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In the title compound, rel-(2R,3S,1'R,2'S,5'S,7'S)-3-allyl-2-(2'-hydroxy-7'-tri­methyl­silylbi­cyclo­[3.3.0]­octan-2'-yl)­cyclo­pen­tan­one, C19H32O2Si, the two rings of the bi­cyclo­[3.3.0]­octane unit adopt an envelope conformation and the cyclo­pentanone ring is in a twist conformation. In the crystal, mol­ecules related by a center of symmetry are hydrogen bonded to form dimers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801006808/cv6020sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801006808/cv6020Isup2.hkl
Contains datablock I

CCDC reference: 165671

Key indicators

  • Single-crystal X-ray study
  • T = 223 K
  • Mean [sigma](C-C) = 0.002 Å
  • Disorder in main residue
  • R factor = 0.041
  • wR factor = 0.115
  • Data-to-parameter ratio = 16.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_301 Alert C Main Residue Disorder ........................ 12.00 Perc.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

In the context of a project described elsewere (Helbling et al., 1999), we investigated the allylation of cyclopentenone (1) with allyltrimethylsilane (2) (Hosomi & Sakurai, 1977). Careful chromatography of the product mixture gave the aldol product rel-(2R,3S,1'R,2'S,5'S,7'S)-3-allyl-2-(2'-hydroxy-7'- trimethylsilylbicyclo[3.3.0]octan-2'-yl)cyclopentanone, (3). In order to determine the stereochemistry of the trimethylsilyl group in (3) and other structural features, its structure was determined by X-ray diffraction.

The distance between the bridgehead atoms 1' and 5' is 1.553 (2) Å and thus in the normal range for C—C bonds. The bond angles C8'—C1'—C2' = 116.47 (13)° and C4'—C5'—C6' = 116.04 (15)°, at the bridgeheads of the bicyclic structure are rather large. The torsion angles C2'—C1'—C5'—C4' and C8'—C1'—C5'—C6' are 5.76 (17) and 4.65 (17)°, respectively. The two five-membered rings of the bicyclo[3.3.0]octane subunit adopt an exo/endo envelope conformation (with the TMS group in the exo-envelope ring), while the cyclopentanone ring adopts a twist conformation. The trimethylsilyl substituent is located exo to the bridgehead H atoms and thus shows the normal stereoselectivity of the Sakurai reaction (Helbling et al., 1999). In the crystal, molecules related by a center of symmetry are linked by hydrogen bonds, involving hydroxyl O2' and carbonyl O1, to form dimers.

Experimental top

A solution of (1) (4.1 g, 50 mmol) and allyltrimethylsilane (2) (11.4 g, 100 mmol) in methylene chloride under argon was cooled to 195 K. TiCl4 (9.5 g, 5.5 ml, 100 mmol) was then added dropwise and the mixture was stirred at 253 K overnight. After warming to 273 K and work up, column chromatography of the crude material (6.4 g) with hexane–ethyl acetate (19:1) gave 630 mg (8%) (3) and some other products (Helbling et al., 1999). Crystallization from hexane gave pure (3). M.p.: 377 K. 1H NMR: 5.7–5.9 (m, 1H), 5.02–5.13 (m, 2H), 3.1–3.2 (broad, 1H), 2.0–2.6 (m, 8H), 1.4–1.85 (m, 7H), 0.95–1.38 (m, 4 H), -0.05 (s, 9H). 13 C NMR (CDCl3): 135.72 (d), 117.07 (t), 83.76, 60.65 (d), 50.03 (d), 46.71 (d), 40.82 (t), 40.76 (t), 39.26 (t), 37.89 (d), 33.94 (t), 30.33 (t), 29.61 (t), 26.77 (t), 26.01 (d), -2.81 (q). MS: 320 (M+, 2), 302 (38), 261 (12), 189 (80), 155 (100), 147 (32), 83 (38), 73 (56); HR—MS: calculated for C19H30OSi [M - H2O]: 302.205510; found: 302.206594. Suitable crystals of (3) were grown from ether–hexane as colourless blocks.

