6β-Acet­oxy-1α,7β,11β,15β-tetra­hydr­oxy-7α,20-ep­oxy-ent-kaur-16-ene

Yan, F.-L.; Li, P.; Di, X.-M.; Feng, C.; Hou, R.-J.

doi:10.1107/S1600536810000231

organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o295

https://doi.org/10.1107/S1600536810000231

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6β-Acetoxy-1α,7β,11β,15β-tetrahydroxy-7α,20-epoxy-ent-kaur-16-ene

Fu-Lin Yan,^a ^* Peng Li,^a Xue-Mei Di,^a Chuang Feng ^a and Rui-Jie Hou ^a

^aSchool of Pharmacy, Xinxiang Medical University, Xinxiang, Henan 453003, People's Republic of China
^*Correspondence e-mail: yannz2009@163.com

(Received 20 December 2009; accepted 4 January 2010; online 9 January 2010)

The title compound, C₂₂H₃₂O₇, a natural ent-kaurane diterpenoid also referred to as Maoyecrystal F, was obtained from the medicinal plant Isodon nervosa. There are four rings with the expected cis and trans junctions. Cyclohexane ring A adopts a chair conformation, rings B and C adopt boat conformations, while the five-membered ring has an envelope conformation. The molecules stack along the a axis in the crystal and are linked together by intermolecular O—H⋯O hydrogen bonds.

Related literature

For related literature on the genus Isodon and diterpenoids, see: Sun et al. (2001 ); Zhang et al. (2003 ); Yan et al. (2008 ).

Experimental

Crystal data

C₂₂H₃₂O₇
M_r = 408.21
Monoclinic, P 2₁
a = 9.759 (3) Å
b = 6.6712 (17) Å
c = 14.927 (4) Å
β = 90.002 (4)°
V = 971.8 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 93 K
0.50 × 0.33 × 0.23 mm

Data collection

Rigaku AFC10 Saturn724+ diffractometer
7880 measured reflections
2412 independent reflections
2262 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.064
S = 1.00
2412 reflections
281 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O5	0.85 (3)	1.75 (3)	2.5539 (19)	156 (2)
O4—H4O⋯O6ⁱ	0.82 (3)	2.03 (3)	2.843 (2)	172 (2)
O5—H5O⋯O2ⁱⁱ	0.82 (2)	1.85 (2)	2.6467 (18)	165 (2)
O6—H6O⋯O3	0.81 (2)	2.07 (3)	2.7743 (18)	145 (2)
Symmetry codes: (i) x, y-1, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z]$ .

Data collection: CrystalClear (Rigaku, 2008 ); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810000231/hg2621sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810000231/hg2621Isup2.hkl

checkCIF report

Comment top

The title compound, 6β-Acetoxy-1α,7β,11β,15β-tetrahydroxy- 7α,20-epoxy-ent-kaur-16-ene, is a natural ent-kaurane diterpenoid isolated from the medicinal plant Isodon nervosa. It is widely distributed in China, and has long been used as a Chinese folk medicine in the treatment of acute jaundice, hepatitis and acute cholecystitis. We re-examined the leaves of Isodon nervosus collected in Henan province of China and obtained the ent-kaurane diterpenoid, named Maoyecrystal F (Yan et al., 2008). The compound has also been isolated from Isodon japonica and its structure was postulated from spectroscopic methods (Zhang et al., 2003). Its X-ray crystallographic analysis confirms this proposed molecular structure (Fig. 1). In the structure there is a trans junction between ring A (C1—C5/C10) and ring B (C5—C10); cis junctions are present between ring B and ring C (C8/C9/C11—C14), and ring C and ring D (C8/C13—C16). Ring A adopts chair conformation, with an average torsion angles of 53.99 (19) °. Rings B and C adopt boat conformation because of the formation of the oxygen bridge at C-7 and C-20. Ring D shows an evenlope conformation. In addition, the six-membered rings O1/C20/C10/C5—C7 and O1/C7—C10/C20 both adopt boat conformations. The four hydroxy groups at C1, C7, C11 and C15 adopt α, β, β, β-orientations respectively, an acetoxy group at C6 adopt β-orientation. Bond lengths and angles are within expected aranges (Allen et al., 1987), with averages values (Å): Csp³—Csp³ = 1.544 (2), Csp³—Csp² = 1.516 (2), Csp²—Csp² (CC) = 1.323 (3), Csp³—O = 1.434 (2).

