(±)-(4aR,5R,8S,8aR)-8-(tert-Butyl­dimethyl­sil­yloxy)-2,5,8a-trimethyl-4a,5,8,8a-tetra­hydro­naphthalene-1,4-dione

Delling, F.N.; Zukerman-Schpector, J.; Brocksom, T.J.; Brocksom, U.; Finelli, F.G.; Tiekink, E.R.T.

doi:10.1107/S1600536813002973

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Page o325

doi:10.1107/S1600536813002973

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(±)-(4aR,5R,8S,8aR)-8-(tert-Butyldimethylsilyloxy)-2,5,8a-trimethyl-4a,5,8,8a-tetrahydronaphthalene-1,4-dione

Felix N. Delling,^a ^* Julio Zukerman-Schpector,^a Timothy J. Brocksom,^a Ursula Brocksom,^a Fernanda G. Finelli ^a and Edward R. T. Tiekink ^b

^aDepartment of Chemistry, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: felixdelling@ufscar.br

(Received 28 January 2013; accepted 29 January 2013; online 2 February 2013)

In the title compound, C₁₉H₃₀O₃Si, both rings adopt a half-boat conformation. Overall, the molecule approximates a U-shape as the cyclo-2-ene-1,4-dione and butyldimethylsilyloxy substituents lie to the same side of the central cyclohexene ring; the methyl substituent lies to the other side of the molecule. In the crystal, linear supramolecular chains along the b axis are sustained by C—H⋯O interactions.

Related literature

For a general description of the synthesis of higher terpenoids using the Diels–Alder reaction, see: Brocksom et al. (2001 ). For the synthesis of a similar compound containing an N atom in place of the O atom, see: Vieira et al. (2007 ). For the synthesis, see: Finelli (2004 ). For additional conformational analysis, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₉H₃₀O₃Si
M_r = 334.52
Monoclinic, P 2/c
a = 15.325 (2) Å
b = 7.1744 (9) Å
c = 17.965 (2) Å
β = 93.577 (9)°
V = 1971.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.15 × 0.10 × 0.08 mm

Data collection

Enraf–Nonius CAD-4 MACH 3 diffractometer
4451 measured reflections
4305 independent reflections
1463 reflections with I > 2σ(I)
R_int = 0.072
3 standard reflections every 30 min intensity decay: 1.4%

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.165
S = 0.93
4305 reflections
216 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O2ⁱ	0.98	2.55	3.524 (5)	171
Symmetry code: (i) x, y+1, z.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: MolEN (Fair, 1990 ); program(s) used to solve structure: SIR92 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and MarvinSketch (ChemAxon, 2009 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813002973/hg5287sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813002973/hg5287Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813002973/hg5287Isup3.cml

checkCIF report

Comment top

The synthesis of polycyclic natural products such as sesqui- and di-terpenes frequently requires the construction of the decalin nucleus. This can be performed using the Diels-Alder reaction between appropriate acyclic dienes and monocyclic dienophiles such as para-benzoquinones. The desired appendages around the decalin nucleus can include oxygen and alkyl substituents, which are conveniently included in the diene and dienophile precursors (Brocksom et al., 2001). It was in this context that the title compound, (I), was investigated (Finelli, 2004). The synthesis of a similar compound, via a multi-component reaction, containing a nitrogen atom in place of the oxygen atom has been published (Vieira et al. 2007). Herein, the crystal structure determination of (I) is described.

In (I), Fig. 1, both rings are in a distorted half-chair conformation. The ring puckering parameters are: q₂ = 0.398 (4), 0.372 (4) Å, q₃ = 0.254 (4), -0.319 (4) Å, QT = 0.472 (4), 0.490 (4) Å, and θ = 236.6 (6), 155.5 (6)° for the cyclo-2-ene-1,4-dione and cyclohexene rings, respectively (Cremer & Pople, 1975). With reference to the cyclohexene ring, the cyclo-2-ene-1,4-dione and butyldimethylsilyloxy substituents lie to the same side so that the molecule approximates a U-shape; the methyl group lies to the other side of the molecule.

