Acta Cryst. (2008). E64, o2121 [ doi:10.1107/S1600536808032923 ]
In the title compound, C23H28OSi2, the five-membered ring is essentially planar and the phenyl rings are oriented with respect to the mean plane of this ring by 56.01 (3) and 56.68 (4)°.
To lithium (32 mg, 4.61 mmol) was added a diethyl ether (2.5 ml) solution of phenyl(trimethylsilyl)acetylene (408 mg, 2.34 mmol) and the resulting mixture was stirred at room temperature for 4 h. To an ether solution of 1,4-dilithio-1,3-butadiene thus obtained was added diethyl ether (8 ml) and unreacted lithium was removed by filtration. Carbon dioxide was bubbled into the filtrate at room temperature for 1 min. After treatment of the resulting mixture with hydrochloric acid (3 N), the organic layer was extracted with diethyl ether and dried over anhydrous magnesium sulfate. After removal of volatile substances, the residue was subjected to column chromatography (SiO2, hexane:ethyl acetate = 30:1) to afford the title compound, 3,4-diphenyl-2,5-bis(trimethylsilyl)cyclopentadienone (I) (22 mg, 5%). Suitable crystals for X-ray crystallographic analysis were obtained by slow evaporation of a hexane solution of (I).
Hydrogen atoms attached to C(sp3) and C(sp2) carbon atoms were treated as riding with C—H distances of 0.96 and 0.93 Å, respectively, and were included in the final cycles of least squares with isotropic Uijs by using a riding model, while all the other atoms were refined anisotropically.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./pv2107fig1thm.gif)
| Fig. 1. A view of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level. |
| C23H28OSi2 | F(000) = 808 |
| Mr = 376.63 | Dx = 1.132 Mg m−3 |
| Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 5798 reflections |
| a = 9.8418 (6) Å | θ = 2.7–27.9° |
| b = 11.8041 (7) Å | µ = 0.17 mm−1 |
| c = 19.0181 (12) Å | T = 103 K |
| V = 2209.4 (2) Å3 | Cube, orange |
| Z = 4 | 0.50 × 0.40 × 0.40 mm |
| Bruker SMART CCD area-detector diffractometer | 5286 independent reflections |
| Radiation source: fine-focus sealed tube | 5181 reflections with I > 2σ(I) |
| graphite | Rint = 0.021 |
| φ and ω scans | θmax = 27.9°, θmin = 2.0° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→11 |
| Tmin = 0.922, Tmax = 0.935 | k = −15→15 |
| 16200 measured reflections | l = −21→25 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
| wR(F2) = 0.075 | w = 1/[σ2(Fo2) + (0.0473P)2 + 0.2508P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.07 | (Δ/σ)max = 0.001 |
| 5286 reflections | Δρmax = 0.28 e Å−3 |
| 241 parameters | Δρmin = −0.20 e Å−3 |
| 0 restraints | Absolute structure: Flack (1983), with 2292 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: 0.01 (6) |
| C23H28OSi2 | V = 2209.4 (2) Å3 |
| Mr = 376.63 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα radiation |
