Crystal structure of 15,16-ep-oxy-7β,9α-di-hydroxy-labdane-13(16),14-dien-6-one.

In the title mol-ecule, C20H30O4, both cyclo-hexane rings adopt chair conformations. In the crystal, mol-ecules are connected by O-H⋯O hydrogen bonds forming chains along [100]. In addtion, an intra-molecular O-H⋯O hydrogen bond forms an S(5) ring.

Related literature

For background to the title compound, see: Al-Musayeib et al. (2000 ▸); Shaw (1985 ▸). For its biological activities, see: Mossa et al. (2000 ▸); Kidane et al. (2013 ▸). For the synthesis and spectroscopic data, see: Savona et al. (1976 ▸,1977 ▸); Hon et al. (1993 ▸).

Experimental

Crystal data

C20H30O4

M = 334.44

Orthorhombic,

a = 8.5757 (7) Å

b = 9.2957 (8) Å

c = 22.994 (2) Å

V = 1833.0 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 293 K

0.30 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▸) T min = 0.865, T max = 1.000

5318 measured reflections

3554 independent reflections

2457 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.115

S = 1.02

3554 reflections

226 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.12 e Å−3

Δρmin = −0.14 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO (Oxford Diffraction, 2010 ▸); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015011214/lh5767sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015011214/lh5767Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S2056989015011214/lh5767fig1.tif

The mol­ecular structure of the title compound with ellipsoids drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii and the dashed line indicates an intra­molecular hydrogen bond.

Click here for additional data file.

b . DOI: 10.1107/S2056989015011214/lh5767fig2.tif

The packing arrangement of mol­ecules viewed along the b axis. Hydrogen bonds are shown as dashed lines.

CCDC reference: 1405794

Additional supporting information: crystallographic information; 3D view; checkCIF report

C20H30O4	F(000) = 728
Mr = 334.44	Dx = 1.212 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	θ = 4.2–27.3°
a = 8.5757 (7) Å	µ = 0.08 mm−1
b = 9.2957 (8) Å	T = 293 K
c = 22.994 (2) Å	Block, white
V = 1833.0 (3) Å3	0.30 × 0.20 × 0.20 mm
Z = 4

Oxford Diffraction Xcalibur Sapphire3 diffractometer	3554 independent reflections
Radiation source: fine-focus sealed tube	2457 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 16.1049 pixels mm-1	θmax = 26.0°, θmin = 3.5°
ω scans	h = −10→6
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −11→9
Tmin = 0.865, Tmax = 1.000	l = −14→28
5318 measured reflections

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)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.115	w = 1/[σ2(Fo2) + (0.0448P)2 + 0.067P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
3554 reflections	Δρmax = 0.12 e Å−3
226 parameters	Δρmin = −0.14 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: 0.0048 (14)