The compound contains ten chiral centers at C1(S), C5(R), C6(S), C7(S), C8(S), C9(S), C10(S), C11(S),C13(S) and C15(R). Although the absolute configuration could not be reliably determined from anomalous dispersion effects, the negative optical rotation showed this compound to be in the ent-kaurane series as reported in genus Isodon (Sun et al., 2001), rather than in the kaurane series, allowing us to assign the correct configuration. In the crystal structure, intermolecular O—H···O hydrogen bond (table 1) are effective in the stabilization of the structure and are responsible for the formation of a three-dimensional network (Fig. 2).

Related literature top

For related literature on the genus Isodon and diterpenoids, see: Sun et al. (2001); Zhang et al. (2003); Yan et al. (2008).

Experimental top

The dried and crushed leaves of Isodon nervosa (12 kg, collected from Henan Province, China) were extracted three times with Me₂CO/H₂O (7:3, v/v) at room temperature over a period of six days. The extract was filtered and the solvent was removed under reduced pressure. The residue was then partitioned between water and AcOEt. After removal of the solvent, the AcOEt residue was separated by repeated silica gel (200–300 mesh) column chromatography and recrystallization from CHCl₃/CH₃OH(8:1), giving 35 mg of the title compound (m.p. 489–491 K. Optical rotation: [α]_D²⁰ -6.1 ° (c 0.52, CH₃OH). Crystals suitable for X-ray analysis were obtained by slow evaporation of a solution of the title compound in CH₃OH at room temperature.

Structure description top

For related literature on the genus Isodon and diterpenoids, see: Sun et al. (2001); Zhang et al. (2003); Yan et al. (2008).

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecular structure of compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing of compound, viewed along the a axis, showing the O—H···O hydrogen bonds as dashed lines.

6β-Acetoxy-1α,7β,11β,15β-tetrahydroxy-7α,20-epoxy-ent-kaur-16-ene top

Crystal data top

C₂₂H₃₂O₇	F(000) = 440
M_r = 408.21	D_x = 1.396 Mg m⁻³
Monoclinic, P2₁	Melting point = 489–491 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 9.759 (3) Å	Cell parameters from 3508 reflections
b = 6.6712 (17) Å	θ = 3.3–27.5°
c = 14.927 (4) Å	µ = 0.10 mm⁻¹
β = 90.002 (4)°	T = 93 K
V = 971.8 (4) Å³	Prism, colorless
Z = 2	0.50 × 0.33 × 0.23 mm

Data collection top

Rigaku AFC10 Saturn724+ diffractometer	2262 reflections with I > 2σ(I)
Radiation source: rotating anode	R_int = 0.025
Graphite monochromator	θ_max = 27.5°, θ_min = 3.3°
Detector resolution: 28.5714 pixels mm^-1	h = −9→12
ω scans	k = −8→8
7880 measured reflections	l = −19→19
2412 independent reflections

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0336P)² + 0.163P] where P = (F_o² + 2F_c²)/3
2412 reflections	(Δ/σ)_max < 0.001
281 parameters	Δρ_max = 0.25 e Å⁻³
1 restraint	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₂₂H₃₂O₇	V = 971.8 (4) Å³
M_r = 408.21	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 9.759 (3) Å	µ = 0.10 mm⁻¹
b = 6.6712 (17) Å	T = 93 K
c = 14.927 (4) Å	0.50 × 0.33 × 0.23 mm
β = 90.002 (4)°

