Hoodigogenin A from Hoodia gordonii

Shukla, Y.J.; Fronczek, F.R.; Pawar, R.S.; Khan, I.A.

doi:10.1107/S1600536808022368

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Pages o1643-o1644

doi:10.1107/S1600536808022368

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Hoodigogenin A from Hoodia gordonii

Yatin J. Shukla,^a Frank R. Fronczek,^b ^* Rahul S. Pawar ^c and Ikhlas A. Khan ^a,^c

^aDepartment of Pharmacognosy, School of Pharmacy, University of Mississippi, University, MS 38677, USA, ^bDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803-1804, USA, and ^cNational Center for Natural Products Research, Research Institute for Pharmaceutical Sciences, University of Mississippi, University, MS 38677, USA
^*Correspondence e-mail: ffroncz@lsu.edu

(Received 25 June 2008; accepted 16 July 2008; online 31 July 2008)

The title molecule (systematic name: 12-O-β-tigloyl-3β,14β-dihydroxypregn-5-en-20-one), C₂₆H₃₈O₅, isolated from aerial parts of Hoodia gordonii, has its steroid A and C rings in chair conformations, its B ring in a half-chair conformation, and its five-membered ring in an envelope conformation. The OH group at the C/D ring junction forms an intramolecular hydrogen bond with the keto substituent. The OH group on the A ring forms an intermolecular hydrogen bond with the tiglate C=O group, propagating [010] chains in the crystal structure.

Related literature

For related literature, see: Allen (2002 ); Consumer Reports (2006 ); Etter (1990 ); MacLean & Luo (2004 ); Muller & Albers (2002 ); Nutrition Business Journal (2007 ); Pawar et al. (2007 ); Shin et al. (1990 ); Van Heerden et al. (1998 ).

Experimental

Crystal data

C₂₆H₃₈O₅
M_r = 430.56
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.6523 (9) Å
b = 10.6885 (12) Å
c = 27.705 (3) Å
V = 2266.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.30 × 0.27 × 0.05 mm

Data collection

Nonius KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer
Absorption correction: none
9377 measured reflections
2677 independent reflections
2156 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.100
S = 1.02
2677 reflections
287 parameters
H-atom parameters constrained
Δρ_max = 0.20 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
O1—H10H⋯O5ⁱ	0.84	2.11	2.941 (3)	173
O2—H20H⋯O3	0.84	2.10	2.886 (2)	156
Symmetry code: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: COLLECT (Nonius, 2000 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808022368/hb2752sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808022368/hb2752Isup2.hkl

checkCIF report

Comment top

Hoodia gordonii, a succulent plant, is one of the 18 species of Hoodia (Fam. Asclepiadaceae) that are indigenous to the summer rainfall regions of the Kalahari Desert in South Africa, Botswana and Namibia (Muller & Albers, 2002). In past few years, Hoodia gordonii has gained popularity as a weight-loss dietary supplement (Van Heerden et al., 1998; Consumer Reports, 2006; Nutrition Business Journal, 2007; MacLean & Luo, 2004). As a part of our ongoing studies on Hoodia, we recently described isolation and characterization of 11 new oxypregnane glycosides (Hoodigosides A—K) along with P57AS3, the reported active oxypregnane glycoside from H. gordonii (Pawar et al., 2007). These glycosides consist of the title compound, hoodigogenin A, (I) as the aglycone. (I) is an unique pregnane derivative, owing to the cis-fusion of rings C and D of the steroid skeleton and the tiglic ester functionality at C12, and is only reported so far from H. gordonii.

The preliminary structure of (I) was elucidated with the help of one-dimensional and two-dimensional NMR, and HRESI-MS methods. The relative configurations were established using the NOESY correlations, in which (I) was characterized as having β-OH groups at C3, and C14. The tiglic ester substitution at C12 and the acetyl side chain at C17 were assigned a β orientation as well (Pawar et al., 2007). Here we report the crystal structure of (I) (Fig. 1), which confirms the relative configurations ascribed by the NMR studies.

