cis,trans,cis,cis-7-tert-Butyl-dimethyl-silyl-oxy-4,10-dimethyl-tetra-cyclo[5.4.1.0.0]dodecan-2-one.

In the structure of the title compound, C(20)H(34)O(2)Si, a cis,trans,cis,cis-[4.5.5.5]fenestrane derivative, the geometry of the central C(C)(4) substructure shows considerable distortion from an ideal tetra-hedral arrangement towards planarity, with two opposite bridgehead bond angles of 128.87 (18) and 122.83 (17)°. The other bridgehead angle of the trans-bicyclo-[3.3.0]octane subunit is also large [126.57 (19)°].

Related literature

For the synthesis and structures of related compounds, see: Thommen et al. (1996 ▶); Wang et al. (1996 ▶); Weyermann (1997 ▶); Weyermann & Keese (2010 ▶). For information on planarizing distortions in the central C(C)4 moiety, see: Keese (2006 ▶). For methods to enhance the planarizing distortions in the central C(C)4 substructure, see: Luef & Keese (1993 ▶). For an analysis of the bond angles and other details concerning trans-fused bicyclo­[3.3.0]octa­nes, see: Hirschi et al. (1992 ▶). For information concerning the Pauson–Khand reaction, see: Khand, Knox, Pauson & Watts (1973 ▶); Khand, Knox, Pauson, Watts & Foreman (1973 ▶).

Experimental

Crystal data

C20H34O2Si

M = 334.56

Orthorhombic,

a = 13.7374 (13) Å

b = 14.7647 (11) Å

c = 19.2829 (12) Å

V = 3911.1 (5) Å3

Z = 8

Mo Kα radiation

μ = 0.13 mm−1

T = 223 K

0.53 × 0.42 × 0.34 mm

Data collection

Stoe AED2 four-circle diffractometer

7284 measured reflections

3642 independent reflections

2718 reflections with I > 2σ(I)

R int = 0.042

3 standard reflections every 60 min intensity decay: <1%

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.116

S = 1.07

3642 reflections

216 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.29 e Å−3

Data collection: STADI-4 (Stoe & Cie, 1997 ▶); cell refinement: STADI-4; data reduction: X-RED (Stoe & Cie, 1997 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810000887/fk2011sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810000887/fk2011Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C20H34O2Si	F(000) = 1472
Mr = 334.56	Dx = 1.136 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 20 reflections
a = 13.7374 (13) Å	θ = 14–17.7°
b = 14.7647 (11) Å	µ = 0.13 mm−1
c = 19.2829 (12) Å	T = 223 K
V = 3911.1 (5) Å3	Block, colourless
Z = 8	0.53 × 0.42 × 0.34 mm

Stoe AED2 four-circle diffractometer	Rint = 0.042
Radiation source: fine-focus sealed tube	θmax = 25.5°, θmin = 2.1°
graphite	h = −16→16
2θ/ω scans	k = 0→17
7284 measured reflections	l = 0→23
3642 independent reflections	3 standard reflections every 60 min
2718 reflections with I > 2σ(I)	intensity decay: <1%

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)] = 0.048	H-atom parameters constrained
wR(F2) = 0.116	w = 1/[σ2(Fo2) + (0.0378P)2 + 2.3403P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
3642 reflections	Δρmax = 0.28 e Å−3
216 parameters	Δρmin = −0.29 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0018 (5)

