2-Hydr­oxy-6,6-dimethyl­bicyclo­[3.1.1]heptane-2-carboxylic acid

Gao, Y.-Q.; Shang, S.-B.; Xu, X.; Rao, X.-P.; Wang, H.-X.

doi:10.1107/S1600536809041385

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2748

https://doi.org/10.1107/S1600536809041385

Open

access

2-Hydroxy-6,6-dimethylbicyclo[3.1.1]heptane-2-carboxylic acid

Yan-Qing Gao,^a Shi-Bin Shang,^a ^* Xu Xu,^a Xiao-Ping Rao ^a and Hong-Xiao Wang ^a

^aInstitute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Nanjing 210042, People's Republic of China
^*Correspondence e-mail: shangsb@hotmail.com

(Received 28 September 2009; accepted 10 October 2009; online 17 October 2009)

The title compound, C₁₀H₁₆O₃, with a bicyclo[3.1.1]heptane unit, was obtained by oxidation of β-pinene. The asymmetric unit contains two independent molecules with similar geometry: the six-membered rings in both molecules adopt envelope conformations. In the crystal, the independent molecules exist as O—H⋯O hydrogen-bonded dimers. The dimers are linked into helical chains along the b axis by O—H⋯O hydrogen bonds.

Related literature

For the preparation of nopinone and nopinic acid, see: Winstein & Holness (1955 ); Ma et al. (2007 ). For the crystal structure of sodium nopinate [sodium (1R,2S,5S)-2-hydroxy-6,6-dimethylbicyclo[3.1.1]heptane-2-carboxylate pentahydrate], see: Ma et al. (2008 ).

Experimental

Crystal data

C₁₀H₁₆O₃
M_r = 184.23
Monoclinic, C 2
a = 26.796 (5) Å
b = 6.6560 (13) Å
c = 12.250 (3) Å
β = 112.23 (3)°
V = 2022.5 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (XCAD4; Harms & Wocadlo, 1995 ) T_min = 0.974, T_max = 0.983
2047 measured reflections
2002 independent reflections
1565 reflections with I > 2σ(I)
R_int = 0.018
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.153
S = 1.00
2002 reflections
242 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2	0.81 (3)	2.38 (8)	2.837 (5)	116 (7)
O2—H2D⋯O6	0.82	1.80	2.621 (5)	175
O4—H4C⋯O1ⁱ	0.84 (5)	2.05 (5)	2.830 (5)	156 (5)
O5—H5C⋯O3	0.82	1.88	2.704 (4)	177
Symmetry code: (i) -x, y-1, -z.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809041385/ci2928sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809041385/ci2928Isup2.hkl

checkCIF report

Comment top

Terpenes are convenient chiral precursors due to their availability and low cost, and among them β-pinene is an important material. Many valuable chemicals were prepared from β-pinene. For instance, nopinone (Winstein & Holness, 1955) and nopinic acid were prepared by oxidation of β-pinene. Although the title compound has been prepared (Ma et al., 2007) and the crystal structure of sodium nopinate has been reported (Ma et al., 2008), the crystal structure of nopinic acid has not been reported. In this paper, we report the crystal structure of the title compound.

The asymmetric unit contains two crystallographically independent molecules (Fig. 1) with similar geometry. The six-membered rings in both the molecules adopt envelope conformations. The independent molecules are linked through a pair of O–H···O hydrogen bonds (Table 1) forming a dimer. The dimers are linked into helical chains along the b axis (Fig. 2) by O—H···O hydrogen bonds.

Related literature top

For the preparation of nopinone and nopinic acid, see: Winstein & Holness (1955); Ma et al. (2007). For the crystal structure of sodium nopinate [sodium (1R,2S,5S)-2-hydroxy-6,6-dimethylbicyclo[3.1.1]heptane-2-carboxylate pentahydrate], see: Ma et al. (2008).

Experimental top

Potassium permanganate (12.0 g) and NaOH (1.5 g) were dissolved in the mixture of water (100 ml) and t-butylalcohol (50 ml). While stirring vigorously, pure (-)-beta-pinene (5.2 g) was added. The reaction was maintained at the temperature of 288–298 K for 0.5 h. The mixture was heated to 353 K, then filtered and the precipitate was washed with hot water. After standing for 12 h at 273 K, sodium nopinate was filtered. The crude sodium nopinate was acidified with dilute hydrochloric acid and extracted with dichloromethane, then the product, crude nopinic acid was obtained. The crude nopinic acid was recrystallized from toluene. Single crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of a ethanol-toluene solution.