The A and C rings (C1—C5, C10; C8, C9, C11—C14 respectively) have chair conformations, with endocyclic torsion-angle magnitudes in the range 42.2 (3) to 60.1 (2)°. The unsaturated B ring (C5—C10) has a half-chair conformation, with C8 displaced by 0.431 (2) Å and C9 by -0.373 (2) Å from the best plane of the other four C atoms. The five-membered D ring has an envelope conformation, with C14 at the flap position, displaced by 0.625 (2) Å from the best plane of the other four C atoms. The conformation of the C(O)Me group with respect to the main skeleton is defined by the torsion angle C16—C17—C20—O3, -37.5 (3)°, and the conformation of the tiglate substituent with respect to the skeleton by C11—C12—O4—C22, -102.8 (2)°. The tiglate is approximately planar, having a slight twist of -5.2 (3)° about its central bond (O4—C22—C23—C25).

The O2—H group forms an intramolecular hydrogen bond with C(O)Me carbonyl O3, making a discrete seven-membered ring, graph set S(7) (Etter, 1990). The O1—H group forms an intermolecular hydrogen bond with tiglate O5 (at 2-x, y-1/2, 3/2-z), thus making chains in the [0 1 0] direction (Table 1).

The Cambridge Structural Database (version 5.29, Nov. 2007; Allen, 2002) contains only one Δ⁵-pregnane steroid having O-substituents at C3, C12, and C14, refcode SENKUR (Shin et al., 1990). SENKUR, like (I) has OH groups at C3 and C14, a benzoate at C12, and also OH groups at C8 and C17. The conformations of the A, B, and C rings in (I) and SENKUR are similar, with 18 endocyclic torsion angles differing by a mean value of 5.7°. The five-membered ring of SENKUR, however, has an envelope conformation with a different atom, C13 at the flap position. This may be a result of the fact that SENKUR has the opposite configuration at C17, with the C(O)Me substituent α oriented (Shin et al., 1990).

Related literature top

For related literature, see: Allen (2002); Consumer Reports (2006); Etter (1990); MacLean & Luo (2004); Muller & Albers (2002); Nutrition Business Journal (2007); Pawar et al. (2007); Shin et al. (1990); Van Heerden et al. (1998).

Experimental top

Powdered aerial parts of H. gordonii were purchased from a commercial supplier. The plant material was authenticated by Vaishali Joshi by comparing with authentic sample of H. gordonii obtained from Missouri Botanical Garden Missouri, USA. A voucher specimen (Voucher No. 2799) has been deposited in the repository of The National Center for Natural Product Research. 4.75 kg of coarsely powdered H. gordonii was extracted by percolation with CHCl₃ (4 × 4 L). These extracts were combined and concentrated to obtain a thick mass (402.1 g). The extract was dissolved in MeOH/H₂O (95:5 v/v) and partitioned with hexane. The polar fraction (136 g) was subjected to VLC on silica gel (1500 g) by eluting with gradients of CHCl₃/MeOH/H₂O from 100:4:0.5 (3L), up to 90:12:0.5 (by increasing MeOH and reducing CHCl₃, each by 1% increments), to generate eight sub-fractions.

The sub-fraction 2 was repeatedly chromatographed on a silica gel column using isocratic solvent systems of hexane: CHCl₃ (2:98) and CH₂Cl₂ (100%) that led to isolation of the title compound as an amorphous solid. Compound (I) displayed a prominent blue spot on TLC upon spraying with anisaldehyde-H₂SO₄ reagent, followed by heating at 100 °C for 1–2 minutes. Further, (I) was dissolved in acetone:hexane (70:30 v/v), which upon standing at room temperature for 24 h yielded 150 mg of colorless crystals. Colorless plates of (I) suitable for X-ray diffraction were obtained by recrystallization in hexane with few drops of acetone. The specific rotation of hoodigogenin A [α]²⁵_D is +1.33 (c0.3, CHCl₃). Detailed HRESI-MS and NMR data for (1) were described previously (Pawar et al., 2007).

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. View of the molecular structure of (I), with displacement ellipsoids at the 50% level (spheres of arbitrary radius for the H atoms).