Refinement top

The H atoms were included in calulated positions and treated as riding atoms using SHELXL default parameters. The allyl side chain is disordered. The occupancies of the two positions for atoms C6, C7 and C8 were refined to be A:B = 0.564:0.436.

Computing details top

Data collection: EXPOSE in IPDS Software (Stoe & Cie, 2000); cell refinement: CELL in IPDS Software; data reduction: INTEGRATE in IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON99 (Spek, 1990); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The structure of (3) showing the numbering scheme and displacement ellipsoids at the 50% probability level.
[Figure 2] Fig. 2. The crystal packing of (3); hydrogen bonding is shown as dotted lines.
(I) top
Crystal data top
C19H32O2SiF(000) = 704
Mr = 320.54Dx = 1.106 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 14.1445 (14) ÅCell parameters from 5000 reflections
b = 6.2718 (4) Åθ = 2.1–25.9°
c = 22.340 (2) ŵ = 0.13 mm1
β = 103.694 (11)°T = 223 K
V = 1925.4 (3) Å3Block, colourless
Z = 40.45 × 0.40 × 0.30 mm
Data collection top
Stoe IPDS
diffractometer
2809 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.036
Graphite monochromatorθmax = 25.9°, θmin = 2.1°
Detector resolution: 0.81Å pixels mm-1h = 1717
ϕ oscillation scansk = 76
13376 measured reflectionsl = 2727
3691 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0736P)2 + 0.0262P]
where P = (Fo2 + 2Fc2)/3
3691 reflections(Δ/σ)max = 0.001
231 parametersΔρmax = 0.31 e Å3
6 restraintsΔρmin = 0.29 e Å3
Crystal data top
C19H32O2SiV = 1925.4 (3) Å3
Mr = 320.54Z = 4
Monoclinic, P21/cMo Kα radiation
a = 14.1445 (14) ŵ = 0.13 mm1
b = 6.2718 (4) ÅT = 223 K
c = 22.340 (2) Å0.45 × 0.40 × 0.30 mm
β = 103.694 (11)°
Data collection top
Stoe IPDS
diffractometer
2809 reflections with I > 2σ(I)
13376 measured reflectionsRint = 0.036
3691 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0416 restraints
wR(F2) = 0.115H-atom parameters constrained
S = 1.05Δρmax = 0.31 e Å3
3691 reflectionsΔρmin = 0.29 e Å3
231 parameters
Special details top