Structure description top

For the preparation of nopinone and nopinic acid, see: Winstein & Holness (1955); Ma et al. (2007). For the crystal structure of sodium nopinate [sodium (1R,2S,5S)-2-hydroxy-6,6-dimethylbicyclo[3.1.1]heptane-2-carboxylate pentahydrate], see: Ma et al. (2008).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines.
	Fig. 2. Crystal packing of the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines.

2-Hydroxy-6,6-dimethylbicyclo[3.1.1]heptane-2-carboxylic acid top

Crystal data top

C₁₀H₁₆O₃	F(000) = 800
M_r = 184.23	D_x = 1.210 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 25 reflections
a = 26.796 (5) Å	θ = 10–13°
b = 6.6560 (13) Å	µ = 0.09 mm⁻¹
c = 12.250 (3) Å	T = 293 K
β = 112.23 (3)°	Block, colourless
V = 2022.5 (9) Å³	0.30 × 0.20 × 0.20 mm
Z = 8

Data collection top

Enraf–Nonius CAD-4 diffractometer	1565 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.018
Graphite monochromator	θ_max = 25.3°, θ_min = 1.6°
ω/2θ scans	h = 0→32
Absorption correction: ψ scan (XCAD4; Harms & Wocadlo, 1995)	k = 0→7
T_min = 0.974, T_max = 0.983	l = −14→13
2047 measured reflections	3 standard reflections every 200 reflections
2002 independent reflections	intensity decay: 1%

Refinement top

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)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.153	w = 1/[σ²(F_o²) + (0.1P)² + 0.3P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
2002 reflections	Δρ_max = 0.21 e Å⁻³
242 parameters	Δρ_min = −0.23 e Å⁻³
3 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: 0.044 (4)