| a = 9.8418 (6) Å | µ = 0.17 mm−1 |
| b = 11.8041 (7) Å | T = 103 K |
| c = 19.0181 (12) Å | 0.50 × 0.40 × 0.40 mm |
| Bruker SMART CCD area-detector diffractometer | 5286 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5181 reflections with I > 2σ(I) |
| Tmin = 0.922, Tmax = 0.935 | Rint = 0.021 |
| 16200 measured reflections | θmax = 27.9° |
| R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
| wR(F2) = 0.075 | Δρmax = 0.28 e Å−3 |
| S = 1.07 | Δρmin = −0.20 e Å−3 |
| 5286 reflections | Absolute structure: Flack (1983), with 2292 Friedel pairs |
| 241 parameters | Flack parameter: 0.01 (6) |
| 0 restraints |
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. The Flack parameter was not changed after least-square refinement without merging the reflections. When the refinement was carried out using the opposite absolute structure, the Flack parameter was 0.99 (7). |
| x | y | z | Uiso*/Ueq | ||
| Si1 | 0.18748 (3) | 1.12044 (3) | 0.976841 (17) | 0.01882 (8) | |
| Si2 | 0.42760 (3) | 0.77489 (3) | 0.787011 (18) | 0.02008 (8) | |
| O1 | 0.42093 (9) | 1.01676 (8) | 0.87657 (5) | 0.0272 (2) | |
| C2 | 0.18860 (12) | 0.99471 (10) | 0.91621 (6) | 0.0180 (2) | |
| C15 | 0.08537 (12) | 0.72378 (10) | 0.82868 (6) | 0.0190 (2) | |
| C7 | 0.03840 (14) | 1.11986 (13) | 1.03721 (7) | 0.0289 (3) | |
| H7A | 0.0361 | 1.0497 | 1.0627 | 0.043* | |
| H7B | −0.0436 | 1.1278 | 1.0103 | 0.043* | |
| H7C | 0.0459 | 1.1818 | 1.0697 | 0.043* | |
| C3 | 0.09673 (12) | 0.91490 (9) | 0.89917 (6) | 0.0176 (2) | |
| C6 | 0.18912 (15) | 1.25143 (10) | 0.92156 (7) | 0.0267 (3) | |
| H6A | 0.1116 | 1.2513 | 0.8909 | 0.040* | |
| H6B | 0.2708 | 1.2533 | 0.8940 | 0.040* | |
| H6C | 0.1858 | 1.3170 | 0.9514 | 0.040* | |
| C16 | −0.03609 (13) | 0.73727 (11) | 0.79091 (7) | 0.0229 (2) | |
| H16 | −0.0694 | 0.8096 | 0.7819 | 0.028* | |
| C12 | −0.31728 (13) | 0.90660 (12) | 0.96478 (7) | 0.0263 (3) | |
| H12 | −0.4070 | 0.9059 | 0.9802 | 0.032* | |
| C9 | −0.04729 (11) | 0.91027 (10) | 0.92063 (6) | 0.0181 (2) | |
| C10 | −0.13363 (12) | 1.00076 (11) | 0.90568 (6) | 0.0209 (2) | |
| H10 | −0.1009 | 1.0628 | 0.8807 | 0.025* | |
| C14 | −0.09904 (13) | 0.81670 (11) | 0.95650 (6) | 0.0227 (2) | |
| H14 | −0.0432 | 0.7548 | 0.9654 | 0.027* | |
| C4 | 0.16243 (12) | 0.82381 (10) | 0.85340 (6) | 0.0181 (2) | |
| C18 | −0.06037 (15) | 0.53448 (11) | 0.78188 (7) | 0.0290 (3) | |
| H18 | −0.1087 | 0.4716 | 0.7662 | 0.035* | |
| C8 | 0.34391 (14) | 1.11229 (13) | 1.03210 (7) | 0.0318 (3) | |
| H8A | 0.3455 | 1.1748 | 1.0644 | 0.048* | |
| H8B | 0.4227 | 1.1154 | 1.0024 | 0.048* | |
| H8C | 0.3440 | 1.0424 | 1.0580 | 0.048* | |
| C1 | 0.31734 (12) | 0.96101 (10) | 0.87823 (6) | 0.0191 (2) | |
| C20 | 0.13106 (14) | 0.61403 (11) | 0.84330 (7) | 0.0228 (2) | |
| H20 | 0.2109 | 0.6037 | 0.8686 | 0.027* | |