Data collection top

Rigaku AFC10 Saturn724+ diffractometer	2262 reflections with I > 2σ(I)
7880 measured reflections	R_int = 0.025
2412 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	1 restraint
wR(F²) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.25 e Å⁻³
2412 reflections	Δρ_min = −0.17 e Å⁻³
281 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	0.71560 (11)	0.24172 (19)	0.19745 (8)	0.0137 (3)
O2	0.39948 (13)	0.6243 (2)	0.07687 (8)	0.0153 (3)
O3	0.76328 (11)	0.54105 (18)	0.39884 (7)	0.0130 (3)
O4	0.91072 (12)	0.2840 (2)	0.27898 (9)	0.0146 (3)
O5	0.57949 (12)	0.90169 (19)	0.06925 (8)	0.0149 (3)
O6	0.87086 (12)	0.86646 (19)	0.30694 (8)	0.0143 (3)
O7	0.78961 (13)	0.2859 (2)	0.49762 (9)	0.0232 (3)
C1	0.41761 (16)	0.6066 (3)	0.17186 (11)	0.0124 (3)
H1	0.4059	0.7432	0.1983	0.015*
C2	0.30078 (17)	0.4772 (3)	0.20568 (11)	0.0157 (4)
H2A	0.3104	0.3398	0.1814	0.019*
H2B	0.2125	0.5326	0.1843	0.019*
C3	0.30058 (17)	0.4693 (3)	0.30758 (11)	0.0162 (4)
H3A	0.2223	0.3867	0.3280	0.019*
H3B	0.2878	0.6065	0.3314	0.019*
C4	0.43380 (16)	0.3814 (3)	0.34543 (11)	0.0132 (3)
C5	0.55753 (16)	0.4991 (3)	0.30404 (11)	0.0116 (3)
H5	0.5535	0.6368	0.3304	0.014*
C6	0.69539 (16)	0.4098 (3)	0.33418 (10)	0.0119 (3)
H6	0.6780	0.2771	0.3632	0.014*
C7	0.78918 (16)	0.3783 (3)	0.25387 (11)	0.0121 (3)
C8	0.82107 (16)	0.5716 (3)	0.20203 (11)	0.0116 (3)
C9	0.68182 (16)	0.6785 (3)	0.17895 (11)	0.0111 (3)
H9	0.6720	0.7965	0.2198	0.013*
C10	0.56065 (16)	0.5289 (3)	0.19985 (11)	0.0111 (3)
C11	0.68778 (17)	0.7582 (3)	0.08150 (11)	0.0132 (3)
H11	0.6716	0.6433	0.0398	0.016*
C12	0.82467 (17)	0.8558 (3)	0.05703 (11)	0.0166 (4)
H12A	0.8296	0.9898	0.0854	0.020*
H12B	0.8285	0.8750	−0.0087	0.020*
C13	0.95062 (17)	0.7303 (3)	0.08700 (11)	0.0160 (4)
H13	1.0228	0.7243	0.0395	0.019*
C14	0.90325 (17)	0.5203 (3)	0.11600 (11)	0.0143 (3)
H14A	0.9820	0.4315	0.1292	0.017*
H14B	0.8444	0.4569	0.0700	0.017*
C15	0.92640 (16)	0.7137 (3)	0.24989 (11)	0.0132 (3)
H15	0.9913	0.6298	0.2857	0.016*
C16	1.00555 (17)	0.8127 (3)	0.17408 (11)	0.0152 (4)
C17	1.10478 (18)	0.9460 (3)	0.18423 (13)	0.0210 (4)
H17A	1.1495	1.0001	0.1332	0.025*
H17B	1.1313	0.9875	0.2426	0.025*
C18	0.43741 (17)	0.4168 (3)	0.44718 (11)	0.0165 (4)
H18A	0.3619	0.3437	0.4756	0.020*
H18B	0.4278	0.5604	0.4595	0.020*
H18C	0.5248	0.3689	0.4713	0.020*
C19	0.43608 (18)	0.1517 (3)	0.32907 (12)	0.0169 (4)
H19A	0.3618	0.0884	0.3630	0.020*
H19B	0.5243	0.0970	0.3488	0.020*
H19C	0.4236	0.1247	0.2651	0.020*
C20	0.59817 (16)	0.3306 (3)	0.15381 (11)	0.0124 (3)
H20A	0.5194	0.2372	0.1568	0.015*