In the crystal molecules are connected through C—H···O interactions that lead to linear supramolecular chains along the b axis, Fig. 2. Chains pack with no specific intermolecular interactions between them, Fig. 3.

Related literature top

For a general description of the synthesis of higher terpenoids using the Diels–Alder reaction, see: Brocksom et al. (2001). For the synthesis of a similar compound containing an N atom in place of the O atom, see: Vieira et al. (2007). For the synthesis, see: Finelli (2004). For additional conformational analysis, see: Cremer & Pople (1975).

Experimental top

The catalytic reaction was carried out using 2,6-dimethylcyclohexa-2,5- diene-1,4-dione (83 mg, 0.61 mmol) in anhydrous dichloromethane (1.2 ml) under nitrogen atmosphere at 293 K, and then zinc chloride (91.5 mg, 0.61 mmol) was added. After 40 min stirring, diastereomeric 5-(tert-butyl-dimethyl-silyloxy)-pentadiene-2,4 (71 mg, 0.36 mmol) was slowly added. After 20 h stirring the reaction was ended by adding a saturated solution of NaHCO₃. The organic phase was extracted with dichloromethane, dried with Na₂SO₄ and concentrated on a rota-vapor. The product was purified using a silica gel chromatography column with hexane/ethyl acetate (98:2) as the eluent, yielding compound (I) (131 mg, 0.39 mmol). Crystals were grown by slow evaporation from a solution of 15% of acetyl acetate in hexane at 293 K; M.pt: 384.3–386.5 K. ¹H-NMR (CDCl₃, p.p.m., 400 MHz): δ 6.58 (d, 1H, J = 1.5 Hz); 5.73 (d, 1H, J = 10.1 Hz); 5.63 (ddd, 1H, J = 10.1 Hz, J = 4.4 Hz, J = 3.1 Hz); 3.85 (d, 1H, J = 4.4 Hz); 2.90 (d, 1H, J = 4.9 Hz); 2.43–2.49 (m, 1H); 1.92 (d, 3H, J = 1.5 Hz); 1.45 (d, 3H, J = 7.6 Hz); 1.32 (s, 3H); 0.73 (s, 9H); -0.03 (s, 3H); -0.13 (s, 3H); ¹³C (CDCl₃, 50 MHz) δ (p.p.m.) 202.1; 197.7; 147.4; 141.1; 133.1; 125.1; 71.6; 54.2; 53.4; 28.8; 25.5; 19.4; 17.8; 17.2; 16.2; -4.6; -5.2. Anal. calcd for C₁₉H₃₀O₃Si₁: C, 68.22; H, 9.04. Found: C, 68.00; H, 9.21.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SIR92 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2006) and MarvinSketch (ChemAxon, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of compound (I) showing atom labelling scheme and displacement ellipsoids at the 50% probability level (arbitrary spheres for the H atoms).
	Fig. 2. A view of the linear supramolecular chain sustained by C—H···O interactions (orange dashed lines) in the crystal structure of (I).
	Fig. 3. A view in projection down the b axis of the unit-cell contents of (I).

(±)-(4aR,5R,8S,8aR)-8-(tert-Butyldimethylsilyloxy)-2,5,8a-trimethyl-4a,5,8,8a-tetrahydronaphthalene-1,4-dione top

Crystal data top

C₁₉H₃₀O₃Si	F(000) = 728
M_r = 334.52	D_x = 1.127 Mg m⁻³
Monoclinic, P2/c	Melting point: 385.4 K
Hall symbol: -P 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 15.325 (2) Å	Cell parameters from 25 reflections
b = 7.1744 (9) Å	θ = 2.8–27.0°
c = 17.965 (2) Å	µ = 0.13 mm⁻¹
β = 93.577 (9)°	T = 293 K
V = 1971.4 (4) Å³	Prism, colourless
Z = 4	0.15 × 0.10 × 0.08 mm