12-O-β-tigloyl-3β,1β-dihydroxypregn-5-en-20-one top

Crystal data top

C₂₆H₃₈O₅	F(000) = 936
M_r = 430.56	D_x = 1.262 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2446 reflections
a = 7.6523 (9) Å	θ = 2.5–26.6°
b = 10.6885 (12) Å	µ = 0.09 mm⁻¹
c = 27.705 (3) Å	T = 100 K
V = 2266.0 (4) Å³	Plate, colorless
Z = 4	0.30 × 0.27 × 0.05 mm

Data collection top

Nonius KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer	2156 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
Graphite monochromator	θ_max = 26.7°, θ_min = 2.7°
ω and ϕ scans	h = −9→9
9377 measured reflections	k = −13→13
2677 independent reflections	l = −34→34

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0516P)² + 0.3846P] where P = (F_o² + 2F_c²)/3
2677 reflections	(Δ/σ)_max < 0.001
287 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₂₆H₃₈O₅	V = 2266.0 (4) Å³
M_r = 430.56	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.6523 (9) Å	µ = 0.09 mm⁻¹
b = 10.6885 (12) Å	T = 100 K
c = 27.705 (3) Å	0.30 × 0.27 × 0.05 mm

Data collection top

Nonius KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer	2156 reflections with I > 2σ(I)
9377 measured reflections	R_int = 0.030
2677 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.02	Δρ_max = 0.20 e Å⁻³
2677 reflections	Δρ_min = −0.17 e Å⁻³
287 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	0.9957 (2)	0.46948 (17)	0.91649 (6)	0.0407 (5)
H10H	1.0621	0.4080	0.9120	0.061*
O2	0.3082 (2)	0.30783 (16)	0.67021 (6)	0.0341 (4)
H20H	0.2534	0.3094	0.6439	0.051*
O3	0.2237 (2)	0.30076 (18)	0.56873 (6)	0.0436 (5)
O4	0.7859 (2)	0.53134 (15)	0.59363 (6)	0.0305 (4)
O5	0.7923 (2)	0.74167 (16)	0.59427 (6)	0.0369 (4)
C1	0.9214 (3)	0.5459 (3)	0.78456 (8)	0.0302 (5)
H1A	1.0060	0.5598	0.7581	0.036*
H1B	0.8524	0.6236	0.7884	0.036*
C2	1.0228 (3)	0.5220 (3)	0.83123 (9)	0.0342 (6)
H2A	1.1021	0.4498	0.8266	0.041*
H2B	1.0951	0.5962	0.8389	0.041*
C3	0.9010 (4)	0.4954 (2)	0.87292 (8)	0.0338 (6)
H3	0.8282	0.5718	0.8785	0.041*
C4	0.7785 (3)	0.3879 (2)	0.86049 (9)	0.0329 (6)
H4A	0.8471	0.3095	0.8585	0.039*
H4B	0.6921	0.3780	0.8868	0.039*
C5	0.6821 (3)	0.4070 (2)	0.81332 (9)	0.0291 (5)
C6	0.5095 (3)	0.3951 (2)	0.81037 (9)	0.0329 (6)