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.18635 (4)	0.81357 (4)	0.04887 (3)	0.0263 (2)
O2	0.27615 (14)	0.95616 (16)	0.38174 (11)	0.0711 (8)
O7	0.17598 (10)	0.86338 (10)	0.12503 (7)	0.0312 (5)
C1	0.21973 (17)	0.97101 (17)	0.26241 (13)	0.0408 (8)
C2	0.21585 (18)	0.93807 (18)	0.33818 (13)	0.0454 (9)
C3	0.12597 (18)	0.87879 (17)	0.35050 (12)	0.0401 (8)
C4	0.09843 (16)	0.84971 (14)	0.27688 (11)	0.0301 (7)
C5	−0.00409 (17)	0.83122 (15)	0.24976 (12)	0.0350 (7)
C6	0.00658 (16)	0.84850 (16)	0.17076 (12)	0.0355 (7)
C7	0.09821 (15)	0.90983 (14)	0.15884 (11)	0.0274 (6)
C8	0.0748 (2)	0.99911 (16)	0.12245 (12)	0.0427 (8)
C9	0.0247 (2)	1.05514 (15)	0.17828 (12)	0.0457 (9)
C10	0.07572 (17)	1.03098 (14)	0.24635 (12)	0.0346 (7)
C11	0.1814 (2)	1.06806 (17)	0.25435 (15)	0.0527 (9)
C12	0.12488 (15)	0.93286 (14)	0.23397 (10)	0.0264 (6)
C13	0.16461 (18)	0.76782 (15)	0.25992 (13)	0.0403 (8)
C14	0.0109 (2)	1.05498 (16)	0.30795 (13)	0.0445 (8)
C15	0.15738 (19)	0.68993 (15)	0.05640 (13)	0.0419 (8)
C16	0.10610 (18)	0.86511 (17)	−0.01811 (12)	0.0418 (8)
C17	0.31834 (16)	0.82806 (16)	0.02537 (12)	0.0340 (7)
C18	0.3464 (2)	0.92884 (18)	0.02703 (16)	0.0554 (10)
C19	0.38166 (19)	0.7765 (2)	0.07777 (15)	0.0543 (10)
C20	0.3373 (2)	0.7910 (2)	−0.04778 (14)	0.0584 (10)
H1	0.27950	0.95590	0.23620	0.0490*
H3A	0.14170	0.82630	0.37960	0.0480*
H3B	0.07340	0.91340	0.37240	0.0480*
H5A	−0.05160	0.87270	0.27060	0.0420*
H5B	−0.02390	0.76870	0.25910	0.0420*
H6A	−0.05180	0.87870	0.15290	0.0430*
H6B	0.01440	0.79090	0.14620	0.0430*
H8A	0.13430	1.02890	0.10630	0.0510*
H8B	0.03140	0.98920	0.08280	0.0510*
H9A	−0.04470	1.04020	0.18070	0.0550*
H9B	0.03140	1.12000	0.16840	0.0550*
H11A	0.20580	1.09900	0.21290	0.0630*
H11B	0.19070	1.10560	0.29570	0.0630*
H13A	0.23230	0.78530	0.26520	0.0600*
H13B	0.15310	0.74850	0.21250	0.0600*
H13C	0.14990	0.71840	0.29140	0.0600*
H14A	0.04770	1.04860	0.35060	0.0670*
H14B	−0.04470	1.01460	0.30900	0.0670*
H14C	−0.01140	1.11700	0.30340	0.0670*
H15A	0.19140	0.66470	0.09600	0.0630*
H15B	0.17790	0.65890	0.01450	0.0630*
H15C	0.08780	0.68220	0.06260	0.0630*
H16A	0.03900	0.86290	−0.00250	0.0630*
H16B	0.11240	0.83170	−0.06120	0.0630*
H16C	0.12510	0.92760	−0.02560	0.0630*
H18A	0.30640	0.96200	−0.00570	0.0830*
H18B	0.41440	0.93540	0.01460	0.0830*
H18C	0.33600	0.95270	0.07330	0.0830*
H19A	0.36730	0.79770	0.12430	0.0810*
H19B	0.44990	0.78700	0.06750	0.0810*
H19C	0.36780	0.71220	0.07460	0.0810*
H20A	0.29860	0.82450	−0.08110	0.0880*
H20B	0.31960	0.72740	−0.04950	0.0880*
H20C	0.40580	0.79760	−0.05900	0.0880*

