Crystal structure of 3a,6,6,9a-tetra­methyl­dodeca­hydro­naphtho­[2,1-b]furan-2-ol

Shi, X.-W.; Li, S.-K.; Li, D.-D.; Lu, Q.-Q.

doi:10.1107/S2056989015016370

organic compounds

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Volume 71| Part 10| October 2015| Pages o710-o711

doi:10.1107/S2056989015016370

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Crystal structure of 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan-2-ol

Xin-Wei Shi,^a Sheng-Kun Li,^b ^* Dang-Dang Li ^b and Qiang-Qiang Lu ^a

^aXi'an Botanical Garden, Institute of Botany of Shaanxi Province, Xi'an 710061, People's Republic of China, and ^bLab for Pesticide Synthesis, Department of Pesticide Science, College of Plant Protection, Nanjing Agricultural University, Weigang 1, Xuanwu District, Nanjing 210095, People's Republic of China
^*Correspondence e-mail: saintkun001@njau.edu.cn

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 29 August 2015; accepted 2 September 2015; online 12 September 2015)

The title compound (common name: sclaral), C₁₆H₂₈O₂, is a sclareolide derivative, which was synthesized from sclareolide itself. In the molecule, the two six-membered rings, A and B, of the labdane skeleton adopt chair conformations and the five-membered O-containing heterocyclic ring C displays an envelope conformation, with the methine C atom of the fused C—C bond as the flap. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, forming chains propagating along [100].

Keywords: crystal structure; sclareolide; sclaral; hydrogen bonding.

CCDC reference: 1421899

1. Related literature

For the chemistry and biological importance of sclareolides and the title compound, see: Dixon et al. (2012 ); Michaudel et al. (2015 ); Sun et al. (2013 ). For previously reported spectroscopic and analytical data for the title compound, see: Margaros et al. (2007 ). For related structures, see: Martínez-Carrera et al. (1978 ); Huang et al. (2008 ).

2. Experimental

2.1. Crystal data

C₁₆H₂₈O₂
M_r = 252.38
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.1675 (8) Å
b = 11.2654 (13) Å
c = 18.144 (2) Å
V = 1465.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 296 K
0.22 × 0.20 × 0.18 mm

2.2. Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.984, T_max = 0.987
9607 measured reflections
2658 independent reflections
2299 reflections with I > 2σ(I)
R_int = 0.030

2.3. Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.127
S = 1.08
2658 reflections
181 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1O⋯O1ⁱ	0.93 (2)	1.90 (2)	2.773 (2)	155 (3)
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1421899

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S2056989015016370/su5201sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015016370/su5201Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015016370/su5201Isup3.cdx

Supporting information file. DOI: 10.1107/S2056989015016370/su5201Isup4.cml

checkCIF report

Comment top

The title compound, sclaral, is an important reaction intermediate in the synthesis of some natural products. It is used as a precursor of borono-sclareolide which makes the direct coupling of a terpenoid "donor" with a non-terpenoid "acceptor" possible (Dixon et al., 2012). It is also used to produce analogs of hongoquercin A, an antibiotic of fungal origin (Michaudel et al., 2015; Sun et al., 2013). Moreover, sclaral is an intermediate in the production of important natural products, such as (+)-premnalane A (Margaros et al., 2007). The title compound has been synthesized and we report herein on its crystal structure,

The molecular structure of the title compound is shown in Fig. 1. The molecule possesses a highly rigid structure, composed of three main rings (A/i>, B and C). The six-membered rings, A/i> (C5/C6/C8—C11) and B (C1—C6), adopt chair conformations, while the five-membered O-containing heterocyclic ring C (C1/C2/C14/C15/O1) displays an envelope conformation, in which atom C1 is the flap.

In the crystal, molecules are linked via O—H···O hydrogen bonds forming chains propagating along the a axis direction (Table 1 and Fig. 2).