H6	0.4469	0.3787	0.8393	0.039*
C7	0.4070 (3)	0.4058 (3)	0.76433 (9)	0.0349 (6)
H7A	0.3450	0.4871	0.7638	0.042*
H7B	0.3182	0.3385	0.7632	0.042*
C8	0.5244 (3)	0.3962 (2)	0.71992 (8)	0.0289 (5)
H8	0.5711	0.3089	0.7191	0.035*
C9	0.6822 (3)	0.4840 (2)	0.72681 (8)	0.0273 (5)
H9	0.6346	0.5680	0.7358	0.033*
C10	0.7967 (3)	0.4390 (2)	0.76984 (8)	0.0276 (5)
C11	0.7907 (3)	0.5023 (2)	0.68051 (8)	0.0292 (6)
H11A	0.8714	0.5738	0.6850	0.035*
H11B	0.8622	0.4266	0.6747	0.035*
C12	0.6770 (3)	0.5265 (2)	0.63685 (8)	0.0284 (5)
H12	0.6155	0.6084	0.6409	0.034*
C13	0.5413 (3)	0.4230 (2)	0.62780 (8)	0.0282 (5)
C14	0.4220 (3)	0.4154 (2)	0.67314 (9)	0.0283 (5)
C15	0.3094 (3)	0.5331 (2)	0.66889 (9)	0.0324 (6)
H15A	0.3745	0.6079	0.6798	0.039*
H15B	0.2013	0.5250	0.6883	0.039*
C16	0.2667 (3)	0.5414 (3)	0.61473 (9)	0.0361 (6)
H16A	0.2616	0.6299	0.6044	0.043*
H16B	0.1522	0.5019	0.6080	0.043*
C17	0.4140 (3)	0.4716 (2)	0.58736 (9)	0.0311 (5)
H17	0.4780	0.5329	0.5666	0.037*
C18	0.6315 (3)	0.2983 (2)	0.61696 (9)	0.0324 (6)
H18A	0.6999	0.2722	0.6451	0.049*
H18B	0.7093	0.3083	0.5891	0.049*
H18C	0.5431	0.2347	0.6097	0.049*
C19	0.9048 (3)	0.3220 (2)	0.75633 (9)	0.0306 (6)
H19A	0.9960	0.3454	0.7332	0.046*
H19B	0.8279	0.2592	0.7418	0.046*
H19C	0.9590	0.2873	0.7854	0.046*
C20	0.3456 (3)	0.3660 (2)	0.55563 (9)	0.0336 (6)
C21	0.4373 (4)	0.3454 (3)	0.50851 (9)	0.0427 (7)
H21A	0.5622	0.3317	0.5144	0.064*
H21B	0.4221	0.4191	0.4879	0.064*
H21C	0.3877	0.2719	0.4924	0.064*
C22	0.8251 (3)	0.6433 (2)	0.57417 (9)	0.0296 (5)
C23	0.9065 (3)	0.6338 (2)	0.52566 (9)	0.0301 (6)
C24	0.9321 (4)	0.7573 (3)	0.50011 (11)	0.0379 (6)
H24A	1.0187	0.8073	0.5176	0.057*
H24B	0.8209	0.8026	0.4990	0.057*
H24C	0.9735	0.7420	0.4672	0.057*
C25	0.9463 (3)	0.5220 (3)	0.50738 (9)	0.0344 (6)
H25	0.9221	0.4519	0.5274	0.041*
C26	1.0243 (4)	0.4940 (3)	0.45924 (9)	0.0412 (7)
H26A	1.0654	0.5719	0.4444	0.062*
H26B	0.9359	0.4553	0.4385	0.062*
H26C	1.1230	0.4364	0.4632	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0448 (11)	0.0395 (11)	0.0377 (10)	0.0083 (10)	−0.0043 (9)	−0.0037 (8)
O2	0.0286 (9)	0.0326 (9)	0.0412 (9)	−0.0092 (8)	−0.0009 (8)	0.0016 (8)
O3	0.0432 (10)	0.0413 (11)	0.0463 (10)	−0.0129 (10)	−0.0051 (10)	0.0009 (9)