Crystal data top

C₁₀H₁₆O₃	V = 2022.5 (9) Å³
M_r = 184.23	Z = 8
Monoclinic, C2	Mo Kα radiation
a = 26.796 (5) Å	µ = 0.09 mm⁻¹
b = 6.6560 (13) Å	T = 293 K
c = 12.250 (3) Å	0.30 × 0.20 × 0.20 mm
β = 112.23 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1565 reflections with I > 2σ(I)
Absorption correction: ψ scan (XCAD4; Harms & Wocadlo, 1995)	R_int = 0.018
T_min = 0.974, T_max = 0.983	3 standard reflections every 200 reflections
2047 measured reflections	intensity decay: 1%
2002 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	3 restraints
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.21 e Å⁻³
2002 reflections	Δρ_min = −0.23 e Å⁻³
242 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
O1	0.03238 (12)	0.4845 (8)	0.2047 (3)	0.0997 (14)
H1A	0.021 (3)	0.504 (15)	0.134 (2)	0.150*
C1	0.2225 (3)	0.6237 (14)	0.2710 (5)	0.116 (2)
H1B	0.2158	0.7519	0.2986	0.174*
H1C	0.2171	0.6336	0.1891	0.174*
H1D	0.2590	0.5836	0.3156	0.174*
O2	0.07227 (15)	0.3644 (5)	0.0307 (3)	0.0842 (10)
H2D	0.0677	0.2896	−0.0255	0.126*
C2	0.1946 (2)	0.2647 (10)	0.2414 (5)	0.0941 (19)
H2A	0.1946	0.2814	0.1635	0.141*
H2B	0.1672	0.1701	0.2391	0.141*
H2C	0.2292	0.2157	0.2931	0.141*
O3	0.06567 (14)	0.0776 (5)	0.1168 (3)	0.0724 (9)
C3	0.18336 (16)	0.4660 (9)	0.2865 (4)	0.0672 (12)
C4	0.18223 (17)	0.4726 (8)	0.4114 (4)	0.0681 (12)
H4A	0.2164	0.5083	0.4747	0.082*
C5	0.14121 (19)	0.6413 (8)	0.3696 (4)	0.0732 (13)
H5A	0.1569	0.7746	0.3781	0.088*
H5B	0.1130	0.6356	0.4009	0.088*
C6	0.12546 (16)	0.5514 (7)	0.2461 (3)	0.0601 (10)
H6A	0.1162	0.6498	0.1820	0.072*
C7	0.08375 (14)	0.3881 (7)	0.2299 (3)	0.0571 (10)
C8	0.0964 (2)	0.2662 (9)	0.3430 (4)	0.0835 (16)
H8A	0.0901	0.1252	0.3223	0.100*
H8B	0.0714	0.3056	0.3794	0.100*
C9	0.1543 (2)	0.2906 (9)	0.4343 (4)	0.0841 (16)
H9A	0.1533	0.3013	0.5124	0.101*
H9B	0.1750	0.1716	0.4330	0.101*
C10	0.07381 (16)	0.2592 (7)	0.1207 (4)	0.0542 (10)
O4	−0.00459 (10)	−0.2034 (5)	−0.3282 (2)	0.0640 (8)
H4C	−0.010 (2)	−0.270 (8)	−0.276 (4)	0.096*
O5	0.05228 (13)	−0.1491 (5)	−0.0754 (2)	0.0677 (8)
H5C	0.0566	−0.0769	−0.0183	0.102*
O6	0.05719 (14)	0.1444 (5)	−0.1566 (3)	0.0714 (9)
C11	0.1765 (2)	−0.5132 (10)	−0.1362 (6)	0.0972 (18)
H11A	0.1808	−0.5215	−0.0549	0.146*
H11B	0.2114	−0.5142	−0.1416	0.146*
H11C	0.1559	−0.6262	−0.1785	0.146*
C12	0.17137 (18)	−0.1448 (10)	−0.1071 (4)	0.0769 (14)
H12A	0.1733	−0.1796	−0.0295	0.115*
H12B	0.1495	−0.0269	−0.1339	0.115*
H12C	0.2070	−0.1186	−0.1048	0.115*
C13	0.14673 (15)	−0.3165 (7)	−0.1904 (4)	0.0591 (11)
C14	0.08439 (14)	−0.3538 (6)	−0.2409 (3)	0.0480 (9)
H14A	0.0720	−0.4534	−0.1978	0.058*
C15	0.08937 (19)	−0.4313 (7)	−0.3542 (4)	0.0660 (11)
H15A	0.0597	−0.3933	−0.4260	0.079*
H15B	0.0973	−0.5737	−0.3532	0.079*
C16	0.13896 (18)	−0.2949 (7)	−0.3219 (4)	0.0650 (12)
H16A	0.1685	−0.3484	−0.3420	0.078*
C17	0.1211 (2)	−0.0838 (8)	−0.3660 (4)	0.0675 (13)
H17A	0.1174	−0.0727	−0.4476	0.081*
H17B	0.1483	0.0115	−0.3200	0.081*
C18	0.06712 (17)	−0.0321 (7)	−0.3564 (3)	0.0599 (11)
H18A	0.0681	0.1080	−0.3339	0.072*
H18B	0.0388	−0.0464	−0.4339	0.072*
C19	0.05197 (13)	−0.1576 (6)	−0.2696 (3)	0.0461 (9)
C20	0.05493 (15)	−0.0405 (6)	−0.1616 (3)	0.0509 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0457 (16)	0.123 (3)	0.119 (3)	0.014 (2)	0.0179 (17)	−0.057 (3)
C1	0.100 (4)	0.146 (7)	0.110 (4)	−0.050 (5)	0.050 (3)	−0.019 (5)
O2	0.131 (3)	0.0553 (19)	0.0582 (17)	−0.002 (2)	0.0263 (16)	−0.0013 (17)
C2	0.056 (3)	0.120 (5)	0.104 (4)	0.024 (3)	0.028 (3)	−0.017 (4)
O3	0.099 (2)	0.0558 (19)	0.0706 (19)	−0.0094 (18)	0.0413 (17)	−0.0104 (16)
C3	0.046 (2)	0.084 (3)	0.071 (3)	0.000 (2)	0.0214 (18)	−0.005 (3)
C4	0.052 (2)	0.080 (3)	0.058 (2)	−0.005 (2)	0.0052 (17)	−0.004 (2)
C5	0.071 (3)	0.066 (3)	0.076 (3)	−0.005 (3)	0.020 (2)	−0.023 (3)
C6	0.063 (2)	0.049 (2)	0.057 (2)	0.010 (2)	0.0102 (17)	0.001 (2)
C7	0.042 (2)	0.065 (3)	0.064 (2)	0.008 (2)	0.0191 (16)	−0.013 (2)
C8	0.101 (4)	0.093 (4)	0.067 (3)	−0.035 (3)	0.044 (3)	−0.019 (3)
C9	0.108 (4)	0.085 (4)	0.051 (2)	−0.004 (3)	0.021 (2)	0.007 (3)
C10	0.051 (2)	0.055 (3)	0.055 (2)	0.0081 (19)	0.0183 (18)	−0.0031 (19)
O4	0.0449 (14)	0.072 (2)	0.0648 (16)	−0.0111 (15)	0.0095 (12)	0.0054 (16)
O5	0.103 (2)	0.0507 (17)	0.0607 (16)	−0.0033 (17)	0.0441 (15)	0.0021 (15)
O6	0.103 (2)	0.0429 (18)	0.0730 (19)	−0.0012 (17)	0.0385 (17)	−0.0001 (15)
C11	0.076 (3)	0.086 (4)	0.126 (5)	0.022 (3)	0.034 (3)	0.021 (4)
C12	0.053 (3)	0.090 (4)	0.072 (3)	−0.004 (3)	0.006 (2)	−0.001 (3)
C13	0.045 (2)	0.059 (3)	0.071 (2)	0.003 (2)	0.0190 (17)	0.000 (2)
C14	0.051 (2)	0.0404 (19)	0.055 (2)	−0.0065 (18)	0.0232 (16)	0.0045 (18)
C15	0.083 (3)	0.049 (2)	0.073 (3)	−0.011 (2)	0.037 (2)	−0.014 (2)
C16	0.070 (3)	0.062 (3)	0.078 (3)	−0.006 (2)	0.046 (2)	−0.007 (2)
C17	0.085 (3)	0.065 (3)	0.062 (2)	−0.022 (2)	0.038 (2)	−0.003 (2)
C18	0.069 (3)	0.054 (2)	0.054 (2)	−0.008 (2)	0.0204 (18)	0.007 (2)
C19	0.0426 (18)	0.047 (2)	0.0460 (18)	−0.0062 (17)	0.0140 (14)	0.0038 (17)
C20	0.049 (2)	0.046 (3)	0.059 (2)	0.0046 (18)	0.0217 (17)	0.0058 (19)

