(4aR,6aS,10aR,10bS)-7,7,10a-Trimethyl-1,4,4a,5,6,6a,7,8,9,10,10a,10b-dodecahydro-2H-naphtho-[2,1-c]pyran (Pyamber).

The crystal structure of the title compound, C(16)H(28)O, features C-H⋯O hydrogen bonds making C(6) zigzag chains along one 2(1) screw axis. Within the limits of the data collection affected by crystal quality, the Hooft parameter gave correct indications of the known molecular chirality based on the single O atom anomalous dispersion in contrast to the indeterminate Flack value. Synthetic steps starting from manool are reported.

Related literature

For details of the synthesis, see: Evans & Grant (1997 ▶); Grant et al. (1988 ▶); Vlad et al. (1978 ▶, 1983 ▶). For the related structure methyl 8,9-ep­oxy-12-oxo-13-oxototarane-14β-carboxyl­ate, see: Cambie et al. (1988 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For determination of absolute configuration, see: Hooft et al. (2008 ▶).

Experimental

Crystal data

C16H28O

M = 236.38

Orthorhombic,

a = 7.3497 (2) Å

b = 11.1642 (3) Å

c = 17.0758 (12) Å

V = 1401.13 (11) Å3

Z = 4

Cu Kα radiation

μ = 0.50 mm−1

T = 123 K

0.70 × 0.40 × 0.13 mm

Data collection

Rigaku Spider diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.687, T max = 1.0

5141 measured reflections

1969 independent reflections

1823 reflections with I > 2σ(I)

R int = 0.033

θmax = 58.9°

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.091

S = 1.06

1969 reflections

158 parameters

H-atom parameters constrained

Δρmax = 0.14 e Å−3

Δρmin = −0.12 e Å−3

Absolute structure: Flack (1983 ▶), 801 Friedel pairs

Flack parameter: −0.4 (4)

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: FSProcess in PROCESS-AUTO (Rigaku, 1998 ▶); data reduction: FSProcess in PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP in WinGX (Farrugia, 1999 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811038694/zj2024sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038694/zj2024Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811038694/zj2024Isup3.cml

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

C16H28O	F(000) = 528
Mr = 236.38	Dx = 1.121 Mg m−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 484 reflections
a = 7.3497 (2) Å	θ = 6.6–72.0°
b = 11.1642 (3) Å	µ = 0.50 mm−1
c = 17.0758 (12) Å	T = 123 K
V = 1401.13 (11) Å3	Needle, colourless
Z = 4	0.70 × 0.40 × 0.13 mm

Rigaku Spider diffractometer	1969 independent reflections
Radiation source: Rigaku MM007 rotating anode	1823 reflections with I > 2σ(I)
Rigaku VariMax-HF Confocal Optical System	Rint = 0.033
Detector resolution: 10 pixels mm-1	θmax = 58.9°, θmin = 6.5°
ω–scans	h = −8→5
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −10→12
Tmin = 0.687, Tmax = 1.0	l = −12→18
5141 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.034	w = 1/[σ2(Fo2) + (0.0509P)2 + 0.0905P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.091	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.14 e Å−3
1969 reflections	Δρmin = −0.12 e Å−3
158 parameters	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0066 (8)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 780 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: −0.4 (4)

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.