Data collection top

Enraf–Nonius CAD-4 MACH 3 diffractometer	R_int = 0.072
Radiation source: fine-focus sealed tube	θ_max = 27.0°, θ_min = 2.8°
Graphite monochromator	h = −19→19
ω–2θ scans	k = 0→9
4451 measured reflections	l = 0→22
4305 independent reflections	3 standard reflections every 30 min
1463 reflections with I > 2σ(I)	intensity decay: 1.4%

Refinement top

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.165	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.0596P)²] where P = (F_o² + 2F_c²)/3
4305 reflections	(Δ/σ)_max < 0.001
216 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₉H₃₀O₃Si	V = 1971.4 (4) Å³
M_r = 334.52	Z = 4
Monoclinic, P2/c	Mo Kα radiation
a = 15.325 (2) Å	µ = 0.13 mm⁻¹
b = 7.1744 (9) Å	T = 293 K
c = 17.965 (2) Å	0.15 × 0.10 × 0.08 mm
β = 93.577 (9)°

Data collection top

Enraf–Nonius CAD-4 MACH 3 diffractometer	R_int = 0.072
4451 measured reflections	3 standard reflections every 30 min
4305 independent reflections	intensity decay: 1.4%
1463 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.165	H-atom parameters constrained
S = 0.93	Δρ_max = 0.17 e Å⁻³
4305 reflections	Δρ_min = −0.21 e Å⁻³
216 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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