O4	0.0285 (8)	0.0268 (9)	0.0363 (9)	0.0004 (8)	0.0056 (8)	0.0033 (8)
O5	0.0416 (10)	0.0273 (10)	0.0417 (10)	−0.0030 (9)	0.0086 (9)	−0.0013 (8)
C1	0.0268 (12)	0.0270 (13)	0.0369 (13)	−0.0032 (11)	0.0028 (11)	−0.0010 (11)
C2	0.0316 (12)	0.0317 (14)	0.0395 (14)	−0.0052 (12)	0.0004 (12)	−0.0019 (12)
C3	0.0355 (13)	0.0312 (15)	0.0346 (13)	0.0060 (12)	−0.0026 (12)	−0.0002 (11)
C4	0.0313 (12)	0.0314 (14)	0.0360 (13)	0.0003 (12)	0.0050 (11)	0.0008 (11)
C5	0.0279 (12)	0.0221 (13)	0.0371 (13)	0.0007 (10)	0.0024 (11)	0.0005 (10)
C6	0.0299 (13)	0.0333 (14)	0.0354 (13)	−0.0004 (12)	0.0046 (11)	0.0028 (12)
C7	0.0264 (13)	0.0380 (15)	0.0403 (15)	−0.0009 (12)	0.0048 (12)	0.0024 (12)
C8	0.0227 (11)	0.0254 (13)	0.0386 (13)	−0.0004 (11)	0.0007 (11)	0.0018 (11)
C9	0.0246 (11)	0.0237 (13)	0.0337 (13)	0.0011 (10)	0.0024 (10)	0.0006 (10)
C10	0.0239 (11)	0.0243 (13)	0.0345 (13)	−0.0002 (10)	0.0027 (10)	−0.0004 (10)
C11	0.0215 (11)	0.0298 (14)	0.0362 (13)	−0.0012 (10)	0.0008 (10)	0.0020 (10)
C12	0.0252 (12)	0.0263 (13)	0.0338 (13)	0.0008 (11)	0.0036 (11)	0.0018 (11)
C13	0.0227 (11)	0.0265 (13)	0.0354 (13)	0.0016 (10)	−0.0007 (10)	0.0025 (11)
C14	0.0200 (11)	0.0269 (13)	0.0381 (13)	−0.0023 (10)	0.0037 (11)	−0.0003 (11)
C15	0.0245 (12)	0.0305 (13)	0.0422 (13)	0.0005 (11)	0.0027 (12)	−0.0007 (12)
C16	0.0327 (13)	0.0323 (14)	0.0434 (15)	0.0060 (12)	0.0001 (12)	0.0011 (12)
C17	0.0277 (11)	0.0288 (13)	0.0369 (13)	0.0004 (11)	−0.0009 (11)	0.0029 (11)
C18	0.0340 (13)	0.0260 (13)	0.0372 (13)	0.0012 (11)	−0.0004 (12)	−0.0009 (11)
C19	0.0267 (12)	0.0280 (14)	0.0372 (13)	0.0000 (11)	0.0017 (11)	0.0006 (11)
C20	0.0333 (13)	0.0289 (14)	0.0388 (14)	0.0014 (12)	−0.0067 (12)	0.0057 (11)
C21	0.0473 (17)	0.0415 (17)	0.0393 (15)	0.0039 (14)	−0.0017 (14)	−0.0023 (13)
C22	0.0238 (12)	0.0273 (13)	0.0379 (13)	−0.0017 (11)	−0.0014 (11)	0.0030 (11)
C23	0.0238 (12)	0.0337 (14)	0.0327 (13)	−0.0027 (11)	−0.0010 (11)	0.0032 (11)
C24	0.0379 (14)	0.0369 (15)	0.0388 (13)	−0.0039 (13)	0.0075 (13)	0.0026 (11)
C25	0.0318 (13)	0.0343 (15)	0.0371 (13)	0.0018 (12)	0.0005 (12)	0.0025 (12)
C26	0.0426 (15)	0.0396 (17)	0.0415 (15)	0.0064 (13)	0.0018 (13)	−0.0021 (12)