	x	y	z	Uiso*/Ueq
O1	0.40780 (17)	0.74765 (10)	0.29584 (7)	0.0466 (4)
C1	0.1359 (2)	0.60896 (15)	0.02512 (10)	0.0351 (4)
H1A	0.0226	0.6177	0.0560	0.042*
H1B	0.1734	0.6899	0.0078	0.042*
C2	0.0957 (2)	0.53268 (15)	−0.04708 (10)	0.0393 (4)
H2A	0.0458	0.4544	−0.0305	0.047*
H2B	0.0030	0.5732	−0.0797	0.047*
C3	0.2675 (2)	0.51266 (16)	−0.09533 (10)	0.0390 (4)
H3A	0.3091	0.5906	−0.1164	0.047*
H3B	0.2377	0.4604	−0.1404	0.047*
C4	0.4228 (2)	0.45576 (14)	−0.04894 (10)	0.0348 (4)
C5	0.4558 (2)	0.53078 (14)	0.02654 (9)	0.0313 (4)
H5	0.4936	0.6113	0.0067	0.038*
C6	0.6176 (2)	0.48888 (15)	0.07615 (9)	0.0347 (4)
H6A	0.5872	0.4114	0.1012	0.042*
H6B	0.7242	0.4760	0.0417	0.042*
C7	0.6663 (2)	0.57965 (16)	0.13907 (10)	0.0368 (4)
H7A	0.7145	0.6529	0.1138	0.044*
H7B	0.7635	0.5461	0.1727	0.044*
C8	0.5036 (2)	0.61297 (15)	0.19000 (10)	0.0352 (4)
H8	0.4655	0.5405	0.2202	0.042*
C9	0.3432 (2)	0.65343 (15)	0.13913 (9)	0.0322 (4)
H9	0.3881	0.7234	0.1081	0.039*
C10	0.2851 (2)	0.55687 (14)	0.07831 (9)	0.0305 (4)
C11	0.1914 (2)	0.70176 (16)	0.19186 (10)	0.0408 (5)
H11A	0.0955	0.7387	0.1591	0.049*
H11B	0.1360	0.6347	0.2214	0.049*
C12	0.2640 (3)	0.79350 (16)	0.24854 (11)	0.0462 (5)
H12A	0.3090	0.8637	0.2189	0.055*
H12B	0.1638	0.8209	0.2829	0.055*
C13	0.5560 (2)	0.71069 (16)	0.24787 (10)	0.0422 (5)
H13A	0.6555	0.6809	0.2818	0.051*
H13B	0.6026	0.7808	0.2186	0.051*
C14	0.5941 (3)	0.46036 (17)	−0.10071 (10)	0.0472 (5)
H14A	0.6897	0.4108	−0.0773	0.071*
H14B	0.6367	0.5433	−0.1047	0.071*
H14C	0.5649	0.4300	−0.1531	0.071*
C15	0.3821 (3)	0.32245 (14)	−0.03348 (11)	0.0431 (5)
H15A	0.3920	0.2775	−0.0826	0.065*
H15B	0.2586	0.3142	−0.0125	0.065*
H15C	0.4698	0.2909	0.0045	0.065*
C16	0.2115 (2)	0.44509 (14)	0.12111 (10)	0.0372 (4)
H16A	0.1403	0.3964	0.0845	0.056*
H16B	0.1338	0.4702	0.1648	0.056*
H16C	0.3135	0.3978	0.1412	0.056*

	U11	U22	U33	U12	U13	U23
O1	0.0496 (8)	0.0512 (7)	0.0389 (6)	0.0050 (7)	−0.0014 (6)	−0.0043 (6)
C1	0.0215 (10)	0.0358 (9)	0.0480 (10)	0.0030 (8)	0.0000 (8)	0.0003 (8)
C2	0.0313 (10)	0.0395 (9)	0.0473 (10)	0.0030 (9)	−0.0102 (8)	0.0012 (8)
C3	0.0339 (10)	0.0411 (9)	0.0421 (9)	0.0012 (8)	−0.0040 (8)	−0.0042 (8)
C4	0.0247 (9)	0.0394 (9)	0.0404 (9)	−0.0013 (8)	0.0005 (8)	−0.0033 (8)
C5	0.0241 (9)	0.0292 (9)	0.0406 (9)	−0.0025 (7)	0.0020 (8)	0.0030 (8)
C6	0.0232 (9)	0.0392 (9)	0.0417 (9)	0.0015 (8)	0.0016 (8)	0.0005 (8)
C7	0.0257 (10)	0.0428 (10)	0.0418 (9)	0.0005 (8)	−0.0036 (8)	0.0030 (8)
C8	0.0286 (9)	0.0396 (10)	0.0373 (9)	−0.0022 (8)	−0.0012 (7)	0.0039 (8)
C9	0.0254 (9)	0.0318 (9)	0.0392 (9)	−0.0021 (7)	0.0031 (7)	0.0009 (8)
C10	0.0214 (9)	0.0314 (9)	0.0389 (9)	−0.0025 (7)	0.0001 (8)	0.0024 (7)
C11	0.0376 (11)	0.0419 (10)	0.0429 (9)	0.0021 (9)	0.0034 (9)	−0.0005 (9)
C12	0.0456 (11)	0.0461 (11)	0.0468 (10)	0.0047 (10)	0.0031 (10)	−0.0040 (9)
C13	0.0409 (11)	0.0449 (11)	0.0407 (9)	0.0009 (9)	−0.0022 (10)	−0.0027 (9)
C14	0.0387 (11)	0.0596 (12)	0.0433 (10)	0.0021 (10)	0.0036 (9)	−0.0082 (9)
C15	0.0340 (11)	0.0349 (9)	0.0604 (11)	0.0052 (8)	−0.0052 (10)	−0.0077 (9)
C16	0.0292 (10)	0.0339 (9)	0.0484 (10)	−0.0016 (8)	0.0026 (8)	0.0015 (8)