H20B	0.6194	0.3554	0.0899	0.015*
C21	0.81536 (17)	0.4540 (3)	0.47425 (11)	0.0158 (4)
C22	0.90964 (19)	0.5955 (3)	0.52190 (12)	0.0221 (4)
H22A	0.9963	0.6051	0.4890	0.027*
H22B	0.9273	0.5457	0.5826	0.027*
H22C	0.8670	0.7283	0.5253	0.027*
H5O	0.597 (2)	0.957 (4)	0.0218 (15)	0.022 (6)*
H6O	0.834 (2)	0.812 (4)	0.3491 (15)	0.025 (6)*
H2O	0.444 (2)	0.730 (4)	0.0632 (15)	0.029 (6)*
H4O	0.892 (2)	0.166 (4)	0.2884 (16)	0.031 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0143 (5)	0.0100 (6)	0.0166 (6)	0.0011 (5)	−0.0030 (4)	−0.0022 (5)
O2	0.0183 (6)	0.0157 (7)	0.0119 (6)	−0.0004 (5)	−0.0039 (5)	−0.0004 (5)
O3	0.0139 (5)	0.0136 (6)	0.0116 (5)	−0.0020 (5)	−0.0024 (4)	−0.0010 (5)
O4	0.0116 (5)	0.0100 (7)	0.0223 (6)	0.0012 (5)	−0.0015 (5)	0.0024 (5)
O5	0.0174 (6)	0.0129 (6)	0.0143 (6)	0.0027 (5)	−0.0016 (5)	0.0034 (5)
O6	0.0178 (6)	0.0108 (6)	0.0145 (6)	−0.0008 (5)	0.0011 (5)	−0.0015 (5)
O7	0.0194 (6)	0.0275 (8)	0.0227 (7)	−0.0025 (6)	−0.0052 (5)	0.0115 (6)
C1	0.0137 (8)	0.0126 (8)	0.0109 (7)	0.0022 (7)	−0.0028 (6)	−0.0008 (6)
C2	0.0127 (7)	0.0170 (9)	0.0174 (8)	−0.0002 (7)	−0.0035 (6)	−0.0001 (7)
C3	0.0116 (7)	0.0191 (9)	0.0179 (8)	0.0000 (7)	0.0011 (6)	0.0005 (7)
C4	0.0118 (7)	0.0144 (9)	0.0135 (7)	−0.0011 (7)	−0.0003 (6)	−0.0003 (7)
C5	0.0118 (7)	0.0112 (8)	0.0117 (7)	0.0005 (7)	−0.0011 (6)	−0.0012 (6)
C6	0.0116 (7)	0.0111 (8)	0.0130 (7)	−0.0015 (7)	−0.0026 (6)	0.0002 (7)
C7	0.0122 (7)	0.0090 (8)	0.0150 (7)	0.0012 (7)	−0.0027 (6)	−0.0013 (7)
C8	0.0116 (7)	0.0100 (8)	0.0132 (7)	0.0013 (6)	0.0007 (6)	−0.0001 (7)
C9	0.0122 (7)	0.0095 (8)	0.0115 (7)	0.0013 (6)	−0.0013 (6)	−0.0003 (6)
C10	0.0114 (7)	0.0102 (8)	0.0116 (7)	0.0003 (7)	−0.0011 (6)	0.0001 (6)
C11	0.0160 (7)	0.0117 (8)	0.0119 (7)	0.0033 (7)	0.0000 (6)	−0.0002 (6)
C12	0.0179 (8)	0.0157 (9)	0.0161 (8)	−0.0009 (8)	0.0016 (6)	0.0014 (7)
C13	0.0157 (8)	0.0155 (9)	0.0169 (8)	0.0006 (7)	0.0042 (6)	0.0010 (7)
C14	0.0149 (7)	0.0128 (9)	0.0154 (8)	0.0023 (7)	0.0031 (6)	−0.0019 (7)
C15	0.0127 (7)	0.0112 (9)	0.0158 (8)	0.0018 (7)	−0.0011 (6)	0.0000 (7)
C16	0.0133 (7)	0.0123 (9)	0.0199 (8)	0.0038 (7)	0.0017 (6)	0.0007 (7)
C17	0.0184 (8)	0.0189 (10)	0.0257 (9)	−0.0017 (8)	0.0036 (7)	0.0006 (8)
C18	0.0158 (8)	0.0189 (10)	0.0147 (8)	−0.0005 (7)	0.0017 (6)	0.0006 (7)
C19	0.0167 (8)	0.0156 (9)	0.0186 (8)	−0.0040 (7)	−0.0005 (7)	0.0028 (7)
C20	0.0134 (7)	0.0103 (8)	0.0136 (7)	0.0010 (7)	−0.0014 (6)	−0.0017 (7)
C21	0.0115 (7)	0.0236 (10)	0.0124 (7)	0.0018 (7)	−0.0002 (6)	0.0026 (7)
C22	0.0190 (9)	0.0298 (11)	0.0175 (8)	0.0000 (8)	−0.0049 (7)	−0.0014 (8)