Synthesis and crystallization top

A solution of (+)-sclareolide (10.0 g, 40.0 mmol,1.0 eq) in CH₂Cl₂ (100ml) was cooled to 195 K and DIBAL-H (1.5M in toluene,32ml, 48.0 mmol, 1.2 eq) was added drop wise over 20 min, and stirring was continued for an additional 60 min. Water was then slowly added until the bubbles vanished then the temperature of the mixture was allow to rise to rt. the mixture was stirred at rt for 30min, and then extracted with CH₂Cl₂ (3 × 100 ml). The combined organic extracts were washed with saturated aqueous NaHCO₃ solution (3 × 50 ml) and washed with brine (3 × 50 ml), dried over MgSO₄, filtered and concentrated under reduced pressure, affording the title compound, sclaral (yield: 9.37 g, 93 %, 3.7:1 lactol:aldehyde) as a white solid. Spectroscopic and analytical data matches reported previously (Margaros et al., 2007). The white solid was recrystallized from EtOH to afford colourless crystals.

Refinement top

The CH H atoms (H1, H5 and H15) and the hydroxyl H atom (H1O) were located in a difference Fourier map. The CH H atoms were freely refined while the OH H atom was refined with U_iso(H) = 1.5U_eq(O). The remaining C-bound H atoms were placed in calculated positions and refined as riding: C—H = 0.96-0.97 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms.

Related literature top

For the chemistry and biological importance of sclareolides and the title compound, see: Dixon et al. (2012); Michaudel et al. (2015); Sun et al. (2013). For the spectroscopic and analytical data of the title compound, reported previously, see: Margaros et al. (2007). For related structures, see: Martínez-Carrera et al. (1978); Huang et al. (2008).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. View along the a axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1), and C-bound H atoms have been omitted for clarity.

3a,6,6,9a-Tetramethyldodecahydronaphtho[2,1-b]furan-2-ol top

Crystal data top

C₁₆H₂₈O₂	F(000) = 560
M_r = 252.38	D_x = 1.144 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2540 reflections
a = 7.1675 (8) Å	θ = 3.1–21.6°
b = 11.2654 (13) Å	µ = 0.07 mm⁻¹
c = 18.144 (2) Å	T = 296 K
V = 1465.0 (3) Å³	Block, colourless
Z = 4	0.22 × 0.20 × 0.18 mm

Data collection top

Bruker SMART CCD diffractometer	2658 independent reflections
Radiation source: fine-focus sealed tube	2299 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
phi and ω scans	θ_max = 25.3°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −8→8
T_min = 0.984, T_max = 0.987	k = −13→13
9607 measured reflections	l = −21→16

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0651P)² + 0.258P] where P = (F_o² + 2F_c²)/3
2658 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.40 e Å⁻³
1 restraint	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₆H₂₈O₂	V = 1465.0 (3) Å³
M_r = 252.38	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.1675 (8) Å	µ = 0.07 mm⁻¹
b = 11.2654 (13) Å	T = 296 K
c = 18.144 (2) Å	0.22 × 0.20 × 0.18 mm

Data collection top

Bruker SMART CCD diffractometer	2658 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	2299 reflections with I > 2σ(I)
T_min = 0.984, T_max = 0.987	R_int = 0.030
9607 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	1 restraint
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.40 e Å⁻³
2658 reflections	Δρ_min = −0.19 e Å⁻³
181 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