Geometric parameters (Å, º) top

O1—C7	1.442 (5)	O4—C19	1.443 (4)
O1—H1A	0.82 (2)	O4—H4C	0.84 (5)
C1—C3	1.546 (8)	O5—C20	1.303 (5)
C1—H1B	0.96	O5—H5C	0.82
C1—H1C	0.96	O6—C20	1.232 (5)
C1—H1D	0.96	C11—C13	1.547 (8)
O2—C10	1.294 (5)	C11—H11A	0.96
O2—H2D	0.82	C11—H11B	0.96
C2—C3	1.523 (8)	C11—H11C	0.96
C2—H2A	0.96	C12—C13	1.508 (7)
C2—H2B	0.96	C12—H12A	0.96
C2—H2C	0.96	C12—H12B	0.96
O3—C10	1.226 (6)	C12—H12C	0.96
C3—C4	1.542 (6)	C13—C16	1.550 (6)
C3—C6	1.547 (6)	C13—C14	1.566 (5)
C4—C9	1.505 (8)	C14—C15	1.533 (5)
C4—C5	1.518 (7)	C14—C19	1.534 (5)
C4—H4A	0.98	C14—H14A	0.98
C5—C6	1.530 (6)	C15—C16	1.533 (6)
C5—H5A	0.97	C15—H15A	0.97
C5—H5B	0.97	C15—H15B	0.97
C6—C7	1.517 (6)	C16—C17	1.517 (7)
C6—H6A	0.98	C16—H16A	0.98
C7—C10	1.526 (6)	C17—C18	1.533 (6)
C7—C8	1.529 (7)	C17—H17A	0.97
C8—C9	1.540 (7)	C17—H17B	0.97
C8—H8A	0.97	C18—C19	1.523 (5)
C8—H8B	0.97	C18—H18A	0.97
C9—H9A	0.97	C18—H18B	0.97
C9—H9B	0.97	C19—C20	1.512 (5)