| C22 | 0.55418 (15) | 0.87927 (12) | 0.75313 (8) | 0.0333 (3) | |
| H22A | 0.6181 | 0.8412 | 0.7232 | 0.050* | |
| H22B | 0.6015 | 0.9131 | 0.7919 | 0.050* | |
| H22C | 0.5081 | 0.9371 | 0.7269 | 0.050* | |
| C13 | −0.23314 (13) | 0.81532 (12) | 0.97897 (7) | 0.0271 (3) | |
| H13 | −0.2665 | 0.7532 | 1.0035 | 0.033* | |
| C11 | −0.26813 (13) | 0.99900 (12) | 0.92774 (7) | 0.0241 (3) | |
| H11 | −0.3251 | 1.0597 | 0.9177 | 0.029* | |
| C5 | 0.29427 (12) | 0.84939 (10) | 0.84058 (6) | 0.0185 (2) | |
| C23 | 0.34694 (14) | 0.70279 (12) | 0.71046 (7) | 0.0292 (3) | |
| H23A | 0.4161 | 0.6693 | 0.6816 | 0.044* | |
| H23B | 0.2967 | 0.7571 | 0.6834 | 0.044* | |
| H23C | 0.2865 | 0.6448 | 0.7270 | 0.044* | |
| C19 | 0.05826 (15) | 0.52031 (11) | 0.82031 (7) | 0.0284 (3) | |
| H19 | 0.0891 | 0.4478 | 0.8307 | 0.034* | |
| C17 | −0.10663 (13) | 0.64309 (12) | 0.76695 (7) | 0.0275 (3) | |
| H17 | −0.1855 | 0.6527 | 0.7407 | 0.033* | |
| C21 | 0.51771 (14) | 0.67089 (12) | 0.84432 (8) | 0.0287 (3) | |
| H21A | 0.4534 | 0.6176 | 0.8630 | 0.043* | |
| H21B | 0.5612 | 0.7102 | 0.8823 | 0.043* | |
| H21C | 0.5849 | 0.6313 | 0.8172 | 0.043* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Si1 | 0.01810 (15) | 0.01801 (15) | 0.02036 (15) | −0.00020 (12) | −0.00082 (12) | −0.00287 (12) |
| Si2 | 0.02101 (15) | 0.01866 (15) | 0.02057 (15) | 0.00210 (12) | 0.00300 (12) | −0.00136 (12) |
| O1 | 0.0186 (4) | 0.0265 (4) | 0.0366 (5) | −0.0041 (4) | 0.0035 (4) | −0.0071 (4) |
| C2 | 0.0175 (5) | 0.0178 (5) | 0.0188 (5) | 0.0023 (4) | −0.0003 (4) | −0.0005 (4) |
| C15 | 0.0209 (5) | 0.0197 (5) | 0.0164 (5) | −0.0020 (5) | 0.0017 (4) | −0.0011 (4) |
| C7 | 0.0289 (6) | 0.0320 (7) | 0.0257 (6) | −0.0020 (6) | 0.0058 (5) | −0.0061 (5) |
| C3 | 0.0185 (5) | 0.0167 (5) | 0.0175 (5) | 0.0021 (4) | −0.0003 (4) | 0.0020 (4) |
| C6 | 0.0322 (6) | 0.0188 (6) | 0.0291 (6) | −0.0009 (5) | 0.0004 (5) | −0.0004 (4) |
| C16 | 0.0236 (6) | 0.0232 (6) | 0.0220 (5) | −0.0004 (5) | −0.0011 (5) | −0.0002 (5) |
| C12 | 0.0178 (5) | 0.0358 (7) | 0.0253 (6) | −0.0019 (5) | 0.0025 (5) | 0.0021 (5) |
| C9 | 0.0171 (5) | 0.0196 (5) | 0.0175 (5) | −0.0005 (4) | −0.0025 (4) | −0.0023 (4) |
| C10 | 0.0200 (5) | 0.0204 (5) | 0.0224 (5) | −0.0003 (5) | −0.0006 (4) | 0.0025 (4) |
| C14 | 0.0232 (6) | 0.0230 (6) | 0.0219 (6) | 0.0017 (5) | 0.0000 (5) | 0.0042 (4) |
| C4 | 0.0216 (6) | 0.0166 (5) | 0.0162 (5) | 0.0022 (4) | −0.0010 (4) | 0.0015 (4) |
| C18 | 0.0361 (7) | 0.0251 (6) | 0.0256 (6) | −0.0110 (5) | 0.0011 (6) | −0.0062 (5) |
| C8 | 0.0267 (6) | 0.0374 (7) | 0.0315 (7) | 0.0009 (6) | −0.0092 (5) | −0.0060 (6) |
| C1 | 0.0180 (5) | 0.0190 (5) | 0.0202 (5) | 0.0028 (4) | −0.0005 (4) | 0.0008 (4) |
| C20 | 0.0265 (6) | 0.0207 (6) | 0.0211 (5) | −0.0003 (5) | −0.0004 (5) | −0.0003 (5) |