O1—C13	1.424 (2)	C8—C13	1.522 (2)
O1—C12	1.425 (2)	C8—C9	1.532 (2)
C1—C2	1.527 (2)	C8—H8	1.0000
C1—C10	1.538 (2)	C9—C11	1.532 (2)
C1—H1A	0.9900	C9—C10	1.557 (2)
C1—H1B	0.9900	C9—H9	1.0000
C2—C3	1.524 (2)	C10—C16	1.544 (2)
C2—H2A	0.9900	C11—C12	1.507 (2)
C2—H2B	0.9900	C11—H11A	0.9900
C3—C4	1.528 (2)	C11—H11B	0.9900
C3—H3A	0.9900	C12—H12A	0.9900
C3—H3B	0.9900	C12—H12B	0.9900
C4—C14	1.539 (2)	C13—H13A	0.9900
C4—C15	1.541 (2)	C13—H13B	0.9900
C4—C5	1.556 (2)	C14—H14A	0.9800
C5—C6	1.533 (2)	C14—H14B	0.9800
C5—C10	1.562 (2)	C14—H14C	0.9800
C5—H5	1.0000	C15—H15A	0.9800
C6—C7	1.520 (2)	C15—H15B	0.9800
C6—H6A	0.9900	C15—H15C	0.9800
C6—H6B	0.9900	C16—H16A	0.9800
C7—C8	1.525 (2)	C16—H16B	0.9800
C7—H7A	0.9900	C16—H16C	0.9800
C7—H7B	0.9900
C13—O1—C12	110.20 (12)	C11—C9—C8	109.31 (13)
C2—C1—C10	113.79 (13)	C11—C9—C10	115.89 (13)
C2—C1—H1A	108.8	C8—C9—C10	112.64 (13)
C10—C1—H1A	108.8	C11—C9—H9	106.1
C2—C1—H1B	108.8	C8—C9—H9	106.1
C10—C1—H1B	108.8	C10—C9—H9	106.1
H1A—C1—H1B	107.7	C1—C10—C16	109.57 (13)
C3—C2—C1	110.99 (13)	C1—C10—C9	109.12 (12)
C3—C2—H2A	109.4	C16—C10—C9	109.88 (12)
C1—C2—H2A	109.4	C1—C10—C5	108.01 (11)
C3—C2—H2B	109.4	C16—C10—C5	113.50 (13)
C1—C2—H2B	109.4	C9—C10—C5	106.64 (12)
H2A—C2—H2B	108.0	C12—C11—C9	111.05 (14)
C2—C3—C4	113.55 (13)	C12—C11—H11A	109.4
C2—C3—H3A	108.9	C9—C11—H11A	109.4
C4—C3—H3A	108.9	C12—C11—H11B	109.4
C2—C3—H3B	108.9	C9—C11—H11B	109.4
C4—C3—H3B	108.9	H11A—C11—H11B	108.0
H3A—C3—H3B	107.7	O1—C12—C11	112.49 (15)
C3—C4—C14	107.42 (13)	O1—C12—H12A	109.1
C3—C4—C15	110.21 (14)	C11—C12—H12A	109.1
C14—C4—C15	106.83 (14)	O1—C12—H12B	109.1
C3—C4—C5	108.80 (13)	C11—C12—H12B	109.1
C14—C4—C5	109.28 (13)	H12A—C12—H12B	107.8
C15—C4—C5	114.09 (14)	O1—C13—C8	112.80 (13)
C6—C5—C4	114.48 (12)	O1—C13—H13A	109.0
C6—C5—C10	111.54 (11)	C8—C13—H13A	109.0
C4—C5—C10	116.34 (12)	O1—C13—H13B	109.0
C6—C5—H5	104.3	C8—C13—H13B	109.0
C4—C5—H5	104.3	H13A—C13—H13B	107.8