Geometric parameters (Å, º) top

O1—C3	1.435 (3)	C11—H11B	0.9900
O1—H10H	0.8400	C12—C13	1.538 (3)
O2—C14	1.445 (3)	C12—H12	1.0000
O2—H20H	0.8400	C13—C18	1.530 (3)
O3—C20	1.220 (3)	C13—C14	1.555 (3)
O4—C22	1.347 (3)	C13—C17	1.573 (3)
O4—C12	1.460 (3)	C14—C15	1.529 (3)
O5—C22	1.216 (3)	C15—C16	1.538 (3)
C1—C2	1.530 (3)	C15—H15A	0.9900
C1—C10	1.543 (3)	C15—H15B	0.9900
C1—H1A	0.9900	C16—C17	1.550 (3)
C1—H1B	0.9900	C16—H16A	0.9900
C2—C3	1.511 (3)	C16—H16B	0.9900
C2—H2A	0.9900	C17—C20	1.523 (4)
C2—H2B	0.9900	C17—H17	1.0000
C3—C4	1.523 (4)	C18—H18A	0.9800
C3—H3	1.0000	C18—H18B	0.9800
C4—C5	1.515 (3)	C18—H18C	0.9800
C4—H4A	0.9900	C19—H19A	0.9800
C4—H4B	0.9900	C19—H19B	0.9800
C5—C6	1.329 (3)	C19—H19C	0.9800
C5—C10	1.529 (3)	C20—C21	1.498 (4)
C6—C7	1.502 (3)	C21—H21A	0.9800
C6—H6	0.9500	C21—H21B	0.9800
C7—C8	1.527 (3)	C21—H21C	0.9800
C7—H7A	0.9900	C22—C23	1.485 (3)
C7—H7B	0.9900	C23—C25	1.333 (4)
C8—C14	1.528 (3)	C23—C24	1.511 (4)
C8—C9	1.542 (3)	C24—H24A	0.9800
C8—H8	1.0000	C24—H24B	0.9800
C9—C11	1.540 (3)	C24—H24C	0.9800
C9—C10	1.555 (3)	C25—C26	1.492 (4)
C9—H9	1.0000	C25—H25	0.9500
C10—C19	1.545 (3)	C26—H26A	0.9800
C11—C12	1.512 (3)	C26—H26B	0.9800
C11—H11A	0.9900	C26—H26C	0.9800