Experimental. CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27–08-2010 CrysAlis171. NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
O3	0.31780 (19)	0.20597 (18)	0.05469 (7)	0.0475 (5)
H3	0.3066	0.2523	0.0246	0.071*
C9	0.2680 (3)	0.2912 (3)	0.10343 (10)	0.0346 (5)
C10	0.2913 (2)	0.1911 (3)	0.15784 (10)	0.0342 (6)
C5	0.1913 (3)	0.0511 (3)	0.14935 (10)	0.0359 (6)
H5	0.2247	0.0130	0.1116	0.043*
C1	0.4627 (3)	0.1443 (3)	0.16192 (12)	0.0477 (7)
H1A	0.4966	0.1127	0.1238	0.057*
H1B	0.5251	0.2274	0.1724	0.057*
C6	0.0239 (3)	0.0936 (3)	0.14021 (11)	0.0412 (6)
O2	−0.1636 (2)	0.2232 (3)	0.08150 (12)	0.0757 (7)
O1	−0.0871 (2)	0.0563 (2)	0.16925 (8)	0.0650 (6)
C8	0.0939 (3)	0.3308 (3)	0.09553 (11)	0.0422 (6)
H8	0.0592	0.3799	0.1309	0.051*
C11	0.3672 (3)	0.4308 (3)	0.10900 (10)	0.0436 (6)
H11A	0.2981	0.5095	0.1192	0.052*
H11B	0.4401	0.4184	0.1408	0.052*
C12	0.4588 (3)	0.4737 (3)	0.05478 (12)	0.0598 (8)
H12A	0.5309	0.3971	0.0449	0.072*
H12B	0.3871	0.4854	0.0225	0.072*
C17	0.0631 (3)	0.4306 (3)	0.04419 (13)	0.0634 (8)
H17A	0.1023	0.3874	0.0092	0.095*
H17B	0.1147	0.5209	0.0506	0.095*
H17C	−0.0471	0.4464	0.0404	0.095*
C4	0.2190 (3)	−0.0753 (3)	0.19275 (11)	0.0488 (7)
C7	−0.0025 (3)	0.1927 (3)	0.08904 (12)	0.0487 (7)
H7	0.0339	0.1429	0.0540	0.058*
C20	0.2425 (3)	0.2737 (3)	0.21285 (10)	0.0457 (7)
H20A	0.1320	0.2644	0.2184	0.068*
H20B	0.2688	0.3735	0.2085	0.068*
H20C	0.2961	0.2348	0.2459	0.068*
C2	0.4949 (3)	0.0249 (3)	0.20529 (14)	0.0648 (9)
H2A	0.6042	−0.0017	0.2034	0.078*
H2B	0.4733	0.0592	0.2443	0.078*
O4	0.6221 (3)	0.8402 (3)	0.05881 (12)	0.1051 (9)
C3	0.3952 (3)	−0.1058 (3)	0.19269 (14)	0.0638 (8)
H3A	0.4174	−0.1790	0.2216	0.077*
H3B	0.4243	−0.1442	0.1550	0.077*
C13	0.5481 (3)	0.6103 (3)	0.06312 (12)	0.0541 (8)
C18	0.1353 (4)	−0.2094 (3)	0.16993 (14)	0.0689 (9)
H18A	0.1656	−0.2266	0.1303	0.103*
H18B	0.0246	−0.1948	0.1718	0.103*
H18C	0.1632	−0.2909	0.1934	0.103*
C19	0.1641 (4)	−0.0495 (3)	0.25525 (11)	0.0653 (9)
H19A	0.1759	−0.1363	0.2774	0.098*
H19B	0.0563	−0.0214	0.2550	0.098*
H19C	0.2255	0.0255	0.2725	0.098*
C14	0.6804 (4)	0.6324 (4)	0.09808 (14)	0.0708 (9)
H14	0.7311	0.5626	0.1200	0.085*
C16	0.5176 (5)	0.7401 (4)	0.04063 (15)	0.0877 (12)
H16	0.4350	0.7594	0.0156	0.105*
C15	0.7203 (4)	0.7698 (4)	0.09435 (15)	0.0841 (11)
H15	0.8043	0.8115	0.1136	0.101*
H2	−0.195 (4)	0.203 (4)	0.1169 (13)	0.076 (12)*