Geometric parameters (Å, º) top

O1—C7	1.434 (2)	C8—C9	1.573 (2)
O1—C20	1.4453 (19)	C9—C11	1.550 (2)
O2—C1	1.4337 (19)	C9—C10	1.578 (2)
O2—H2O	0.85 (3)	C9—H9	1.0000
O3—C21	1.365 (2)	C10—C20	1.535 (2)
O3—C6	1.4620 (19)	C11—C12	1.530 (2)
O4—C7	1.394 (2)	C11—H11	1.0000
O4—H4O	0.82 (3)	C12—C13	1.553 (2)
O5—C11	1.438 (2)	C12—H12A	0.9900
O5—H5O	0.82 (2)	C12—H12B	0.9900
O6—C15	1.434 (2)	C13—C16	1.510 (2)
O6—H6O	0.81 (2)	C13—C14	1.537 (3)
O7—C21	1.201 (2)	C13—H13	1.0000
C1—C2	1.517 (2)	C14—H14A	0.9900
C1—C10	1.546 (2)	C14—H14B	0.9900
C1—H1	1.0000	C15—C16	1.521 (2)
C2—C3	1.522 (2)	C15—H15	1.0000
C2—H2A	0.9900	C16—C17	1.323 (3)
C2—H2B	0.9900	C17—H17A	0.9500
C3—C4	1.534 (2)	C17—H17B	0.9500
C3—H3A	0.9900	C18—H18A	0.9800
C3—H3B	0.9900	C18—H18B	0.9800
C4—C18	1.538 (2)	C18—H18C	0.9800
C4—C19	1.552 (3)	C19—H19A	0.9800
C4—C5	1.567 (2)	C19—H19B	0.9800
C5—C6	1.539 (2)	C19—H19C	0.9800
C5—C10	1.568 (2)	C20—H20A	0.9900
C5—H5	1.0000	C20—H20B	0.9900
C6—C7	1.523 (2)	C21—C22	1.498 (3)
C6—H6	1.0000	C22—H22A	0.9800
C7—C8	1.535 (2)	C22—H22B	0.9800
C8—C14	1.552 (2)	C22—H22C	0.9800
C8—C15	1.570 (2)

