 (3) | C20—Si2—C21—C22 | −52.5 (4) |
C1—Si1—C7—C8 | −5.7 (3) | C27—Si2—C21—C22 | 68.9 (3) |
C13—Si1—C7—C8 | 113.8 (3) | C26—C21—C22—C23 | 0.4 (6) |
C19—Si1—C7—C12 | 55.4 (3) | Si2—C21—C22—C23 | −179.1 (3) |
C1—Si1—C7—C12 | 174.1 (3) | C21—C22—C23—C24 | −0.4 (8) |
C13—Si1—C7—C12 | −66.4 (3) | C22—C23—C24—C25 | 1.0 (10) |
C12—C7—C8—C9 | 2.2 (5) | C23—C24—C25—C26 | −1.6 (10) |
Si1—C7—C8—C9 | −177.9 (3) | C24—C25—C26—C21 | 1.8 (9) |
C7—C8—C9—C10 | −1.1 (7) | C22—C21—C26—C25 | −1.1 (6) |
C8—C9—C10—C11 | 0.0 (7) | Si2—C21—C26—C25 | 178.4 (4) |
C9—C10—C11—C12 | −0.1 (7) | C21—Si2—C27—C28 | 9.0 (4) |
C10—C11—C12—C7 | 1.4 (6) | C20—Si2—C27—C28 | 131.7 (3) |
C8—C7—C12—C11 | −2.4 (5) | C21—Si2—C27—C32 | −171.0 (3) |
Si1—C7—C12—C11 | 177.7 (3) | C20—Si2—C27—C32 | −48.3 (4) |
C19—Si1—C13—C18 | 51.7 (3) | C32—C27—C28—C29 | −0.3 (6) |
C1—Si1—C13—C18 | −68.1 (3) | Si2—C27—C28—C29 | 179.7 (3) |
C7—Si1—C13—C18 | 172.0 (3) | C27—C28—C29—C30 | −0.1 (7) |
C19—Si1—C13—C14 | −133.1 (3) | C28—C29—C30—C31 | 0.2 (7) |
C1—Si1—C13—C14 | 107.1 (3) | C29—C30—C31—C32 | 0.2 (7) |
C7—Si1—C13—C14 | −12.8 (3) | C30—C31—C32—C27 | −0.6 (7) |
C18—C13—C14—C15 | 0.8 (5) | C28—C27—C32—C31 | 0.6 (6) |
Si1—C13—C14—C15 | −174.6 (3) | Si2—C27—C32—C31 | −179.3 (3) |
Experimental details
Crystal data | |
Chemical formula | C32H28Si2 |
Mr | 468.72 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 11.1046 (12), 11.4205 (11), 12.7004 (9) |
α, β, γ (°) | 72.632 (7), 78.905 (7), 62.198 (11) |
V (Å3) | 1357.1 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.15 |
Crystal size (mm) | 0.40 × 0.26 × 0.13 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.944, 0.981 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4973, 4739, 2575 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.146, 1.02 |
No. of reflections | 4739 |
No. of parameters | 321 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.18 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
Si1—C19 | 1.852 (4) | Si2—C20 | 1.865 (4) |
Si1—C1 | 1.864 (3) | Si2—C27 | 1.869 (4) |
Si1—C13 | 1.868 (3) | Si2—H1 | 1.35 (3) |
Si1—C7 | 1.875 (3) | C19—C20 | 1.292 (5) |
Si2—C21 | 1.855 (4) | ||
C19—Si1—C1 | 108.84 (18) | C21—Si2—C20 | 111.20 (19) |
C19—Si1—C13 | 111.04 (18) | C21—Si2—C27 | 110.76 (17) |
C1—Si1—C13 | 108.81 (15) | C20—Si2—C27 | 109.02 (18) |
C19—Si1—C7 | 108.66 (16) | C21—Si2—H1 | 108.6 (11) |
C1—Si1—C7 | 109.48 (15) | C20—Si2—H1 | 108.4 (11) |
C13—Si1—C7 | 109.98 (15) | C27—Si2—H1 | 108.8 (11) |
Transition metal-catalyzed hydrosilylation of alkynes provides the most straightforward method for the preparation of vinylsilanes. In the course of our studies (Lee & Han, 1998; Lee et al., 1996), we recently synthesized various (E)-vinylsilanes via stereoselective hydrosilylation using an Rh/CO catalytic system. These vinylsilanes have synthetic value because they are very versatile intermediates in organic synthesis, as well as in organosilicon chemistry. Particularly, the title (E)-vinylsilane, (I), containing an Si—H bond has the possibilities of further transformations. We present here the synthesis and the X-ray structure of (I).
Compound (I) consists of diphenylsilyl- and triphenylsilyl groups interconnected by \ C═C double bond, as shown in Fig. 1.
The Si—C bond lengths range from 1.852 (4) to 1.875 (3) Å, with a mean value of 1.864 (1) Å and the C—Si—C angles range from 108.66 (16) to 111.20 (19)°, with a mean value of 109.75 (6)° (see Table 1). All these values are similiar to those found in platinum-catalyzed hydrosilylation of alkynes (Lewis et al., 1991). The geometries of the five phenyl rings are very similar to one another; the C—C bond lengths average to a value of 1.374 (1) Å and are all planar with a maximum deviation of 0.012 (3) Å from the mean plane. The dihedral angles between neighbouring phenyl rings range from 72.91 (14) to 74.12 (11)°, with an average of 73.58 (6)°. The C19═C20 bond length [1.292 (5) Å] bridging the two silyl groups clearly displays double-bond character, and the similiar bond length 1.294 (7) Å was found in platinum-catalyzed hydrosilylation of alkynes (Lewis et al.,. 1991). The four atoms Si1, C19, C20 and Si2, are planar within 0.007 (2) Å with a torsion angle Si1—C19—C20—Si2 of -179.1 (2)°.
The Si2—H length is 1.35 (3) Å which is somewhat shorter than the value of 1.42 (6) Å in tris[8-(dimethylamino)naphthyl]silane (Breliere et al., 1994), but only 1σ different from it.
The closest intermolecular distance H24···H30(-1 + x,1 + y,z) of 2.52 Å suggests that the molcecular packing is governed only by van der Waals forces.