	U11	U22	U33	U12	U13	U23
O3	0.0644 (11)	0.0427 (11)	0.0354 (9)	−0.0007 (10)	0.0092 (8)	−0.0046 (8)
C9	0.0398 (12)	0.0324 (14)	0.0317 (12)	−0.0025 (12)	0.0025 (10)	−0.0027 (10)
C10	0.0322 (11)	0.0365 (14)	0.0337 (13)	−0.0049 (11)	0.0018 (10)	0.0005 (10)
C5	0.0356 (12)	0.0343 (14)	0.0377 (13)	−0.0017 (12)	−0.0004 (11)	−0.0019 (11)
C1	0.0355 (13)	0.0496 (17)	0.0581 (17)	−0.0036 (13)	−0.0021 (12)	0.0088 (14)
C6	0.0405 (13)	0.0324 (15)	0.0509 (16)	−0.0077 (13)	−0.0044 (12)	−0.0072 (11)
O2	0.0461 (11)	0.0863 (19)	0.0947 (19)	−0.0021 (12)	−0.0218 (12)	0.0208 (14)
O1	0.0430 (10)	0.0689 (15)	0.0832 (14)	−0.0102 (11)	0.0058 (10)	0.0128 (12)
C8	0.0454 (13)	0.0374 (16)	0.0437 (15)	0.0028 (13)	−0.0043 (12)	−0.0006 (11)
C11	0.0549 (15)	0.0384 (16)	0.0375 (14)	−0.0099 (14)	0.0024 (12)	−0.0008 (12)
C12	0.077 (2)	0.055 (2)	0.0471 (16)	−0.0151 (17)	0.0081 (15)	0.0007 (14)
C17	0.0685 (18)	0.054 (2)	0.068 (2)	−0.0020 (18)	−0.0158 (15)	0.0139 (15)
C4	0.0489 (14)	0.0418 (18)	0.0556 (17)	−0.0050 (14)	−0.0046 (13)	0.0104 (13)
C7	0.0411 (14)	0.0544 (19)	0.0507 (16)	−0.0001 (14)	−0.0141 (12)	−0.0001 (13)
C20	0.0518 (14)	0.0462 (17)	0.0390 (14)	−0.0087 (14)	−0.0015 (12)	−0.0012 (12)
C2	0.0417 (14)	0.073 (2)	0.079 (2)	0.0017 (16)	−0.0102 (16)	0.0243 (17)
O4	0.134 (2)	0.0734 (18)	0.1079 (19)	−0.0477 (18)	−0.0138 (19)	0.0282 (16)
C3	0.0555 (16)	0.051 (2)	0.085 (2)	0.0089 (16)	−0.0046 (16)	0.0230 (16)
C13	0.0673 (18)	0.0552 (19)	0.0396 (15)	−0.0193 (16)	0.0063 (14)	0.0062 (14)
C18	0.078 (2)	0.0350 (18)	0.094 (2)	−0.0063 (17)	−0.0047 (18)	0.0069 (16)
C19	0.0691 (18)	0.071 (2)	0.0562 (19)	−0.0155 (19)	0.0009 (16)	0.0186 (16)
C14	0.0682 (19)	0.074 (3)	0.070 (2)	−0.011 (2)	−0.0080 (17)	0.0168 (18)
C16	0.103 (3)	0.075 (3)	0.085 (3)	−0.037 (2)	−0.030 (2)	0.032 (2)
C15	0.085 (2)	0.090 (3)	0.077 (2)	−0.043 (2)	−0.010 (2)	0.008 (2)