C7—O1—C20	113.65 (13)	C5—C10—C9	106.89 (12)
C1—O2—H2O	104.1 (16)	O5—C11—C12	109.13 (14)
C21—O3—C6	117.28 (14)	O5—C11—C9	108.68 (13)
C7—O4—H4O	106.7 (17)	C12—C11—C9	113.75 (13)
C11—O5—H5O	104.9 (16)	O5—C11—H11	108.4
C15—O6—H6O	108.2 (17)	C12—C11—H11	108.4
O2—C1—C2	106.46 (13)	C9—C11—H11	108.4
O2—C1—C10	113.96 (13)	C11—C12—C13	113.12 (14)
C2—C1—C10	113.43 (14)	C11—C12—H12A	109.0
O2—C1—H1	107.6	C13—C12—H12A	109.0
C2—C1—H1	107.6	C11—C12—H12B	109.0
C10—C1—H1	107.6	C13—C12—H12B	109.0
C1—C2—C3	110.70 (14)	H12A—C12—H12B	107.8
C1—C2—H2A	109.5	C16—C13—C14	101.32 (14)
C3—C2—H2A	109.5	C16—C13—C12	109.43 (15)
C1—C2—H2B	109.5	C14—C13—C12	109.54 (14)
C3—C2—H2B	109.5	C16—C13—H13	112.0
H2A—C2—H2B	108.1	C14—C13—H13	112.0
C2—C3—C4	112.34 (14)	C12—C13—H13	112.0
C2—C3—H3A	109.1	C13—C14—C8	100.80 (13)
C4—C3—H3A	109.1	C13—C14—H14A	111.6
C2—C3—H3B	109.1	C8—C14—H14A	111.6
C4—C3—H3B	109.1	C13—C14—H14B	111.6
H3A—C3—H3B	107.9	C8—C14—H14B	111.6
C3—C4—C18	108.92 (14)	H14A—C14—H14B	109.4
C3—C4—C19	109.37 (15)	O6—C15—C16	108.98 (15)
C18—C4—C19	107.88 (15)	O6—C15—C8	116.86 (13)
C3—C4—C5	108.42 (14)	C16—C15—C8	104.85 (13)
C18—C4—C5	107.14 (13)	O6—C15—H15	108.6
C19—C4—C5	114.95 (14)	C16—C15—H15	108.6
C6—C5—C4	111.35 (14)	C8—C15—H15	108.6
C6—C5—C10	108.79 (13)	C17—C16—C13	127.09 (17)
C4—C5—C10	117.99 (13)	C17—C16—C15	125.33 (16)
C6—C5—H5	106.0	C13—C16—C15	107.58 (14)
C4—C5—H5	106.0	C16—C17—H17A	120.0
C10—C5—H5	106.0	C16—C17—H17B	120.0
O3—C6—C7	109.26 (12)	H17A—C17—H17B	120.0
O3—C6—C5	110.92 (14)	C4—C18—H18A	109.5
C7—C6—C5	110.41 (13)	C4—C18—H18B	109.5
O3—C6—H6	108.7	H18A—C18—H18B	109.5
C7—C6—H6	108.7	C4—C18—H18C	109.5
C5—C6—H6	108.7	H18A—C18—H18C	109.5
O4—C7—O1	107.27 (13)	H18B—C18—H18C	109.5
O4—C7—C6	111.22 (13)	C4—C19—H19A	109.5
O1—C7—C6	104.41 (12)	C4—C19—H19B	109.5
O4—C7—C8	110.02 (13)	H19A—C19—H19B	109.5
O1—C7—C8	109.84 (13)	C4—C19—H19C	109.5
C6—C7—C8	113.76 (14)	H19A—C19—H19C	109.5
C7—C8—C14	109.67 (14)	H19B—C19—H19C	109.5
C7—C8—C15	114.24 (13)	O1—C20—C10	109.92 (12)
C14—C8—C15	99.86 (13)	O1—C20—H20A	109.7
C7—C8—C9	108.42 (13)	C10—C20—H20A	109.7
C14—C8—C9	111.41 (13)	O1—C20—H20B	109.7
C15—C8—C9	113.04 (14)	C10—C20—H20B	109.7
C11—C9—C8	109.19 (12)	H20A—C20—H20B	108.2
C11—C9—C10	115.50 (13)	O7—C21—O3	123.98 (17)
C8—C9—C10	108.50 (13)	O7—C21—C22	125.39 (16)
C11—C9—H9	107.8	O3—C21—C22	110.63 (16)
C8—C9—H9	107.8	C21—C22—H22A	109.5
C10—C9—H9	107.8	C21—C22—H22B	109.5
C20—C10—C1	112.54 (13)	H22A—C22—H22B	109.5
C20—C10—C5	109.85 (14)	C21—C22—H22C	109.5
C1—C10—C5	107.03 (12)	H22A—C22—H22C	109.5
C20—C10—C9	106.13 (13)	H22B—C22—H22C	109.5
C1—C10—C9	114.25 (14)