	x	y	z	U_iso*/U_eq
Si1	0.70796 (7)	0.41802 (16)	0.45217 (6)	0.0549 (4)
O3	0.76651 (14)	0.3088 (3)	0.51880 (11)	0.0453 (6)
O1	0.70503 (18)	0.4837 (5)	0.68020 (16)	0.0882 (10)
O2	0.83093 (19)	−0.1189 (4)	0.57148 (16)	0.0785 (9)
C5	0.8725 (2)	0.1309 (5)	0.65576 (18)	0.0487 (10)
H5	0.8723	0.1034	0.7092	0.058*
C10	0.8338 (2)	0.3308 (5)	0.64516 (18)	0.0455 (9)
C9	0.8372 (2)	0.3907 (5)	0.56306 (18)	0.0492 (10)
H9	0.8317	0.5266	0.5602	0.059*
C8	0.9210 (2)	0.3353 (6)	0.5317 (2)	0.0617 (12)
H8	0.9339	0.3873	0.4863	0.074*
C6	0.9670 (2)	0.1243 (6)	0.6364 (2)	0.0596 (11)
H6	0.9993	0.2009	0.6740	0.072*
C1	0.7382 (3)	0.3361 (7)	0.6645 (2)	0.0576 (11)
C7	0.9777 (3)	0.2191 (6)	0.5632 (2)	0.0642 (12)
H7	1.0279	0.1935	0.5385	0.077*
C4	0.8100 (3)	−0.0050 (6)	0.6171 (2)	0.0569 (11)
C2	0.6855 (3)	0.1634 (8)	0.6628 (2)	0.0618 (12)
C16	0.6517 (2)	0.2288 (6)	0.3974 (2)	0.0602 (11)
C3	0.7200 (3)	0.0080 (7)	0.6393 (2)	0.0666 (12)
H3	0.6856	−0.0988	0.6367	0.080*
C13	0.8858 (2)	0.4707 (6)	0.6949 (2)	0.0721 (13)
H13A	0.8557	0.5881	0.6940	0.108*
H13B	0.9429	0.4873	0.6766	0.108*
H13C	0.8914	0.4244	0.7451	0.108*
C17	0.5897 (3)	0.3084 (7)	0.3356 (2)	0.1014 (17)
H17A	0.6225	0.3792	0.3016	0.152*
H17B	0.5476	0.3880	0.3571	0.152*
H17C	0.5599	0.2083	0.3092	0.152*
C12	1.0098 (3)	−0.0693 (6)	0.6413 (2)	0.0899 (15)
H12A	1.0013	−0.1231	0.6893	0.135*
H12B	1.0713	−0.0578	0.6348	0.135*
H12C	0.9835	−0.1481	0.6029	0.135*
C18	0.5973 (3)	0.1114 (6)	0.4485 (3)	0.1031 (17)
H18A	0.5694	0.0120	0.4203	0.155*
H18B	0.5536	0.1884	0.4691	0.155*
H18C	0.6348	0.0601	0.4882	0.155*
C14	0.6293 (3)	0.5766 (6)	0.4944 (2)	0.0964 (16)
H14A	0.5923	0.5059	0.5250	0.145*
H14B	0.5942	0.6378	0.4556	0.145*
H14C	0.6608	0.6681	0.5244	0.145*
C15	0.7796 (3)	0.5561 (7)	0.3940 (2)	0.0972 (17)
H15A	0.8082	0.6518	0.4239	0.146*
H15B	0.7451	0.6122	0.3536	0.146*
H15C	0.8228	0.4759	0.3744	0.146*
C11	0.5927 (2)	0.1811 (7)	0.6844 (2)	0.1013 (17)
H11A	0.5651	0.0610	0.6819	0.152*
H11B	0.5615	0.2653	0.6509	0.152*
H11C	0.5922	0.2283	0.7344	0.152*
C19	0.7175 (3)	0.1042 (8)	0.3628 (3)	0.135 (2)
H19A	0.6879	0.0001	0.3391	0.202*
H19B	0.7591	0.0599	0.4009	0.202*
H19C	0.7475	0.1734	0.3264	0.202*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Si1	0.0648 (7)	0.0482 (7)	0.0504 (6)	−0.0054 (6)	−0.0060 (5)	0.0073 (6)
O3	0.0514 (14)	0.0420 (16)	0.0413 (13)	−0.0090 (13)	−0.0070 (11)	0.0005 (12)
O1	0.093 (2)	0.083 (3)	0.090 (2)	0.018 (2)	0.0228 (18)	−0.013 (2)
O2	0.109 (2)	0.051 (2)	0.074 (2)	−0.0013 (18)	0.0003 (17)	−0.0124 (17)
C5	0.057 (2)	0.054 (3)	0.035 (2)	0.001 (2)	0.0004 (18)	0.0003 (19)
C10	0.049 (2)	0.046 (2)	0.041 (2)	−0.001 (2)	−0.0005 (17)	−0.0072 (19)
C9	0.056 (2)	0.044 (2)	0.047 (2)	−0.011 (2)	−0.0034 (19)	0.002 (2)
C8	0.054 (3)	0.081 (3)	0.050 (2)	−0.020 (2)	0.006 (2)	0.012 (2)
C6	0.057 (3)	0.068 (3)	0.053 (2)	0.007 (2)	−0.004 (2)	−0.006 (2)
C1	0.072 (3)	0.061 (3)	0.039 (2)	0.006 (3)	0.000 (2)	−0.004 (2)
C7	0.048 (3)	0.080 (3)	0.064 (3)	−0.007 (2)	0.004 (2)	−0.004 (3)
C4	0.086 (3)	0.040 (3)	0.044 (2)	0.002 (3)	−0.003 (2)	0.006 (2)
C2	0.054 (3)	0.083 (4)	0.049 (2)	−0.005 (3)	0.002 (2)	0.014 (3)
C16	0.062 (3)	0.060 (3)	0.056 (2)	−0.002 (2)	−0.017 (2)	0.001 (2)
C3	0.070 (3)	0.064 (3)	0.066 (3)	−0.020 (3)	0.005 (2)	0.012 (3)
C13	0.086 (3)	0.067 (3)	0.060 (3)	−0.004 (3)	−0.016 (2)	−0.021 (2)
C17	0.110 (4)	0.106 (4)	0.082 (3)	−0.016 (3)	−0.048 (3)	0.015 (3)
C12	0.088 (3)	0.099 (4)	0.082 (3)	0.040 (3)	0.001 (3)	0.008 (3)
C18	0.125 (4)	0.083 (4)	0.097 (4)	−0.044 (3)	−0.032 (3)	0.019 (3)
C14	0.103 (4)	0.077 (4)	0.107 (4)	0.027 (3)	−0.008 (3)	−0.012 (3)
C15	0.104 (3)	0.108 (4)	0.077 (3)	−0.031 (3)	−0.013 (3)	0.050 (3)
C11	0.061 (3)	0.145 (5)	0.100 (4)	−0.007 (3)	0.020 (3)	0.019 (4)
C19	0.129 (5)	0.143 (6)	0.128 (4)	0.038 (4)	−0.026 (4)	−0.080 (4)