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) top
xyzUiso*/UeqOcc. (<1)
Si10.66534 (3)0.63460 (7)0.21123 (2)0.03578 (15)
C1'0.82283 (11)0.2185 (3)0.12615 (7)0.0361 (3)
H1'0.80270.06750.11930.043*
C2'0.88120 (11)0.2850 (2)0.07837 (7)0.0357 (3)
O2'0.86121 (7)0.50559 (17)0.06421 (5)0.0389 (3)
H2'0.90900.56160.05500.058*
C3'0.98698 (12)0.2578 (3)0.11428 (8)0.0497 (4)
H3'A1.00670.10770.11620.060*
H3'B1.03130.34120.09570.060*
C4'0.98515 (11)0.3424 (3)0.17772 (8)0.0518 (4)
H4'A0.98100.49840.17760.062*
H4'B1.04330.29800.20850.062*
C5'0.89358 (12)0.2420 (3)0.19056 (7)0.0443 (4)
H5'0.90910.09980.20960.053*
C6'0.83947 (12)0.3758 (3)0.22918 (7)0.0423 (4)
H6'A0.88490.46680.25820.051*
H6'B0.80500.28380.25250.051*
C7'0.76722 (10)0.5115 (2)0.18233 (6)0.0333 (3)
H7'0.80410.62790.16830.040*
C8'0.73344 (10)0.3562 (3)0.12847 (6)0.0369 (3)
H8'A0.71080.43450.08980.044*
H8'B0.68020.26670.13530.044*
C10.90798 (14)0.2368 (3)0.02923 (8)0.0498 (4)
O10.99521 (9)0.2637 (2)0.01939 (6)0.0562 (4)
C20.85458 (12)0.1553 (3)0.01809 (7)0.0460 (4)
H20.87500.00590.02800.055*
C30.74763 (15)0.1533 (5)0.01618 (8)0.0758 (7)
H3A0.71290.27960.00560.091*0.564 (6)
H3B0.73230.30410.01180.091*0.436 (6)
C40.7483 (2)0.1520 (6)0.08502 (10)0.0968 (10)
H4A0.75290.00600.09970.116*
H4B0.68910.21820.10980.116*
C50.83684 (17)0.2794 (5)0.08872 (9)0.0795 (7)
H5A0.86260.23250.12360.095*
H5B0.82140.43170.09330.095*
C6A0.7037 (3)0.0685 (8)0.00554 (19)0.0615 (13)0.564 (6)
H6A0.74400.18950.00080.074*0.564 (6)
H6B0.70460.06090.04950.074*0.564 (6)
C7A0.6020 (3)0.0995 (7)0.03112 (17)0.0644 (14)0.564 (6)
H7AA0.55940.01650.03280.077*0.564 (6)
C8A0.5665 (5)0.2681 (15)0.0606 (6)0.095 (2)0.564 (6)
H8A0.60610.38860.06030.114*0.564 (6)
H8B0.50100.27100.08240.114*0.564 (6)
C6B0.6572 (3)0.0576 (8)0.00667 (18)0.0495 (15)0.436 (6)
H6C0.60030.11740.03560.059*0.436 (6)
H6D0.65080.08250.03550.059*0.436 (6)
C7B0.6669 (5)0.1723 (9)0.0181 (3)0.0666 (18)0.436 (6)
H7B0.72450.23940.00320.080*0.436 (6)
C8B0.6038 (8)0.289 (2)0.0545 (8)0.121 (5)0.436 (6)
H8C0.54520.22850.07670.145*0.436 (6)
H8D0.61630.43450.05890.145*0.436 (6)
C100.59107 (13)0.4230 (3)0.23706 (9)0.0542 (5)
H10A0.53990.48880.25290.081*
H10B0.63240.33840.26920.081*
H10C0.56230.33170.20250.081*
C90.58525 (13)0.7890 (3)0.14757 (8)0.0547 (5)
H9A0.62170.90680.13600.082*
H9B0.52990.84390.16130.082*
H9C0.56260.69650.11230.082*
C110.71678 (14)0.8137 (3)0.27794 (9)0.0563 (5)
H11A0.75740.73110.31090.084*
H11B0.66410.87830.29250.084*
H11C0.75550.92440.26500.084*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Si10.0399 (2)0.0337 (3)0.0387 (2)0.00322 (18)0.01918 (17)0.00023 (18)
C1'0.0428 (8)0.0294 (8)0.0382 (8)0.0011 (6)0.0139 (6)0.0002 (6)