C7—O1—H1A	103 (6)	C19—O4—H4C	100 (4)
C3—C1—H1B	109.5	C20—O5—H5C	109.5
C3—C1—H1C	109.5	C13—C11—H11A	109.5
H1B—C1—H1C	109.5	C13—C11—H11B	109.5
C3—C1—H1D	109.5	H11A—C11—H11B	109.5
H1B—C1—H1D	109.5	C13—C11—H11C	109.5
H1C—C1—H1D	109.5	H11A—C11—H11C	109.5
C10—O2—H2D	109.5	H11B—C11—H11C	109.5
C3—C2—H2A	109.5	C13—C12—H12A	109.5
C3—C2—H2B	109.5	C13—C12—H12B	109.5
H2A—C2—H2B	109.5	H12A—C12—H12B	109.5
C3—C2—H2C	109.5	C13—C12—H12C	109.5
H2A—C2—H2C	109.5	H12A—C12—H12C	109.5
H2B—C2—H2C	109.5	H12B—C12—H12C	109.5
C2—C3—C4	117.8 (5)	C12—C13—C11	109.2 (4)
C2—C3—C1	108.4 (4)	C12—C13—C16	119.0 (4)
C4—C3—C1	111.8 (4)	C11—C13—C16	111.6 (4)
C2—C3—C6	121.3 (4)	C12—C13—C14	121.0 (4)
C4—C3—C6	85.0 (3)	C11—C13—C14	109.6 (4)
C1—C3—C6	110.9 (5)	C16—C13—C14	84.3 (3)
C9—C4—C5	108.1 (4)	C15—C14—C19	108.3 (3)
C9—C4—C3	111.1 (4)	C15—C14—C13	88.0 (3)
C5—C4—C3	88.3 (3)	C19—C14—C13	112.5 (3)
C9—C4—H4A	115.4	C15—C14—H14A	115.0
C5—C4—H4A	115.4	C19—C14—H14A	115.0
C3—C4—H4A	115.4	C13—C14—H14A	115.0
C4—C5—C6	86.4 (3)	C14—C15—C16	86.0 (3)
C4—C5—H5A	114.2	C14—C15—H15A	114.3
C6—C5—H5A	114.2	C16—C15—H15A	114.3
C4—C5—H5B	114.2	C14—C15—H15B	114.3
C6—C5—H5B	114.2	C16—C15—H15B	114.3
H5A—C5—H5B	111.4	H15A—C15—H15B	111.5
C7—C6—C5	108.9 (4)	C17—C16—C15	109.3 (4)
C7—C6—C3	112.2 (4)	C17—C16—C13	110.8 (4)
C5—C6—C3	87.7 (3)	C15—C16—C13	88.6 (3)
C7—C6—H6A	115.0	C17—C16—H16A	115.1
C5—C6—H6A	115.0	C15—C16—H16A	115.1
C3—C6—H6A	115.0	C13—C16—H16A	115.1
O1—C7—C6	107.8 (4)	C16—C17—C18	111.1 (4)
O1—C7—C10	103.1 (3)	C16—C17—H17A	109.4
C6—C7—C10	113.1 (3)	C18—C17—H17A	109.4
O1—C7—C8	107.2 (4)	C16—C17—H17B	109.4
C6—C7—C8	111.2 (3)	C18—C17—H17B	109.4
C10—C7—C8	113.7 (4)	H17A—C17—H17B	108.0
C7—C8—C9	114.7 (4)	C19—C18—C17	116.0 (4)
C7—C8—H8A	108.6	C19—C18—H18A	108.3
C9—C8—H8A	108.6	C17—C18—H18A	108.3
C7—C8—H8B	108.6	C19—C18—H18B	108.3
C9—C8—H8B	108.6	C17—C18—H18B	108.3
H8A—C8—H8B	107.6	H18A—C18—H18B	107.4
C4—C9—C8	112.7 (4)	O4—C19—C20	104.0 (3)
C4—C9—H9A	109.1	O4—C19—C18	106.0 (3)
C8—C9—H9A	109.1	C20—C19—C18	112.9 (3)
C4—C9—H9B	109.1	O4—C19—C14	109.3 (3)
C8—C9—H9B	109.1	C20—C19—C14	113.6 (3)
H9A—C9—H9B	107.8	C18—C19—C14	110.5 (3)
O3—C10—O2	123.6 (4)	O6—C20—O5	122.0 (4)
O3—C10—C7	123.9 (4)	O6—C20—C19	122.9 (4)
O2—C10—C7	112.4 (4)	O5—C20—C19	115.0 (3)