O3—C9	1.438 (3)	C17—H17B	0.9600
O3—H3	0.8200	C17—H17C	0.9600
C9—C8	1.548 (3)	C4—C18	1.531 (4)
C9—C11	1.556 (3)	C4—C19	1.531 (4)
C9—C10	1.572 (3)	C4—C3	1.537 (3)
C10—C1	1.536 (3)	C7—H7	0.9800
C10—C20	1.538 (3)	C20—H20A	0.9600
C10—C5	1.571 (3)	C20—H20B	0.9600
C5—C6	1.504 (3)	C20—H20C	0.9600
C5—C4	1.560 (3)	C2—C3	1.514 (4)
C5—H5	0.9800	C2—H2A	0.9700
C1—C2	1.518 (4)	C2—H2B	0.9700
C1—H1A	0.9700	O4—C15	1.344 (4)
C1—H1B	0.9700	O4—C16	1.358 (4)
C6—O1	1.213 (3)	C3—H3A	0.9700
C6—C7	1.511 (4)	C3—H3B	0.9700
O2—C7	1.421 (3)	C13—C16	1.339 (4)
O2—H2	0.88 (3)	C13—C14	1.406 (4)
C8—C17	1.525 (4)	C18—H18A	0.9600
C8—C7	1.534 (4)	C18—H18B	0.9600
C8—H8	0.9800	C18—H18C	0.9600
C11—C12	1.527 (3)	C19—H19A	0.9600
C11—H11A	0.9700	C19—H19B	0.9600
C11—H11B	0.9700	C19—H19C	0.9600
C12—C13	1.495 (4)	C14—C15	1.325 (4)
C12—H12A	0.9700	C14—H14	0.9300
C12—H12B	0.9700	C16—H16	0.9300
C17—H17A	0.9600	C15—H15	0.9300
C9—O3—H3	109.5	C18—C4—C3	108.1 (2)
O3—C9—C8	109.01 (18)	C19—C4—C3	109.4 (2)
O3—C9—C11	111.19 (17)	C18—C4—C5	108.8 (2)
C8—C9—C11	109.78 (19)	C19—C4—C5	115.8 (2)
O3—C9—C10	104.86 (18)	C3—C4—C5	106.8 (2)
C8—C9—C10	110.88 (18)	O2—C7—C6	111.2 (2)
C11—C9—C10	111.01 (18)	O2—C7—C8	111.7 (2)
C1—C10—C20	110.6 (2)	C6—C7—C8	110.69 (19)
C1—C10—C5	107.2 (2)	O2—C7—H7	107.7
C20—C10—C5	111.54 (18)	C6—C7—H7	107.7
C1—C10—C9	109.75 (18)	C8—C7—H7	107.7
C20—C10—C9	108.94 (19)	C10—C20—H20A	109.5
C5—C10—C9	108.79 (17)	C10—C20—H20B	109.5
C6—C5—C4	115.7 (2)	H20A—C20—H20B	109.5
C6—C5—C10	108.70 (19)	C10—C20—H20C	109.5
C4—C5—C10	117.47 (18)	H20A—C20—H20C	109.5
C6—C5—H5	104.5	H20B—C20—H20C	109.5
C4—C5—H5	104.5	C3—C2—C1	111.0 (2)
C10—C5—H5	104.5	C3—C2—H2A	109.4
C2—C1—C10	114.9 (2)	C1—C2—H2A	109.4
C2—C1—H1A	108.5	C3—C2—H2B	109.4
C10—C1—H1A	108.5	C1—C2—H2B	109.4
C2—C1—H1B	108.5	H2A—C2—H2B	108.0
C10—C1—H1B	108.5	C15—O4—C16	105.5 (3)
H1A—C1—H1B	107.5	C2—C3—C4	114.0 (3)
O1—C6—C5	126.6 (2)	C2—C3—H3A	108.7
O1—C6—C7	119.0 (2)	C4—C3—H3A	108.7
C5—C6—C7	114.3 (2)	C2—C3—H3B	108.7
C7—O2—H2	98 (2)	C4—C3—H3B	108.7
C17—C8—C7	109.9 (2)	H3A—C3—H3B	107.6
C17—C8—C9	113.7 (2)	C16—C13—C14	104.3 (3)
C7—C8—C9	109.4 (2)	C16—C13—C12	128.0 (3)
C17—C8—H8	107.9	C14—C13—C12	127.6 (3)
C7—C8—H8	107.9	C4—C18—H18A	109.5
C9—C8—H8	107.9	C4—C18—H18B	109.5
C12—C11—C9	115.6 (2)	H18A—C18—H18B	109.5
C12—C11—H11A	108.4	C4—C18—H18C	109.5
C9—C11—H11A	108.4	H18A—C18—H18C	109.5