O2—C1—C2—C3	−173.23 (14)	C2—C1—C10—C9	−170.68 (14)
C10—C1—C2—C3	60.63 (19)	C6—C5—C10—C20	54.20 (17)
C1—C2—C3—C4	−60.1 (2)	C4—C5—C10—C20	−73.84 (17)
C2—C3—C4—C18	168.91 (15)	C6—C5—C10—C1	176.66 (14)
C2—C3—C4—C19	−73.40 (19)	C4—C5—C10—C1	48.62 (19)
C2—C3—C4—C5	52.65 (19)	C6—C5—C10—C9	−60.52 (17)
C3—C4—C5—C6	−176.20 (14)	C4—C5—C10—C9	171.44 (14)
C18—C4—C5—C6	66.39 (18)	C11—C9—C10—C20	73.03 (17)
C19—C4—C5—C6	−53.47 (19)	C8—C9—C10—C20	−49.90 (16)
C3—C4—C5—C10	−49.38 (19)	C11—C9—C10—C1	−51.57 (18)
C18—C4—C5—C10	−166.79 (15)	C8—C9—C10—C1	−174.50 (13)
C19—C4—C5—C10	73.35 (19)	C11—C9—C10—C5	−169.77 (14)
C21—O3—C6—C7	−104.90 (15)	C8—C9—C10—C5	67.31 (16)
C21—O3—C6—C5	133.16 (14)	C8—C9—C11—O5	−163.90 (13)
C4—C5—C6—O3	−107.33 (15)	C10—C9—C11—O5	73.54 (17)
C10—C5—C6—O3	120.97 (14)	C8—C9—C11—C12	−42.11 (19)
C4—C5—C6—C7	131.41 (15)	C10—C9—C11—C12	−164.67 (15)
C10—C5—C6—C7	−0.29 (19)	O5—C11—C12—C13	167.63 (13)
C20—O1—C7—O4	−170.16 (13)	C9—C11—C12—C13	46.1 (2)
C20—O1—C7—C6	71.74 (15)	C11—C12—C13—C16	−98.54 (17)
C20—O1—C7—C8	−50.61 (16)	C11—C12—C13—C14	11.7 (2)
O3—C6—C7—O4	62.10 (17)	C16—C13—C14—C8	47.88 (15)
C5—C6—C7—O4	−175.65 (14)	C12—C13—C14—C8	−67.65 (16)
O3—C6—C7—O1	177.48 (13)	C7—C8—C14—C13	−168.02 (13)
C5—C6—C7—O1	−60.27 (17)	C15—C8—C14—C13	−47.72 (15)
O3—C6—C7—C8	−62.79 (17)	C9—C8—C14—C13	71.94 (16)
C5—C6—C7—C8	59.46 (18)	C7—C8—C15—O6	−92.48 (18)
O4—C7—C8—C14	60.79 (17)	C14—C8—C15—O6	150.59 (14)
O1—C7—C8—C14	−57.07 (17)	C9—C8—C15—O6	32.1 (2)
C6—C7—C8—C14	−173.68 (13)	C7—C8—C15—C16	146.76 (14)
O4—C7—C8—C15	−50.34 (18)	C14—C8—C15—C16	29.83 (16)
O1—C7—C8—C15	−168.19 (13)	C9—C8—C15—C16	−88.63 (15)
C6—C7—C8—C15	75.20 (17)	C14—C13—C16—C17	150.63 (18)
O4—C7—C8—C9	−177.37 (13)	C12—C13—C16—C17	−93.8 (2)
O1—C7—C8—C9	64.77 (16)	C14—C13—C16—C15	−29.05 (16)
C6—C7—C8—C9	−51.83 (17)	C12—C13—C16—C15	86.56 (17)
C7—C8—C9—C11	−137.89 (14)	O6—C15—C16—C17	53.7 (2)
C14—C8—C9—C11	−17.12 (19)	C8—C15—C16—C17	179.54 (17)
C15—C8—C9—C11	94.40 (16)	O6—C15—C16—C13	−126.61 (14)
C7—C8—C9—C10	−11.23 (17)	C8—C15—C16—C13	−0.78 (18)
C14—C8—C9—C10	109.54 (15)	C7—O1—C20—C10	−15.94 (18)
C15—C8—C9—C10	−138.94 (14)	C1—C10—C20—O1	−166.48 (13)
O2—C1—C10—C20	−53.85 (19)	C5—C10—C20—O1	−47.35 (17)
C2—C1—C10—C20	68.20 (17)	C9—C10—C20—O1	67.87 (16)
O2—C1—C10—C5	−174.62 (14)	C6—O3—C21—O7	−12.8 (2)
C2—C1—C10—C5	−52.56 (18)	C6—O3—C21—C22	166.23 (14)
O2—C1—C10—C9	67.26 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O5	0.85 (3)	1.75 (3)	2.5539 (19)	156 (2)
O4—H4O···O6ⁱ	0.82 (3)	2.03 (3)	2.843 (2)	172 (2)
O5—H5O···O2ⁱⁱ	0.82 (2)	1.85 (2)	2.6467 (18)	165 (2)
O6—H6O···O3	0.81 (2)	2.07 (3)	2.7743 (18)	145 (2)