Geometric parameters (Å, º) top

Si1—O3	1.649 (2)	C16—C17	1.527 (5)
Si1—C15	1.850 (4)	C16—C18	1.531 (5)
Si1—C14	1.853 (4)	C3—H3	0.9300
Si1—C16	1.858 (4)	C13—H13A	0.9600
O3—C9	1.430 (3)	C13—H13B	0.9600
O1—C1	1.215 (4)	C13—H13C	0.9600
O2—C4	1.215 (4)	C17—H17A	0.9600
C5—C4	1.505 (5)	C17—H17B	0.9600
C5—C6	1.511 (4)	C17—H17C	0.9600
C5—C10	1.559 (5)	C12—H12A	0.9600
C5—H5	0.9800	C12—H12B	0.9600
C10—C1	1.528 (5)	C12—H12C	0.9600
C10—C13	1.533 (4)	C18—H18A	0.9600
C10—C9	1.540 (4)	C18—H18B	0.9600
C9—C8	1.487 (4)	C18—H18C	0.9600
C9—H9	0.9800	C14—H14A	0.9600
C8—C7	1.307 (5)	C14—H14B	0.9600
C8—H8	0.9300	C14—H14C	0.9600
C6—C7	1.500 (5)	C15—H15A	0.9600
C6—C12	1.536 (5)	C15—H15B	0.9600
C6—H6	0.9800	C15—H15C	0.9600
C1—C2	1.478 (6)	C11—H11A	0.9600
C7—H7	0.9300	C11—H11B	0.9600
C4—C3	1.462 (5)	C11—H11C	0.9600
C2—C3	1.315 (5)	C19—H19A	0.9600
C2—C11	1.503 (5)	C19—H19B	0.9600
C16—C19	1.510 (5)	C19—H19C	0.9600