| C22 | 0.0341 (7) | 0.0291 (6) | 0.0367 (7) | −0.0043 (6) | 0.0147 (6) | −0.0016 (6) |
| C13 | 0.0251 (6) | 0.0316 (7) | 0.0246 (6) | −0.0039 (5) | 0.0021 (5) | 0.0075 (5) |
| C11 | 0.0194 (6) | 0.0264 (6) | 0.0264 (6) | 0.0035 (5) | −0.0020 (5) | 0.0007 (5) |
| C5 | 0.0205 (6) | 0.0167 (5) | 0.0183 (5) | 0.0015 (4) | −0.0007 (4) | 0.0002 (4) |
| C23 | 0.0331 (7) | 0.0327 (7) | 0.0217 (6) | −0.0001 (5) | 0.0027 (5) | −0.0064 (5) |
| C19 | 0.0383 (7) | 0.0183 (6) | 0.0285 (6) | −0.0024 (5) | 0.0024 (6) | −0.0005 (5) |
| C17 | 0.0251 (6) | 0.0340 (7) | 0.0234 (6) | −0.0052 (5) | −0.0028 (5) | −0.0023 (5) |
| C21 | 0.0269 (6) | 0.0269 (6) | 0.0323 (7) | 0.0074 (5) | −0.0012 (5) | 0.0004 (5) |
| Si1—C7 | 1.8630 (13) | C9—C14 | 1.3946 (17) |
| Si1—C8 | 1.8666 (14) | C10—C11 | 1.3887 (17) |
| Si1—C6 | 1.8699 (13) | C10—H10 | 0.9300 |
| Si1—C2 | 1.8795 (12) | C14—C13 | 1.3873 (19) |
| Si2—C23 | 1.8640 (14) | C14—H14 | 0.9300 |
| Si2—C21 | 1.8659 (14) | C4—C5 | 1.3544 (17) |
| Si2—C22 | 1.8668 (14) | C18—C19 | 1.388 (2) |
| Si2—C5 | 1.8796 (12) | C18—C17 | 1.390 (2) |
| O1—C1 | 1.2139 (15) | C18—H18 | 0.9300 |
| C2—C3 | 1.3454 (16) | C8—H8A | 0.9600 |
| C2—C1 | 1.5117 (16) | C8—H8B | 0.9600 |
| C15—C20 | 1.3993 (17) | C8—H8C | 0.9600 |
| C15—C16 | 1.4037 (17) | C1—C5 | 1.5166 (16) |
| C15—C4 | 1.4799 (16) | C20—C19 | 1.3886 (18) |
| C7—H7A | 0.9600 | C20—H20 | 0.9300 |
| C7—H7B | 0.9600 | C22—H22A | 0.9600 |
| C7—H7C | 0.9600 | C22—H22B | 0.9600 |
| C3—C9 | 1.4760 (16) | C22—H22C | 0.9600 |
| C3—C4 | 1.5271 (16) | C13—H13 | 0.9300 |
| C6—H6A | 0.9600 | C11—H11 | 0.9300 |
| C6—H6B | 0.9600 | C23—H23A | 0.9600 |
| C6—H6C | 0.9600 | C23—H23B | 0.9600 |
| C16—C17 | 1.3876 (18) | C23—H23C | 0.9600 |
| C16—H16 | 0.9300 | C19—H19 | 0.9300 |
| C12—C11 | 1.3855 (19) | C17—H17 | 0.9300 |
| C12—C13 | 1.3855 (19) | C21—H21A | 0.9600 |
| C12—H12 | 0.9300 | C21—H21B | 0.9600 |
| C9—C10 | 1.3942 (16) | C21—H21C | 0.9600 |
| C7—Si1—C8 | 107.60 (6) | C15—C4—C3 | 121.72 (10) |
| C7—Si1—C6 | 110.88 (7) | C19—C18—C17 | 119.63 (12) |
| C8—Si1—C6 | 110.62 (7) | C19—C18—H18 | 120.2 |
| C7—Si1—C2 | 112.32 (6) | C17—C18—H18 | 120.2 |
| C8—Si1—C2 | 107.45 (6) | Si1—C8—H8A | 109.5 |
| C6—Si1—C2 | 107.94 (5) | Si1—C8—H8B | 109.5 |
| C23—Si2—C21 | 110.99 (6) | H8A—C8—H8B | 109.5 |
| C23—Si2—C22 | 108.42 (7) | Si1—C8—H8C | 109.5 |
| C21—Si2—C22 | 108.58 (7) | H8A—C8—H8C | 109.5 |
| C23—Si2—C5 | 109.86 (6) | H8B—C8—H8C | 109.5 |
| C21—Si2—C5 | 108.84 (6) | O1—C1—C2 | 125.01 (11) |
| C22—Si2—C5 | 110.13 (6) | O1—C1—C5 | 125.76 (11) |
| C3—C2—C1 | 105.30 (10) | C2—C1—C5 | 109.19 (10) |
| C3—C2—Si1 | 134.17 (9) | C19—C20—C15 | 120.61 (12) |
| C1—C2—Si1 | 120.39 (8) | C19—C20—H20 | 119.7 |
| C20—C15—C16 | 118.71 (11) | C15—C20—H20 | 119.7 |
| C20—C15—C4 | 120.72 (11) | Si2—C22—H22A | 109.5 |
| C16—C15—C4 | 120.56 (11) | Si2—C22—H22B | 109.5 |