Symmetry codes: (i) x, y−1, z; (ii) −x+1, y+1/2, −z.

Experimental details

Crystal data
Chemical formula	C₂₂H₃₂O₇
M_r	408.21
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	93
a, b, c (Å)	9.759 (3), 6.6712 (17), 14.927 (4)
β (°)	90.002 (4)
V (Å³)	971.8 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.50 × 0.33 × 0.23

Data collection
Diffractometer	Rigaku AFC10 Saturn724+
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7880, 2412, 2262
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.064, 1.00
No. of reflections	2412
No. of parameters	281
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.17

Computer programs: CrystalClear (Rigaku, 2008), 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
O2—H2O···O5	0.85 (3)	1.75 (3)	2.5539 (19)	156 (2)
O4—H4O···O6ⁱ	0.82 (3)	2.03 (3)	2.843 (2)	172 (2)
O5—H5O···O2ⁱⁱ	0.82 (2)	1.85 (2)	2.6467 (18)	165 (2)
O6—H6O···O3	0.81 (2)	2.07 (3)	2.7743 (18)	145 (2)

Symmetry codes: (i) x, y−1, z; (ii) −x+1, y+1/2, −z.

Acknowledgements

This work was supported by the Henan Province Science and Technology Foundation of China (No. 611042600)

References

Rigaku (2008). CrystalClear. Rigaku Corporation, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, H. D., Xu, Y. L. & Jiang, B. (2001). Diterpenoids from Isodon Species, pp. 4–17. Beijing: Science Press. Google Scholar
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Zhang, J. X., Han, Q. B., Zhao, A. H. & Sun, H. D. (2003). Fitoterapia, 74, 435–438. Web of Science CrossRef PubMed CAS Google Scholar