	U11	U22	U33	U12	U13	U23
Si1	0.0267 (3)	0.0288 (3)	0.0234 (3)	0.0009 (3)	−0.0002 (2)	−0.0016 (2)
O2	0.0468 (12)	0.1080 (18)	0.0584 (13)	0.0074 (12)	−0.0202 (10)	−0.0360 (12)
O7	0.0315 (8)	0.0354 (8)	0.0266 (8)	0.0075 (7)	0.0024 (6)	−0.0031 (6)
C1	0.0288 (12)	0.0511 (15)	0.0425 (14)	−0.0097 (11)	0.0079 (10)	−0.0142 (12)
C2	0.0339 (13)	0.0608 (17)	0.0415 (14)	0.0103 (12)	−0.0048 (11)	−0.0216 (13)
C3	0.0426 (14)	0.0460 (14)	0.0318 (13)	0.0112 (12)	−0.0006 (11)	0.0006 (11)
C4	0.0323 (12)	0.0287 (11)	0.0292 (11)	0.0019 (10)	0.0013 (9)	0.0004 (9)
C5	0.0323 (12)	0.0314 (12)	0.0414 (12)	−0.0064 (10)	0.0077 (10)	−0.0011 (10)
C6	0.0271 (12)	0.0399 (13)	0.0394 (13)	0.0012 (10)	−0.0039 (10)	−0.0063 (11)
C7	0.0284 (11)	0.0281 (11)	0.0256 (11)	0.0048 (9)	0.0022 (9)	−0.0019 (9)
C8	0.0627 (17)	0.0343 (13)	0.0310 (12)	0.0148 (12)	0.0064 (12)	0.0048 (10)
C9	0.0645 (17)	0.0298 (13)	0.0429 (14)	0.0164 (12)	0.0083 (13)	0.0055 (11)
C10	0.0435 (14)	0.0248 (11)	0.0355 (12)	−0.0003 (10)	0.0094 (11)	−0.0008 (10)
C11	0.0632 (18)	0.0436 (14)	0.0512 (15)	−0.0225 (14)	0.0151 (14)	−0.0114 (13)
C12	0.0238 (10)	0.0266 (10)	0.0287 (11)	−0.0010 (9)	0.0032 (9)	−0.0028 (9)
C13	0.0480 (15)	0.0355 (13)	0.0375 (14)	0.0132 (11)	−0.0011 (11)	0.0034 (11)
C14	0.0577 (16)	0.0332 (13)	0.0427 (14)	0.0102 (12)	0.0110 (13)	−0.0047 (11)
C15	0.0503 (15)	0.0333 (12)	0.0421 (14)	−0.0037 (11)	0.0075 (12)	−0.0053 (11)
C16	0.0405 (14)	0.0484 (15)	0.0365 (13)	0.0056 (12)	−0.0095 (11)	−0.0016 (11)
C17	0.0288 (11)	0.0417 (13)	0.0314 (11)	0.0007 (10)	−0.0003 (10)	−0.0056 (10)
C18	0.0435 (15)	0.0518 (17)	0.0710 (19)	−0.0147 (13)	0.0071 (14)	−0.0009 (15)
C19	0.0355 (14)	0.0663 (19)	0.0610 (17)	0.0126 (13)	−0.0082 (13)	−0.0025 (15)
C20	0.0459 (16)	0.085 (2)	0.0443 (15)	−0.0068 (14)	0.0161 (13)	−0.0147 (15)