C2'0.0370 (7)0.0312 (8)0.0418 (8)0.0036 (6)0.0149 (6)0.0003 (6)
O2'0.0386 (6)0.0325 (6)0.0503 (6)0.0047 (4)0.0201 (5)0.0042 (5)
C3'0.0397 (9)0.0509 (12)0.0605 (10)0.0130 (7)0.0158 (8)0.0001 (8)
C4'0.0353 (8)0.0621 (12)0.0538 (10)0.0120 (8)0.0021 (7)0.0015 (9)
C5'0.0502 (9)0.0395 (10)0.0411 (9)0.0112 (7)0.0064 (7)0.0069 (7)
C6'0.0480 (9)0.0450 (10)0.0329 (7)0.0004 (7)0.0072 (6)0.0001 (7)
C7'0.0347 (7)0.0321 (9)0.0353 (7)0.0039 (6)0.0130 (6)0.0006 (6)
C8'0.0336 (7)0.0448 (9)0.0339 (7)0.0031 (6)0.0110 (6)0.0030 (7)
C10.0659 (12)0.0386 (10)0.0554 (10)0.0020 (8)0.0355 (9)0.0072 (8)
O10.0622 (8)0.0432 (8)0.0764 (9)0.0032 (6)0.0425 (7)0.0000 (6)
C20.0575 (10)0.0404 (10)0.0482 (9)0.0036 (7)0.0286 (8)0.0070 (7)
C30.0646 (12)0.124 (2)0.0445 (10)0.0364 (13)0.0251 (9)0.0349 (12)
C40.0954 (18)0.154 (3)0.0467 (12)0.0386 (18)0.0274 (12)0.0288 (14)
C50.0872 (16)0.110 (2)0.0481 (11)0.0068 (14)0.0300 (11)0.0007 (12)
C6A0.046 (2)0.068 (3)0.060 (2)0.013 (2)0.0082 (17)0.008 (2)
C7A0.041 (2)0.078 (3)0.065 (2)0.001 (2)0.0053 (17)0.006 (2)
C8A0.055 (4)0.073 (4)0.127 (5)0.004 (3)0.036 (4)0.019 (3)
C6B0.040 (2)0.068 (3)0.037 (2)0.003 (2)0.0019 (17)0.004 (2)
C7B0.060 (4)0.057 (4)0.072 (3)0.001 (3)0.005 (3)0.007 (3)
C8B0.085 (8)0.092 (6)0.143 (7)0.016 (7)0.061 (8)0.025 (5)
C100.0565 (10)0.0560 (12)0.0594 (11)0.0118 (9)0.0327 (8)0.0016 (9)
C90.0558 (10)0.0582 (12)0.0549 (10)0.0148 (9)0.0230 (8)0.0090 (9)
C110.0653 (12)0.0505 (12)0.0579 (11)0.0055 (9)0.0242 (9)0.0147 (9)
Geometric parameters (Å, º) top
Si1—C91.8655 (18)C7'—C8'1.534 (2)
Si1—C101.8671 (17)C1—O11.213 (2)
Si1—C111.8704 (18)C1—C51.489 (3)
Si1—C7'1.8788 (15)C1—C21.526 (2)
C1'—C8'1.542 (2)C2—C31.525 (3)
C1'—C5'1.553 (2)C3—C6B1.473 (4)
C1'—C2'1.553 (2)C3—C41.540 (3)
C2'—O2'1.4321 (19)C3—C6A1.643 (5)
C2'—C3'1.531 (2)C4—C51.504 (3)
C2'—C21.542 (2)C6A—C7A1.490 (5)
C3'—C4'1.519 (3)C7A—C8A1.283 (10)
C4'—C5'1.527 (2)C6B—C7B1.477 (8)
C5'—C6'1.532 (2)C7B—C8B1.283 (12)
C6'—C7'1.535 (2)
C9—Si1—C10108.67 (9)C8'—C7'—Si1114.12 (10)
C9—Si1—C11110.32 (10)C6'—C7'—Si1115.75 (10)
C10—Si1—C11108.77 (9)C7'—C8'—C1'106.05 (12)
C9—Si1—C7'109.15 (7)O1—C1—C5125.48 (16)
C10—Si1—C7'110.34 (8)O1—C1—C2124.78 (17)
C11—Si1—C7'109.58 (8)C5—C1—C2109.74 (16)
C8'—C1'—C5'105.61 (12)C3—C2—C1104.47 (15)
C8'—C1'—C2'116.47 (13)C3—C2—C2'116.79 (14)
C5'—C1'—C2'106.28 (12)C1—C2—C2'111.70 (14)
O2'—C2'—C3'109.93 (13)C6B—C3—C2136.3 (3)
O2'—C2'—C2108.79 (13)C6B—C3—C4110.6 (2)
C3'—C2'—C2113.90 (13)C2—C3—C4105.16 (16)
O2'—C2'—C1'107.60 (11)C6B—C3—C6A37.8 (2)
C3'—C2'—C1'102.86 (13)C2—C3—C6A105.0 (2)
C2—C2'—C1'113.49 (13)C4—C3—C6A112.5 (2)
C4'—C3'—C2'102.68 (12)C5—C4—C3104.71 (17)
C3'—C4'—C5'103.52 (14)C1—C5—C4104.56 (19)