C10—C5—H5	104.3	C4—C14—H14A	109.5
C7—C6—C5	111.71 (13)	C4—C14—H14B	109.5
C7—C6—H6A	109.3	H14A—C14—H14B	109.5
C5—C6—H6A	109.3	C4—C14—H14C	109.5
C7—C6—H6B	109.3	H14A—C14—H14C	109.5
C5—C6—H6B	109.3	H14B—C14—H14C	109.5
H6A—C6—H6B	107.9	C4—C15—H15A	109.5
C6—C7—C8	112.41 (13)	C4—C15—H15B	109.5
C6—C7—H7A	109.1	H15A—C15—H15B	109.5
C8—C7—H7A	109.1	C4—C15—H15C	109.5
C6—C7—H7B	109.1	H15A—C15—H15C	109.5
C8—C7—H7B	109.1	H15B—C15—H15C	109.5
H7A—C7—H7B	107.9	C10—C16—H16A	109.5
C13—C8—C7	110.28 (13)	C10—C16—H16B	109.5
C13—C8—C9	110.59 (13)	H16A—C16—H16B	109.5
C7—C8—C9	110.61 (13)	C10—C16—H16C	109.5
C13—C8—H8	108.4	H16A—C16—H16C	109.5
C7—C8—H8	108.4	H16B—C16—H16C	109.5
C9—C8—H8	108.4
C10—C1—C2—C3	−56.49 (18)	C2—C1—C10—C9	168.00 (13)
C1—C2—C3—C4	56.36 (18)	C2—C1—C10—C5	52.44 (17)
C2—C3—C4—C14	−170.86 (13)	C11—C9—C10—C1	58.17 (17)
C2—C3—C4—C15	73.11 (18)	C8—C9—C10—C1	−174.92 (12)
C2—C3—C4—C5	−52.67 (18)	C11—C9—C10—C16	−61.98 (18)
C3—C4—C5—C6	−175.92 (12)	C8—C9—C10—C16	64.93 (16)
C14—C4—C5—C6	−58.92 (17)	C11—C9—C10—C5	174.60 (13)
C15—C4—C5—C6	60.59 (18)	C8—C9—C10—C5	−58.48 (15)
C3—C4—C5—C10	51.59 (17)	C6—C5—C10—C1	174.96 (12)
C14—C4—C5—C10	168.59 (13)	C4—C5—C10—C1	−51.21 (17)
C15—C4—C5—C10	−71.91 (18)	C6—C5—C10—C16	−63.35 (17)
C4—C5—C6—C7	168.28 (13)	C4—C5—C10—C16	70.48 (16)
C10—C5—C6—C7	−56.98 (17)	C6—C5—C10—C9	57.78 (16)
C5—C6—C7—C8	53.70 (17)	C4—C5—C10—C9	−168.39 (13)
C6—C7—C8—C13	−175.75 (14)	C8—C9—C11—C12	50.94 (18)
C6—C7—C8—C9	−53.10 (19)	C10—C9—C11—C12	179.51 (14)
C13—C8—C9—C11	−50.14 (17)	C13—O1—C12—C11	60.46 (18)
C7—C8—C9—C11	−172.61 (13)	C9—C11—C12—O1	−56.93 (18)
C13—C8—C9—C10	179.51 (13)	C12—O1—C13—C8	−60.03 (18)
C7—C8—C9—C10	57.04 (17)	C7—C8—C13—O1	178.54 (14)
C2—C1—C10—C16	−71.65 (16)	C9—C8—C13—O1	55.88 (17)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O1i	0.99	2.54	3.474 (2)	158

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯O1i	0.99	2.54	3.474 (2)	158

Symmetry code: (i) .