Si1—O7	1.6486 (15)	C5—H5B	0.9800
Si1—C15	1.874 (2)	C6—H6A	0.9800
Si1—C16	1.861 (2)	C6—H6B	0.9800
Si1—C17	1.881 (2)	C8—H8A	0.9800
O2—C2	1.210 (3)	C8—H8B	0.9800
O7—C7	1.427 (3)	C9—H9A	0.9800
C1—C2	1.541 (4)	C9—H9B	0.9800
C1—C11	1.535 (4)	C11—H11A	0.9800
C1—C12	1.522 (3)	C11—H11B	0.9800
C2—C3	1.532 (4)	C13—H13A	0.9700
C3—C4	1.531 (3)	C13—H13B	0.9700
C4—C5	1.527 (3)	C13—H13C	0.9700
C4—C12	1.524 (3)	C14—H14A	0.9700
C4—C13	1.548 (3)	C14—H14B	0.9700
C5—C6	1.552 (3)	C14—H14C	0.9700
C6—C7	1.568 (3)	C15—H15A	0.9700
C7—C8	1.528 (3)	C15—H15B	0.9700
C7—C12	1.533 (3)	C15—H15C	0.9700
C8—C9	1.522 (3)	C16—H16A	0.9700
C9—C10	1.530 (3)	C16—H16B	0.9700
C10—C11	1.559 (4)	C16—H16C	0.9700
C10—C12	1.616 (3)	C18—H18A	0.9700
C10—C14	1.526 (3)	C18—H18B	0.9700
C17—C18	1.537 (4)	C18—H18C	0.9700
C17—C19	1.535 (4)	C19—H19A	0.9700
C17—C20	1.535 (4)	C19—H19B	0.9700
C1—H1	0.9900	C19—H19C	0.9700
C3—H3A	0.9800	C20—H20A	0.9700
C3—H3B	0.9800	C20—H20B	0.9700
C5—H5A	0.9800	C20—H20C	0.9700
O7—Si1—C15	110.32 (10)	C5—C6—H6A	110.00
O7—Si1—C16	112.62 (9)	C5—C6—H6B	110.00
O7—Si1—C17	104.31 (9)	C7—C6—H6A	110.00
C15—Si1—C16	109.05 (11)	C7—C6—H6B	110.00
C15—Si1—C17	109.52 (11)	H6A—C6—H6B	108.00
C16—Si1—C17	110.94 (11)	C7—C8—H8A	111.00
Si1—O7—C7	133.31 (13)	C7—C8—H8B	111.00
C2—C1—C11	112.3 (2)	C9—C8—H8A	111.00
C2—C1—C12	101.26 (18)	C9—C8—H8B	111.00
C11—C1—C12	90.88 (18)	H8A—C8—H8B	109.00
O2—C2—C1	124.4 (2)	C8—C9—H9A	111.00
O2—C2—C3	124.8 (2)	C8—C9—H9B	111.00
C1—C2—C3	110.8 (2)	C10—C9—H9A	111.00
C2—C3—C4	102.45 (18)	C10—C9—H9B	111.00
C3—C4—C5	126.57 (19)	H9A—C9—H9B	109.00
C3—C4—C12	102.63 (17)	C1—C11—H11A	114.00
C3—C4—C13	105.66 (18)	C1—C11—H11B	114.00
C5—C4—C12	100.25 (17)	C10—C11—H11A	114.00
C5—C4—C13	109.25 (18)	C10—C11—H11B	114.00
C12—C4—C13	111.99 (18)	H11A—C11—H11B	111.00
C4—C5—C6	102.69 (18)	C4—C13—H13A	109.00
C5—C6—C7	108.35 (18)	C4—C13—H13B	109.00
O7—C7—C6	112.99 (17)	C4—C13—H13C	109.00
O7—C7—C8	111.25 (17)	H13A—C13—H13B	109.00
O7—C7—C12	111.07 (16)	H13A—C13—H13C	110.00
C6—C7—C8	113.38 (18)	H13B—C13—H13C	110.00
C6—C7—C12	100.46 (17)	C10—C14—H14A	109.00
C8—C7—C12	107.04 (17)	C10—C14—H14B	109.00
C7—C8—C9	103.85 (18)	C10—C14—H14C	109.00
C8—C9—C10	105.8 (2)	H14A—C14—H14B	109.00
C9—C10—C11	115.4 (2)	H14A—C14—H14C	109.00
C9—C10—C12	105.88 (17)	H14B—C14—H14C	110.00
C9—C10—C14	110.3 (2)	Si1—C15—H15A	109.00
C11—C10—C12	86.58 (16)	Si1—C15—H15B	109.00
C11—C10—C14	112.6 (2)	Si1—C15—H15C	109.00
C12—C10—C14	124.53 (18)	H15A—C15—H15B	110.00
C1—C11—C10	90.09 (18)	H15A—C15—H15C	109.00
C1—C12—C4	107.85 (17)	H15B—C15—H15C	109.00
C1—C12—C7	128.87 (18)	Si1—C16—H16A	109.00
C1—C12—C10	88.44 (16)	Si1—C16—H16B	109.00
C4—C12—C7	106.11 (17)	Si1—C16—H16C	109.00