C4'—C5'—C6'116.04 (15)C7A—C6A—C3109.4 (3)
C4'—C5'—C1'104.74 (12)C8A—C7A—C6A126.8 (5)
C6'—C5'—C1'106.00 (12)C3—C6B—C7B104.7 (4)
C5'—C6'—C7'105.08 (12)C8B—C7B—C6B125.9 (8)
C8'—C7'—C6'102.49 (12)
C8'—C1'—C2'—O2'22.39 (17)O1—C1—C2—C3179.07 (18)
C5'—C1'—C2'—O2'94.91 (14)C5—C1—C2—C30.5 (2)
C8'—C1'—C2'—C3'138.44 (14)O1—C1—C2—C2'51.9 (2)
C5'—C1'—C2'—C3'21.14 (16)C5—C1—C2—C2'127.60 (18)
C8'—C1'—C2'—C298.03 (16)O2'—C2'—C2—C364.13 (19)
C5'—C1'—C2'—C2144.67 (13)C3'—C2'—C2—C3172.87 (17)
O2'—C2'—C3'—C4'74.06 (16)C1'—C2'—C2—C355.6 (2)
C2—C2'—C3'—C4'163.56 (14)O2'—C2'—C2—C156.02 (17)
C1'—C2'—C3'—C4'40.31 (17)C3'—C2'—C2—C166.97 (19)
C2'—C3'—C4'—C5'44.70 (17)C1'—C2'—C2—C1175.76 (14)
C3'—C4'—C5'—C6'147.30 (14)C1—C2—C3—C6B164.6 (3)
C3'—C4'—C5'—C1'30.83 (17)C2'—C2—C3—C6B71.5 (4)
C8'—C1'—C5'—C4'118.56 (14)C1—C2—C3—C420.3 (3)
C2'—C1'—C5'—C4'5.76 (17)C2'—C2—C3—C4144.2 (2)
C8'—C1'—C5'—C6'4.65 (17)C1—C2—C3—C6A139.2 (2)
C2'—C1'—C5'—C6'128.97 (14)C2'—C2—C3—C6A96.9 (3)
C4'—C5'—C6'—C7'89.10 (16)C6B—C3—C4—C5172.5 (3)
C1'—C5'—C6'—C7'26.67 (17)C2—C3—C4—C533.0 (3)
C5'—C6'—C7'—C8'38.13 (15)C6A—C3—C4—C5146.7 (3)
C5'—C6'—C7'—Si1162.99 (11)O1—C1—C5—C4160.5 (2)
C9—Si1—C7'—C8'60.63 (13)C2—C1—C5—C420.0 (3)
C10—Si1—C7'—C8'58.71 (13)C3—C4—C5—C132.3 (3)
C11—Si1—C7'—C8'178.45 (11)C6B—C3—C6A—C7A35.7 (3)
C9—Si1—C7'—C6'179.26 (12)C2—C3—C6A—C7A173.2 (3)
C10—Si1—C7'—C6'59.91 (13)C4—C3—C6A—C7A59.4 (4)
C11—Si1—C7'—C6'59.83 (14)C3—C6A—C7A—C8A129.1 (9)
C6'—C7'—C8'—C1'35.28 (14)C2—C3—C6B—C7B71.7 (4)
Si1—C7'—C8'—C1'161.20 (10)C4—C3—C6B—C7B71.3 (4)
C5'—C1'—C8'—C7'19.13 (16)C6A—C3—C6B—C7B29.1 (3)
C2'—C1'—C8'—C7'98.54 (14)C3—C6B—C7B—C8B128.7 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.832.042.8605 (16)168
Symmetry code: (i) x+2, y+1, z.

Experimental details

Crystal data
Chemical formulaC19H32O2Si
Mr320.54
Crystal system, space groupMonoclinic, P21/c
Temperature (K)223
a, b, c (Å)14.1445 (14), 6.2718 (4), 22.340 (2)
β (°) 103.694 (11)
V3)1925.4 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.45 × 0.40 × 0.30
Data collection
DiffractometerStoe IPDS
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
13376, 3691, 2809
Rint0.036
(sin θ/λ)max1)0.614
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.115, 1.05
No. of reflections3691
No. of parameters231
No. of restraints6
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.29

Computer programs: EXPOSE in IPDS Software (Stoe & Cie, 2000), CELL in IPDS Software, INTEGRATE in IPDS Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON99 (Spek, 1990), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2'—H2'···O1i0.832.042.8605 (16)167.7
Symmetry code: (i) x+2, y+1, z.
 

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