| Si1—C7—H7A | 109.5 | H22A—C22—H22B | 109.5 |
| Si1—C7—H7B | 109.5 | Si2—C22—H22C | 109.5 |
| H7A—C7—H7B | 109.5 | H22A—C22—H22C | 109.5 |
| Si1—C7—H7C | 109.5 | H22B—C22—H22C | 109.5 |
| H7A—C7—H7C | 109.5 | C12—C13—C14 | 119.96 (12) |
| H7B—C7—H7C | 109.5 | C12—C13—H13 | 120.0 |
| C2—C3—C9 | 127.20 (11) | C14—C13—H13 | 120.0 |
| C2—C3—C4 | 110.23 (10) | C12—C11—C10 | 119.88 (12) |
| C9—C3—C4 | 122.56 (10) | C12—C11—H11 | 120.1 |
| Si1—C6—H6A | 109.5 | C10—C11—H11 | 120.1 |
| Si1—C6—H6B | 109.5 | C4—C5—C1 | 104.61 (10) |
| H6A—C6—H6B | 109.5 | C4—C5—Si2 | 131.46 (9) |
| Si1—C6—H6C | 109.5 | C1—C5—Si2 | 123.91 (9) |
| H6A—C6—H6C | 109.5 | Si2—C23—H23A | 109.5 |
| H6B—C6—H6C | 109.5 | Si2—C23—H23B | 109.5 |
| C17—C16—C15 | 120.21 (11) | H23A—C23—H23B | 109.5 |
| C17—C16—H16 | 119.9 | Si2—C23—H23C | 109.5 |
| C15—C16—H16 | 119.9 | H23A—C23—H23C | 109.5 |
| C11—C12—C13 | 120.17 (12) | H23B—C23—H23C | 109.5 |
| C11—C12—H12 | 119.9 | C18—C19—C20 | 120.27 (12) |
| C13—C12—H12 | 119.9 | C18—C19—H19 | 119.9 |
| C10—C9—C14 | 118.95 (11) | C20—C19—H19 | 119.9 |
| C10—C9—C3 | 120.03 (11) | C16—C17—C18 | 120.54 (12) |
| C14—C9—C3 | 121.02 (11) | C16—C17—H17 | 119.7 |
| C11—C10—C9 | 120.52 (12) | C18—C17—H17 | 119.7 |
| C11—C10—H10 | 119.7 | Si2—C21—H21A | 109.5 |
| C9—C10—H10 | 119.7 | Si2—C21—H21B | 109.5 |
| C13—C14—C9 | 120.49 (12) | H21A—C21—H21B | 109.5 |
| C13—C14—H14 | 119.8 | Si2—C21—H21C | 109.5 |
| C9—C14—H14 | 119.8 | H21A—C21—H21C | 109.5 |
| C5—C4—C15 | 127.71 (11) | H21B—C21—H21C | 109.5 |
| C5—C4—C3 | 110.56 (10) |
This work was partially supported by a Grant-in-Aid for Young Scientists (B), No. 17750032 (to MS), from the Ministry of Education, Culture, Sports, Science and Technology of Japan.
Barnes, J. C., Horspool, W. M. & Mackie, F. I. (1991). Acta Cryst. C47, 164–168.
Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
Rajesh, T. & Periasamy, M. (1999). Organometallics, 18, 5709–5712.
Ruffani, A., Schwarzer, A. & Weber, E. (2006). Acta Cryst. E62, o2281o2282.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Although the synthesis of the title compound, (I), was already reported (Rajesh & Periasamy, 1999), the reported NMR data were incorrect. Thus, we report herein the molecular structure of the title compound and revise its NMR data. The five-membered ring and four bonds derived from the each of carbon atoms in the five-membered ring are situated in a planar geometry, as was observed in the tetraphenylcyclopentadienone (Barnes et al., 1991). Bond alternation of the C—C bonds in the five-membered ring of (I) is found, as was observed in other cyclopentadienones (Barnes et al., 1991; Ruffani et al., 2006). The C1—O1 distance (1.2139 (15) Å) in (I), is quite similar to that found in the tetraphenyl derivative (Barnes et al., 1991).