C3—O1—H10H	109.5	C12—C13—C14	107.59 (19)
C14—O2—H20H	109.5	C18—C13—C17	115.3 (2)
C22—O4—C12	119.14 (18)	C12—C13—C17	107.28 (19)
C2—C1—C10	114.4 (2)	C14—C13—C17	103.22 (18)
C2—C1—H1A	108.7	O2—C14—C8	104.46 (18)
C10—C1—H1A	108.7	O2—C14—C15	108.09 (18)
C2—C1—H1B	108.7	C8—C14—C15	117.7 (2)
C10—C1—H1B	108.7	O2—C14—C13	110.49 (19)
H1A—C1—H1B	107.6	C8—C14—C13	113.02 (17)
C3—C2—C1	111.38 (19)	C15—C14—C13	103.07 (19)
C3—C2—H2A	109.4	C14—C15—C16	104.0 (2)
C1—C2—H2A	109.4	C14—C15—H15A	111.0
C3—C2—H2B	109.4	C16—C15—H15A	111.0
C1—C2—H2B	109.4	C14—C15—H15B	111.0
H2A—C2—H2B	108.0	C16—C15—H15B	111.0
O1—C3—C2	111.6 (2)	H15A—C15—H15B	109.0
O1—C3—C4	110.8 (2)	C15—C16—C17	107.2 (2)
C2—C3—C4	110.4 (2)	C15—C16—H16A	110.3
O1—C3—H3	108.0	C17—C16—H16A	110.3
C2—C3—H3	108.0	C15—C16—H16B	110.3
C4—C3—H3	108.0	C17—C16—H16B	110.3
C5—C4—C3	113.1 (2)	H16A—C16—H16B	108.5
C5—C4—H4A	109.0	C20—C17—C16	112.9 (2)
C3—C4—H4A	109.0	C20—C17—C13	112.3 (2)
C5—C4—H4B	109.0	C16—C17—C13	105.12 (19)
C3—C4—H4B	109.0	C20—C17—H17	108.8
H4A—C4—H4B	107.8	C16—C17—H17	108.8
C6—C5—C4	121.6 (2)	C13—C17—H17	108.8
C6—C5—C10	122.9 (2)	C13—C18—H18A	109.5
C4—C5—C10	115.52 (19)	C13—C18—H18B	109.5
C5—C6—C7	124.3 (2)	H18A—C18—H18B	109.5
C5—C6—H6	117.8	C13—C18—H18C	109.5
C7—C6—H6	117.8	H18A—C18—H18C	109.5
C6—C7—C8	111.86 (19)	H18B—C18—H18C	109.5
C6—C7—H7A	109.2	C10—C19—H19A	109.5
C8—C7—H7A	109.2	C10—C19—H19B	109.5
C6—C7—H7B	109.2	H19A—C19—H19B	109.5
C8—C7—H7B	109.2	C10—C19—H19C	109.5
H7A—C7—H7B	107.9	H19A—C19—H19C	109.5
C7—C8—C14	111.91 (18)	H19B—C19—H19C	109.5
C7—C8—C9	108.7 (2)	O3—C20—C21	122.2 (2)
C14—C8—C9	115.15 (19)	O3—C20—C17	121.0 (2)
C7—C8—H8	106.9	C21—C20—C17	116.8 (2)
C14—C8—H8	106.9	C20—C21—H21A	109.5
C9—C8—H8	106.9	C20—C21—H21B	109.5
C11—C9—C8	113.34 (18)	H21A—C21—H21B	109.5
C11—C9—C10	111.96 (18)	C20—C21—H21C	109.5
C8—C9—C10	110.35 (19)	H21A—C21—H21C	109.5
C11—C9—H9	106.9	H21B—C21—H21C	109.5
C8—C9—H9	106.9	O5—C22—O4	122.6 (2)
C10—C9—H9	106.9	O5—C22—C23	124.1 (2)
C5—C10—C1	108.17 (19)	O4—C22—C23	113.2 (2)
C5—C10—C19	108.47 (19)	C25—C23—C22	120.1 (2)
C1—C10—C19	109.41 (19)	C25—C23—C24	125.1 (2)
C5—C10—C9	110.49 (19)	C22—C23—C24	114.7 (2)
C1—C10—C9	108.76 (19)	C23—C24—H24A	109.5
C19—C10—C9	111.48 (19)	C23—C24—H24B	109.5
C12—C11—C9	112.20 (18)	H24A—C24—H24B	109.5
C12—C11—H11A	109.2	C23—C24—H24C	109.5
C9—C11—H11A	109.2	H24A—C24—H24C	109.5
C12—C11—H11B	109.2	H24B—C24—H24C	109.5
C9—C11—H11B	109.2	C23—C25—C26	127.7 (2)
H11A—C11—H11B	107.9	C23—C25—H25	116.2
O4—C12—C11	109.50 (17)	C26—C25—H25	116.2
O4—C12—C13	106.10 (18)	C25—C26—H26A	109.5
C11—C12—C13	113.3 (2)	C25—C26—H26B	109.5
O4—C12—H12	109.3	H26A—C26—H26B	109.5
C11—C12—H12	109.3	C25—C26—H26C	109.5
C13—C12—H12	109.3	H26A—C26—H26C	109.5
C18—C13—C12	110.73 (19)	H26B—C26—H26C	109.5
C18—C13—C14	112.2 (2)