	x	y	z	U_iso*/U_eq
C1	0.0482 (3)	0.86847 (19)	0.67801 (12)	0.0348 (5)
C2	0.2058 (3)	0.8474 (2)	0.62309 (12)	0.0392 (5)
C3	0.3421 (3)	0.7594 (2)	0.65591 (13)	0.0469 (6)
H3A	0.4488	0.7504	0.6235	0.056*
H3B	0.2825	0.6826	0.6612	0.056*
C4	0.4067 (3)	0.8050 (2)	0.73202 (13)	0.0443 (5)
H4A	0.4901	0.7471	0.7539	0.053*
H4B	0.4759	0.8783	0.7255	0.053*
C5	0.2429 (3)	0.82737 (18)	0.78462 (12)	0.0342 (5)
C6	0.1029 (3)	0.91962 (17)	0.75332 (11)	0.0339 (5)
C7	0.1778 (4)	1.04780 (19)	0.74731 (14)	0.0515 (6)
H7A	0.1100	1.0896	0.7098	0.077*
H7B	0.3078	1.0459	0.7347	0.077*
H7C	0.1620	1.0875	0.7937	0.077*
C8	−0.0711 (3)	0.9208 (3)	0.80299 (14)	0.0519 (6)
H8A	−0.1541	0.9836	0.7869	0.062*
H8B	−0.1368	0.8460	0.7976	0.062*
C9	−0.0233 (4)	0.9397 (3)	0.88443 (15)	0.0655 (8)
H9A	0.0283	1.0186	0.8910	0.079*
H9B	−0.1363	0.9343	0.9136	0.079*
C10	0.1147 (4)	0.8493 (3)	0.91114 (14)	0.0620 (8)
H10A	0.0560	0.7717	0.9097	0.074*
H10B	0.1444	0.8665	0.9622	0.074*
C11	0.2970 (3)	0.8434 (2)	0.86729 (13)	0.0462 (6)
C12	0.4061 (5)	0.7330 (3)	0.89311 (17)	0.0775 (9)
H12A	0.5323	0.7377	0.8756	0.116*
H12B	0.3480	0.6628	0.8738	0.116*
H12C	0.4059	0.7298	0.9460	0.116*
C13	0.4176 (4)	0.9519 (3)	0.88354 (15)	0.0579 (7)
H13A	0.5198	0.9547	0.8494	0.087*
H13B	0.4652	0.9468	0.9329	0.087*
H13C	0.3438	1.0226	0.8786	0.087*
C14	−0.1012 (4)	0.9213 (2)	0.62815 (14)	0.0520 (6)
H14A	−0.0739	1.0033	0.6157	0.062*
H14B	−0.2240	0.9166	0.6504	0.062*
C15	−0.0850 (3)	0.8402 (2)	0.56099 (14)	0.0495 (6)
H15	−0.112 (4)	0.884 (2)	0.5155 (15)	0.059*
C16	0.3106 (4)	0.9544 (3)	0.59153 (15)	0.0622 (7)
H16A	0.3743	0.9313	0.5472	0.093*
H16B	0.3997	0.9823	0.6270	0.093*
H16C	0.2234	1.0166	0.5805	0.093*
H1	0.007 (3)	0.7879 (18)	0.6884 (10)	0.024 (5)*
H5	0.168 (3)	0.751 (2)	0.7848 (12)	0.040 (6)*
O1	0.1024 (2)	0.79612 (16)	0.56104 (8)	0.0520 (5)
O2	−0.2051 (3)	0.7454 (2)	0.56902 (11)	0.0678 (6)
H1O	−0.242 (4)	0.715 (3)	0.5234 (11)	0.081*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0291 (10)	0.0358 (11)	0.0396 (11)	0.0007 (9)	0.0009 (9)	−0.0037 (9)
C2	0.0342 (10)	0.0491 (12)	0.0342 (11)	−0.0040 (10)	0.0055 (10)	−0.0055 (10)
C3	0.0352 (11)	0.0571 (14)	0.0485 (14)	0.0072 (11)	0.0082 (11)	−0.0129 (11)
C4	0.0313 (10)	0.0529 (13)	0.0485 (14)	0.0097 (10)	0.0001 (10)	−0.0055 (10)
C5	0.0331 (10)	0.0328 (10)	0.0368 (11)	−0.0020 (9)	0.0018 (9)	−0.0018 (9)
C6	0.0270 (9)	0.0355 (10)	0.0393 (11)	0.0012 (9)	0.0011 (9)	−0.0073 (9)
C7	0.0607 (15)	0.0336 (12)	0.0601 (15)	0.0041 (11)	−0.0055 (13)	−0.0088 (11)
C8	0.0304 (11)	0.0749 (16)	0.0503 (14)	0.0045 (11)	0.0059 (11)	−0.0221 (13)
C9	0.0430 (13)	0.104 (2)	0.0498 (15)	−0.0091 (15)	0.0137 (12)	−0.0322 (16)
C10	0.0613 (16)	0.090 (2)	0.0352 (13)	−0.0243 (16)	0.0041 (13)	−0.0063 (13)
C11	0.0474 (13)	0.0528 (13)	0.0385 (12)	−0.0035 (11)	−0.0058 (11)	−0.0025 (10)
C12	0.092 (2)	0.078 (2)	0.0620 (18)	0.0127 (19)	−0.0247 (18)	0.0158 (15)
C13	0.0434 (13)	0.0751 (17)	0.0551 (15)	−0.0065 (13)	−0.0103 (13)	−0.0149 (14)
C14	0.0439 (13)	0.0601 (15)	0.0520 (14)	0.0096 (12)	−0.0092 (12)	−0.0063 (12)
C15	0.0407 (12)	0.0673 (15)	0.0404 (13)	−0.0035 (12)	−0.0050 (11)	−0.0024 (12)
C16	0.0648 (16)	0.0754 (18)	0.0463 (14)	−0.0191 (15)	0.0090 (14)	0.0086 (13)
O1	0.0417 (8)	0.0749 (11)	0.0393 (9)	−0.0020 (9)	0.0020 (8)	−0.0166 (8)
O2	0.0591 (11)	0.0950 (15)	0.0494 (11)	−0.0205 (11)	−0.0057 (10)	−0.0045 (10)