C12—C11—H11B	108.4	H18B—C18—H18C	109.5
C9—C11—H11B	108.4	C4—C19—H19A	109.5
H11A—C11—H11B	107.4	C4—C19—H19B	109.5
C13—C12—C11	112.4 (2)	H19A—C19—H19B	109.5
C13—C12—H12A	109.1	C4—C19—H19C	109.5
C11—C12—H12A	109.1	H19A—C19—H19C	109.5
C13—C12—H12B	109.1	H19B—C19—H19C	109.5
C11—C12—H12B	109.1	C15—C14—C13	108.2 (3)
H12A—C12—H12B	107.9	C15—C14—H14	125.9
C8—C17—H17A	109.5	C13—C14—H14	125.9
C8—C17—H17B	109.5	C13—C16—O4	111.7 (3)
H17A—C17—H17B	109.5	C13—C16—H16	124.1
C8—C17—H17C	109.5	O4—C16—H16	124.1
H17A—C17—H17C	109.5	C14—C15—O4	110.3 (3)
H17B—C17—H17C	109.5	C14—C15—H15	124.8
C18—C4—C19	107.7 (2)	O4—C15—H15	124.8
O3—C9—C10—C1	58.2 (2)	C10—C9—C11—C12	133.9 (2)
C8—C9—C10—C1	175.7 (2)	C9—C11—C12—C13	178.7 (2)
C11—C9—C10—C1	−62.0 (3)	C6—C5—C4—C18	60.4 (3)
O3—C9—C10—C20	179.43 (17)	C10—C5—C4—C18	−169.0 (2)
C8—C9—C10—C20	−63.1 (2)	C6—C5—C4—C19	−61.1 (3)
C11—C9—C10—C20	59.3 (2)	C10—C5—C4—C19	69.5 (3)
O3—C9—C10—C5	−58.8 (2)	C6—C5—C4—C3	176.8 (2)
C8—C9—C10—C5	58.7 (2)	C10—C5—C4—C3	−52.5 (3)
C11—C9—C10—C5	−178.96 (18)	O1—C6—C7—O2	−2.5 (3)
C1—C10—C5—C6	−175.4 (2)	C5—C6—C7—O2	177.4 (2)
C20—C10—C5—C6	63.4 (2)	O1—C6—C7—C8	122.3 (3)
C9—C10—C5—C6	−56.8 (2)	C5—C6—C7—C8	−57.8 (3)
C1—C10—C5—C4	50.9 (3)	C17—C8—C7—O2	−54.3 (3)
C20—C10—C5—C4	−70.3 (3)	C9—C8—C7—O2	−179.9 (2)
C9—C10—C5—C4	169.49 (19)	C17—C8—C7—C6	−178.8 (2)
C20—C10—C1—C2	71.2 (3)	C9—C8—C7—C6	55.6 (3)
C5—C10—C1—C2	−50.6 (3)	C10—C1—C2—C3	55.8 (3)
C9—C10—C1—C2	−168.6 (2)	C1—C2—C3—C4	−57.4 (3)
C4—C5—C6—O1	12.5 (4)	C18—C4—C3—C2	171.0 (2)
C10—C5—C6—O1	−122.2 (3)	C19—C4—C3—C2	−72.0 (3)
C4—C5—C6—C7	−167.4 (2)	C5—C4—C3—C2	54.1 (3)
C10—C5—C6—C7	57.9 (3)	C11—C12—C13—C16	−107.2 (4)
O3—C9—C8—C17	−66.3 (3)	C11—C12—C13—C14	70.4 (4)
C11—C9—C8—C17	55.7 (3)	C16—C13—C14—C15	−0.2 (4)
C10—C9—C8—C17	178.7 (2)	C12—C13—C14—C15	−178.3 (3)
O3—C9—C8—C7	57.0 (2)	C14—C13—C16—O4	0.5 (4)
C11—C9—C8—C7	179.04 (19)	C12—C13—C16—O4	178.5 (3)
C10—C9—C8—C7	−57.9 (3)	C15—O4—C16—C13	−0.5 (4)
O3—C9—C11—C12	17.6 (3)	C13—C14—C15—O4	−0.1 (4)
C8—C9—C11—C12	−103.1 (2)	C16—O4—C15—C14	0.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.88 (3)	2.06 (4)	2.628 (3)	122 (3)
O3—H3···O2i	0.82	2.46	3.203 (3)	151

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O2H2O1	0.88(3)	2.06(4)	2.628(3)	122(3)
O3H3O2i	0.82	2.46	3.203(3)	151

Symmetry code: (i) .