C2—C3—C4—C9	−40.5 (5)	C12—C13—C14—C15	147.2 (4)
C1—C3—C4—C9	−167.1 (5)	C11—C13—C14—C15	−84.4 (4)
C6—C3—C4—C9	82.4 (4)	C16—C13—C14—C15	26.6 (3)
C2—C3—C4—C5	−149.2 (4)	C12—C13—C14—C19	38.2 (5)
C1—C3—C4—C5	84.2 (5)	C11—C13—C14—C19	166.6 (4)
C6—C3—C4—C5	−26.3 (3)	C16—C13—C14—C19	−82.4 (3)
C9—C4—C5—C6	−85.0 (4)	C19—C14—C15—C16	86.2 (3)
C3—C4—C5—C6	26.6 (3)	C13—C14—C15—C16	−26.9 (3)
C4—C5—C6—C7	86.2 (4)	C14—C15—C16—C17	−84.5 (4)
C4—C5—C6—C3	−26.5 (4)	C14—C15—C16—C13	27.2 (3)
C2—C3—C6—C7	36.3 (5)	C12—C13—C16—C17	−39.0 (5)
C4—C3—C6—C7	−83.3 (4)	C11—C13—C16—C17	−167.6 (4)
C1—C3—C6—C7	165.2 (4)	C14—C13—C16—C17	83.5 (4)
C2—C3—C6—C5	145.8 (5)	C12—C13—C16—C15	−149.1 (4)
C4—C3—C6—C5	26.1 (4)	C11—C13—C16—C15	82.2 (4)
C1—C3—C6—C5	−85.4 (4)	C14—C13—C16—C15	−26.6 (3)
C5—C6—C7—O1	78.6 (4)	C15—C16—C17—C18	35.4 (5)
C3—C6—C7—O1	174.0 (3)	C13—C16—C17—C18	−60.7 (4)
C5—C6—C7—C10	−168.0 (4)	C16—C17—C18—C19	20.9 (5)
C3—C6—C7—C10	−72.7 (4)	C17—C18—C19—O4	−137.5 (4)
C5—C6—C7—C8	−38.6 (5)	C17—C18—C19—C20	109.3 (4)
C3—C6—C7—C8	56.7 (5)	C17—C18—C19—C14	−19.2 (5)
O1—C7—C8—C9	−134.0 (5)	C15—C14—C19—O4	77.7 (3)
C6—C7—C8—C9	−16.4 (6)	C13—C14—C19—O4	173.3 (3)
C10—C7—C8—C9	112.7 (5)	C15—C14—C19—C20	−166.6 (3)
C5—C4—C9—C8	38.3 (6)	C13—C14—C19—C20	−71.0 (4)
C3—C4—C9—C8	−57.0 (6)	C15—C14—C19—C18	−38.6 (4)
C7—C8—C9—C4	16.9 (7)	C13—C14—C19—C18	57.0 (4)
O1—C7—C10—O3	−101.6 (5)	O4—C19—C20—O6	−99.0 (5)
C6—C7—C10—O3	142.3 (5)	C18—C19—C20—O6	15.5 (5)
C8—C7—C10—O3	14.1 (6)	C14—C19—C20—O6	142.2 (4)
O1—C7—C10—O2	75.2 (5)	O4—C19—C20—O5	77.9 (4)
C6—C7—C10—O2	−40.9 (5)	C18—C19—C20—O5	−167.7 (3)
C8—C7—C10—O2	−169.1 (4)	C14—C19—C20—O5	−40.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.81 (3)	2.38 (8)	2.837 (5)	116 (7)
O2—H2D···O6	0.82	1.80	2.621 (5)	175
O4—H4C···O1ⁱ	0.84 (5)	2.05 (5)	2.830 (5)	156 (5)
O5—H5C···O3	0.82	1.88	2.704 (4)	177

Symmetry code: (i) −x, y−1, −z.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₆O₃
M_r	184.23
Crystal system, space group	Monoclinic, C2
Temperature (K)	293
a, b, c (Å)	26.796 (5), 6.6560 (13), 12.250 (3)
β (°)	112.23 (3)
V (Å³)	2022.5 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (XCAD4; Harms & Wocadlo, 1995)
T_min, T_max	0.974, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	2047, 2002, 1565
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.153, 1.00
No. of reflections	2002
No. of parameters	242
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.23

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.81 (3)	2.38 (8)	2.837 (5)	116 (7)
O2—H2D···O6	0.82	1.80	2.621 (5)	175
O4—H4C···O1ⁱ	0.84 (5)	2.05 (5)	2.830 (5)	156 (5)
O5—H5C···O3	0.82	1.88	2.704 (4)	177

Symmetry code: (i) −x, y−1, −z.

References

Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Ma, S. Y., Shen, M. M. & Ha, C. Y. (2007). Chem. Ind. For. Prod. 27, 114–116. CAS Google Scholar
Ma, S.-Y., Zheng, Z.-B. & Li, J.-K. (2008). Acta Cryst. E64, m92. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Winstein, S. & Holness, N. J. (1955). J. Am. Chem. Soc. 77, 3054–3061. CrossRef CAS Web of Science Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2748

https://doi.org/10.1107/S1600536809041385

Open

access