O3—Si1—C15	110.43 (15)	C2—C3—C4	123.2 (4)
O3—Si1—C14	109.46 (17)	C2—C3—H3	118.4
C15—Si1—C14	109.1 (2)	C4—C3—H3	118.4
O3—Si1—C16	104.54 (16)	C10—C13—H13A	109.5
C15—Si1—C16	111.4 (2)	C10—C13—H13B	109.5
C14—Si1—C16	111.9 (2)	H13A—C13—H13B	109.5
C9—O3—Si1	124.6 (2)	C10—C13—H13C	109.5
C4—C5—C6	117.7 (3)	H13A—C13—H13C	109.5
C4—C5—C10	108.3 (3)	H13B—C13—H13C	109.5
C6—C5—C10	111.3 (3)	C16—C17—H17A	109.5
C4—C5—H5	106.3	C16—C17—H17B	109.5
C6—C5—H5	106.3	H17A—C17—H17B	109.5
C10—C5—H5	106.3	C16—C17—H17C	109.5
C1—C10—C13	108.8 (3)	H17A—C17—H17C	109.5
C1—C10—C9	107.5 (3)	H17B—C17—H17C	109.5
C13—C10—C9	109.1 (3)	C6—C12—H12A	109.5
C1—C10—C5	111.0 (3)	C6—C12—H12B	109.5
C13—C10—C5	110.6 (3)	H12A—C12—H12B	109.5
C9—C10—C5	109.8 (3)	C6—C12—H12C	109.5
O3—C9—C8	108.8 (3)	H12A—C12—H12C	109.5
O3—C9—C10	110.4 (3)	H12B—C12—H12C	109.5
C8—C9—C10	111.7 (3)	C16—C18—H18A	109.5
O3—C9—H9	108.6	C16—C18—H18B	109.5
C8—C9—H9	108.6	H18A—C18—H18B	109.5
C10—C9—H9	108.6	C16—C18—H18C	109.5
C7—C8—C9	125.0 (4)	H18A—C18—H18C	109.5
C7—C8—H8	117.5	H18B—C18—H18C	109.5
C9—C8—H8	117.5	Si1—C14—H14A	109.5
C7—C6—C5	110.2 (3)	Si1—C14—H14B	109.5
C7—C6—C12	113.0 (3)	H14A—C14—H14B	109.5
C5—C6—C12	115.3 (3)	Si1—C14—H14C	109.5
C7—C6—H6	105.8	H14A—C14—H14C	109.5
C5—C6—H6	105.8	H14B—C14—H14C	109.5
C12—C6—H6	105.8	Si1—C15—H15A	109.5
O1—C1—C2	119.9 (4)	Si1—C15—H15B	109.5
O1—C1—C10	119.7 (4)	H15A—C15—H15B	109.5
C2—C1—C10	120.3 (4)	Si1—C15—H15C	109.5
C8—C7—C6	124.2 (4)	H15A—C15—H15C	109.5
C8—C7—H7	117.9	H15B—C15—H15C	109.5
C6—C7—H7	117.9	C2—C11—H11A	109.5
O2—C4—C3	121.4 (4)	C2—C11—H11B	109.5
O2—C4—C5	124.0 (4)	H11A—C11—H11B	109.5
C3—C4—C5	114.6 (4)	C2—C11—H11C	109.5
C3—C2—C1	119.1 (4)	H11A—C11—H11C	109.5
C3—C2—C11	124.1 (5)	H11B—C11—H11C	109.5
C1—C2—C11	116.7 (5)	C16—C19—H19A	109.5
C19—C16—C17	108.9 (4)	C16—C19—H19B	109.5
C19—C16—C18	108.9 (4)	H19A—C19—H19B	109.5
C17—C16—C18	107.8 (3)	C16—C19—H19C	109.5
C19—C16—Si1	110.5 (3)	H19A—C19—H19C	109.5
C17—C16—Si1	111.0 (3)	H19B—C19—H19C	109.5
C18—C16—Si1	109.6 (3)