C4—C12—C10	122.83 (17)	H16A—C16—H16B	109.00
C7—C12—C10	103.81 (16)	H16A—C16—H16C	110.00
Si1—C17—C18	110.29 (16)	H16B—C16—H16C	109.00
Si1—C17—C19	109.34 (16)	C17—C18—H18A	109.00
Si1—C17—C20	110.14 (16)	C17—C18—H18B	109.00
C18—C17—C19	108.9 (2)	C17—C18—H18C	109.00
C18—C17—C20	108.8 (2)	H18A—C18—H18B	110.00
C19—C17—C20	109.4 (2)	H18A—C18—H18C	109.00
C2—C1—H1	116.00	H18B—C18—H18C	109.00
C11—C1—H1	116.00	C17—C19—H19A	109.00
C12—C1—H1	116.00	C17—C19—H19B	109.00
C2—C3—H3A	111.00	C17—C19—H19C	109.00
C2—C3—H3B	111.00	H19A—C19—H19B	109.00
C4—C3—H3A	111.00	H19A—C19—H19C	110.00
C4—C3—H3B	111.00	H19B—C19—H19C	109.00
H3A—C3—H3B	109.00	C17—C20—H20A	110.00
C4—C5—H5A	111.00	C17—C20—H20B	109.00
C4—C5—H5B	111.00	C17—C20—H20C	109.00
C6—C5—H5A	111.00	H20A—C20—H20B	109.00
C6—C5—H5B	111.00	H20A—C20—H20C	109.00
H5A—C5—H5B	109.00	H20B—C20—H20C	109.00
C15—Si1—O7—C7	−92.99 (19)	C5—C4—C12—C1	170.87 (17)
C16—Si1—O7—C7	29.1 (2)	C5—C4—C12—C7	−47.9 (2)
C17—Si1—O7—C7	149.49 (18)	C5—C4—C12—C10	70.9 (2)
O7—Si1—C17—C18	−55.54 (19)	C13—C4—C12—C1	−73.4 (2)
O7—Si1—C17—C19	64.20 (18)	C13—C4—C12—C7	67.8 (2)
O7—Si1—C17—C20	−175.58 (16)	C13—C4—C12—C10	−173.39 (19)
C15—Si1—C17—C18	−173.61 (17)	C4—C5—C6—C7	−21.3 (2)
C15—Si1—C17—C19	−53.9 (2)	C5—C6—C7—O7	111.29 (19)
C15—Si1—C17—C20	66.4 (2)	C5—C6—C7—C8	−121.0 (2)
C16—Si1—C17—C18	66.0 (2)	C5—C6—C7—C12	−7.1 (2)
C16—Si1—C17—C19	−174.29 (17)	O7—C7—C8—C9	−157.49 (18)
C16—Si1—C17—C20	−54.1 (2)	C6—C7—C8—C9	73.9 (2)
Si1—O7—C7—C6	60.9 (2)	C12—C7—C8—C9	−36.0 (2)
Si1—O7—C7—C8	−67.9 (2)	O7—C7—C12—C1	43.8 (3)
Si1—O7—C7—C12	172.93 (14)	O7—C7—C12—C4	−86.14 (19)
C11—C1—C2—O2	−81.3 (3)	O7—C7—C12—C10	143.17 (16)
C11—C1—C2—C3	99.2 (2)	C6—C7—C12—C1	163.6 (2)
C12—C1—C2—O2	−177.0 (3)	C6—C7—C12—C4	33.6 (2)
C12—C1—C2—C3	3.5 (3)	C6—C7—C12—C10	−97.06 (18)
C2—C1—C11—C10	−86.9 (2)	C8—C7—C12—C1	−77.8 (3)
C12—C1—C11—C10	15.64 (18)	C8—C7—C12—C4	152.24 (18)
C2—C1—C12—C4	−26.3 (2)	C8—C7—C12—C10	21.5 (2)
C2—C1—C12—C7	−155.6 (2)	C7—C8—C9—C10	35.9 (2)
C2—C1—C12—C10	97.84 (18)	C8—C9—C10—C11	71.4 (2)
C11—C1—C12—C4	−139.21 (19)	C8—C9—C10—C12	−22.4 (2)
C11—C1—C12—C7	91.5 (2)	C8—C9—C10—C14	−159.60 (19)
C11—C1—C12—C10	−15.08 (18)	C9—C10—C11—C1	−120.7 (2)
O2—C2—C3—C4	−159.7 (3)	C12—C10—C11—C1	−14.73 (17)
C1—C2—C3—C4	19.8 (3)	C14—C10—C11—C1	111.5 (2)
C2—C3—C4—C5	−147.8 (2)	C9—C10—C12—C1	130.35 (19)
C2—C3—C4—C12	−34.7 (2)	C9—C10—C12—C4	−119.3 (2)
C2—C3—C4—C13	82.8 (2)	C9—C10—C12—C7	0.6 (2)
C3—C4—C5—C6	155.0 (2)	C11—C10—C12—C1	14.86 (18)
C12—C4—C5—C6	40.8 (2)	C11—C10—C12—C4	125.2 (2)
C13—C4—C5—C6	−77.0 (2)	C11—C10—C12—C7	−114.91 (18)
C3—C4—C12—C1	39.5 (2)	C14—C10—C12—C1	−100.4 (2)
C3—C4—C12—C7	−179.32 (17)	C14—C10—C12—C4	9.9 (3)
C3—C4—C12—C10	−60.5 (2)	C14—C10—C12—C7	129.8 (2)