C10—C1—C2—C3	−56.4 (3)	O4—C12—C13—C17	−69.3 (2)
C1—C2—C3—O1	178.4 (2)	C11—C12—C13—C17	170.54 (19)
C1—C2—C3—C4	54.7 (3)	C7—C8—C14—O2	−67.2 (2)
O1—C3—C4—C5	−176.92 (19)	C9—C8—C14—O2	168.12 (18)
C2—C3—C4—C5	−52.8 (3)	C7—C8—C14—C15	52.7 (3)
C3—C4—C5—C6	−128.9 (3)	C9—C8—C14—C15	−72.1 (3)
C3—C4—C5—C10	51.8 (3)	C7—C8—C14—C13	172.7 (2)
C4—C5—C6—C7	−176.5 (2)	C9—C8—C14—C13	48.0 (3)
C10—C5—C6—C7	2.7 (4)	C18—C13—C14—O2	−49.4 (2)
C5—C6—C7—C8	15.6 (4)	C12—C13—C14—O2	−171.42 (18)
C6—C7—C8—C14	−176.4 (2)	C17—C13—C14—O2	75.3 (2)
C6—C7—C8—C9	−48.1 (3)	C18—C13—C14—C8	67.3 (3)
C7—C8—C9—C11	−168.6 (2)	C12—C13—C14—C8	−54.8 (2)
C14—C8—C9—C11	−42.2 (3)	C17—C13—C14—C8	−168.0 (2)
C7—C8—C9—C10	64.9 (2)	C18—C13—C14—C15	−164.7 (2)
C14—C8—C9—C10	−168.70 (19)	C12—C13—C14—C15	73.3 (2)
C6—C5—C10—C1	131.8 (3)	C17—C13—C14—C15	−39.9 (2)
C4—C5—C10—C1	−48.9 (3)	O2—C14—C15—C16	−76.7 (2)
C6—C5—C10—C19	−109.6 (3)	C8—C14—C15—C16	165.4 (2)
C4—C5—C10—C19	69.7 (3)	C13—C14—C15—C16	40.3 (2)
C6—C5—C10—C9	12.9 (3)	C14—C15—C16—C17	−25.1 (3)
C4—C5—C10—C9	−167.9 (2)	C15—C16—C17—C20	122.9 (2)
C2—C1—C10—C5	51.3 (3)	C15—C16—C17—C13	0.2 (3)
C2—C1—C10—C19	−66.7 (3)	C18—C13—C17—C20	23.8 (3)
C2—C1—C10—C9	171.30 (19)	C12—C13—C17—C20	147.6 (2)
C11—C9—C10—C5	−173.29 (19)	C14—C13—C17—C20	−98.9 (2)
C8—C9—C10—C5	−46.0 (2)	C18—C13—C17—C16	147.0 (2)
C11—C9—C10—C1	68.1 (2)	C12—C13—C17—C16	−89.2 (2)
C8—C9—C10—C1	−164.62 (18)	C14—C13—C17—C16	24.2 (2)
C11—C9—C10—C19	−52.6 (3)	C16—C17—C20—O3	−37.5 (3)
C8—C9—C10—C19	74.7 (2)	C13—C17—C20—O3	81.1 (3)
C8—C9—C11—C12	45.5 (3)	C16—C17—C20—C21	143.6 (2)
C10—C9—C11—C12	171.1 (2)	C13—C17—C20—C21	−97.7 (2)
C22—O4—C12—C11	−102.8 (2)	C12—O4—C22—O5	9.5 (3)
C22—O4—C12—C13	134.6 (2)	C12—O4—C22—C23	−168.83 (18)
C9—C11—C12—O4	−174.75 (19)	O5—C22—C23—C25	176.5 (3)
C9—C11—C12—C13	−56.5 (3)	O4—C22—C23—C25	−5.2 (3)
O4—C12—C13—C18	57.3 (2)	O5—C22—C23—C24	−5.4 (4)
C11—C12—C13—C18	−62.9 (2)	O4—C22—C23—C24	172.9 (2)
O4—C12—C13—C14	−179.76 (17)	C22—C23—C25—C26	178.5 (2)
C11—C12—C13—C14	60.1 (2)	C24—C23—C25—C26	0.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H10H···O5ⁱ	0.84	2.11	2.941 (3)	173
O2—H20H···O3	0.84	2.10	2.886 (2)	156

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

Experimental details

Crystal data
Chemical formula	C₂₆H₃₈O₅
M_r	430.56
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	7.6523 (9), 10.6885 (12), 27.705 (3)
V (Å³)	2266.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.27 × 0.05

Data collection
Diffractometer	Nonius KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9377, 2677, 2156
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.632

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.100, 1.02
No. of reflections	2677
No. of parameters	287
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.17

Computer programs: COLLECT (Nonius, 2000), SCALEPACK (Otwinowski & Minor 1997), SCALEPACK and DENZO (Otwinowski & Minor 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H10H···O5ⁱ	0.84	2.11	2.941 (3)	173
O2—H20H···O3	0.84	2.10	2.886 (2)	156

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

Acknowledgements

The purchase of the diffractometer was made possible by grant No. LEQSF (1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents. Phytochemical research on H. gordonii was funded by USFDA `Botanical Dietary Supplements: Science-Base for Authentication' grant No. FD-U-002071-07. The authors thank Missouri Botanical Garden, USA for authentic plant material. YJS is thankful to the NCNPR for a graduate research assistantship.

References

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