C15—Si1—O3—C9	43.4 (3)	C9—C10—C1—C2	97.9 (4)
C14—Si1—O3—C9	−76.6 (3)	C5—C10—C1—C2	−22.1 (4)
C16—Si1—O3—C9	163.3 (2)	C9—C8—C7—C6	−0.4 (6)
C4—C5—C10—C1	48.9 (4)	C5—C6—C7—C8	18.3 (5)
C6—C5—C10—C1	179.8 (3)	C12—C6—C7—C8	148.9 (4)
C4—C5—C10—C13	169.7 (3)	C6—C5—C4—O2	−0.1 (5)
C6—C5—C10—C13	−59.4 (4)	C10—C5—C4—O2	127.1 (4)
C4—C5—C10—C9	−69.8 (4)	C6—C5—C4—C3	179.2 (3)
C6—C5—C10—C9	61.1 (4)	C10—C5—C4—C3	−53.5 (4)
Si1—O3—C9—C8	−98.3 (3)	O1—C1—C2—C3	174.0 (4)
Si1—O3—C9—C10	138.8 (2)	C10—C1—C2—C3	−4.9 (5)
C1—C10—C9—O3	−41.2 (4)	O1—C1—C2—C11	−2.5 (5)
C13—C10—C9—O3	−159.0 (3)	C10—C1—C2—C11	178.6 (3)
C5—C10—C9—O3	79.6 (3)	O3—Si1—C16—C19	−62.5 (3)
C1—C10—C9—C8	−162.3 (3)	C15—Si1—C16—C19	56.7 (4)
C13—C10—C9—C8	79.8 (4)	C14—Si1—C16—C19	179.1 (3)
C5—C10—C9—C8	−41.5 (4)	O3—Si1—C16—C17	176.5 (3)
O3—C9—C8—C7	−109.2 (4)	C15—Si1—C16—C17	−64.3 (3)
C10—C9—C8—C7	12.9 (5)	C14—Si1—C16—C17	58.1 (4)
C4—C5—C6—C7	78.1 (4)	O3—Si1—C16—C18	57.5 (3)
C10—C5—C6—C7	−47.7 (4)	C15—Si1—C16—C18	176.8 (3)
C4—C5—C6—C12	−51.2 (4)	C14—Si1—C16—C18	−60.9 (3)
C10—C5—C6—C12	−177.0 (3)	C1—C2—C3—C4	2.4 (6)
C13—C10—C1—O1	37.1 (5)	C11—C2—C3—C4	178.7 (3)
C9—C10—C1—O1	−81.0 (4)	O2—C4—C3—C2	−151.9 (4)
C5—C10—C1—O1	159.0 (3)	C5—C4—C3—C2	28.7 (5)
C13—C10—C1—C2	−144.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O2ⁱ	0.98	2.55	3.524 (5)	171

Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₉H₃₀O₃Si
M_r	334.52
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	293
a, b, c (Å)	15.325 (2), 7.1744 (9), 17.965 (2)
β (°)	93.577 (9)
V (Å³)	1971.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.15 × 0.10 × 0.08

Data collection
Diffractometer	Enraf–Nonius CAD-4 MACH 3 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4451, 4305, 1463
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.165, 0.93
No. of reflections	4305
No. of parameters	216
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.21

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), MolEN (Fair, 1990), SIR92 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2006) and MarvinSketch (ChemAxon, 2009), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O2ⁱ	0.98	2.55	3.524 (5)	171

Symmetry code: (i) x, y+1, z.

Acknowledgements

We thank CNPq (142088/2011–0 to FND, 306532/2009–3 to JZS), FAPESP (2011/13993–2 to TJB), and CAPES (grant No. 808/2009 to JZS) for financial support. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR-MOHE/SC/12)

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Brocksom, T. J., Correa, A. G., Naves, R. M., Silva, F. Jr, Catani, V., Ceschi, M. A., Zukerman-Schpector, J., Toloi, A. P., Ferreira, M. L. & Brocksom, U. (2001). Diels–Alder Reactions in the Synthesis of Higher Terpenes, in Organic Synthesis: Theory and Applications, Vol. 5, edited by T. Hudlicky, pp. 390–87. London: JAI/Elsevier Science. Google Scholar
ChemAxon (2009). MarvinSketch. www.chemaxon.com. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Fair, C. K. (1990). MolEN. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Finelli, F. G. (2004). MSc thesis, Universidade Federal de São Carlos, Brazil. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vieira, Y. W., Nakamura, J., Finelli, F. G., Brocksom, U. & Brocksom, T. J. (2007). J. Braz. Chem. Soc. 18, 448–451. Web of Science CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(±)-(4aR,5R,8S,8aR)-8-(tert-Butyl­di­methyl­sil­yl­oxy)-2,5,8a-tri­methyl-4a,5,8,8a-tetra­hydro­naphthalene-1,4-dione

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(±)-(4aR,5R,8S,8aR)-8-(tert-Butyldimethylsilyloxy)-2,5,8a-trimethyl-4a,5,8,8a-tetrahydronaphthalene-1,4-dione