Geometric parameters (Å, º) top

C1—C14	1.523 (3)	C6—C8	1.539 (3)
C1—C2	1.525 (3)	C6—C7	1.544 (3)
C1—C6	1.534 (3)	C8—C9	1.532 (4)
C2—O1	1.466 (3)	C9—C10	1.500 (4)
C2—C3	1.513 (3)	C10—C11	1.531 (3)
C2—C16	1.531 (3)	C11—C13	1.526 (3)
C3—C4	1.544 (3)	C11—C12	1.542 (4)
C4—C5	1.534 (3)	C14—C15	1.527 (3)
C5—C6	1.552 (3)	C15—O2	1.380 (3)
C5—C11	1.560 (3)	C15—O1	1.432 (3)

C14—C1—C2	101.16 (18)	C1—C6—C5	103.87 (16)
C14—C1—C6	124.19 (19)	C8—C6—C5	108.38 (18)
C2—C1—C6	116.81 (16)	C7—C6—C5	115.30 (17)
O1—C2—C3	111.75 (18)	C9—C8—C6	112.63 (18)
O1—C2—C1	100.87 (15)	C10—C9—C8	111.4 (2)
C3—C2—C1	108.84 (18)	C9—C10—C11	115.1 (2)
O1—C2—C16	105.71 (18)	C13—C11—C10	110.4 (2)
C3—C2—C16	110.26 (19)	C13—C11—C12	107.4 (2)
C1—C2—C16	119.00 (19)	C10—C11—C12	108.0 (2)
C2—C3—C4	109.12 (18)	C13—C11—C5	114.8 (2)
C5—C4—C3	112.42 (17)	C10—C11—C5	107.00 (18)
C4—C5—C6	112.15 (17)	C12—C11—C5	109.0 (2)
C4—C5—C11	115.27 (17)	C1—C14—C15	100.75 (19)
C6—C5—C11	115.79 (17)	O2—C15—O1	108.5 (2)
C1—C6—C8	108.51 (17)	O2—C15—C14	109.4 (2)
C1—C6—C7	112.17 (19)	O1—C15—C14	106.16 (19)
C8—C6—C7	108.36 (19)	C15—O1—C2	109.75 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O···O1ⁱ	0.93 (2)	1.90 (2)	2.773 (2)	155 (3)

Symmetry code: (i) x−1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O···O1ⁱ	0.934 (18)	1.90 (2)	2.773 (2)	155 (3)

Symmetry code: (i) x−1/2, −y+3/2, −z+1.

Acknowledgements

This project was supported by the National Natural Science Foundation of China (Nos. 3140177 and 31200257), the West Light Foundation of The Chinese Academy of Sciences (No. 2012DF05), and the National Science Foundation of Jiangsu Province (No. BK20140684).

References

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Volume 71| Part 10| October 2015| Pages o710-o711

doi:10.1107/S2056989015016370

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Crystal structure of 3a,6,6,9a-tetra­methyl­dodeca­hydro­naphtho­[2,1-b]furan-2-ol

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

Crystal structure of 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan-2-ol