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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2945.
Published online 2010 October 30. doi:  10.1107/S1600536810042686
PMCID: PMC3009124

[1R-(1α,2α,4α,5β,6α,7α)]-4-Benzoyl­oxymethyl-5,6-dihy­droxy-3,8-dioxa­tricyclo­[5.1.0.02,4]octan-5-yl acetate (3-deacetyl­crotepoxide) from Kaempferia rotunda Val.

Abstract

The title compound, C16H16O7, isolated from Kaempferia rotunda rhizomes, features a six-membered cyclo­hexane ring that adopts a twisted-boat conformation owing to the presence of two adjacent epoxide attachments that lock in four of the six axial positions. The CH3CO2– and HO– substituents occupy equatorial positions. However, the bond angles at the ring carbon connected to the C6H5CO2CH2– substituent deviate signifcantly from the idealized tetra­hedral angles as the carbon atom is part of an epoxide ring. In the crystal, the molecules are linked into chains by O—H(...)O hydrogen bonds.

Related literature

For the isolation of the compound from Kaempferia rotunda, see: Pancharoen et al. (1996 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2945-scheme1.jpg

Experimental

Crystal data

  • C16H16O7
  • M r = 320.29
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2945-efi1.jpg
  • a = 5.7451 (7) Å
  • b = 7.1746 (9) Å
  • c = 35.708 (5) Å
  • V = 1471.9 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 100 K
  • 0.35 × 0.05 × 0.05 mm

Data collection

  • Bruker SMART APEX diffractometer
  • 14228 measured reflections
  • 2011 independent reflections
  • 1730 reflections with I > 2σ(I)
  • R int = 0.073

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.117
  • S = 1.12
  • 2011 reflections
  • 213 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.33 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810042686/bt5386sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810042686/bt5386Isup2.hkl

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

Acknowledgments

We thank the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

Kaempferia rotunda is one of the four Malaysian Kaempferia of the Zingiberaceae family; among the constitutents isolated is 3-deacetylcrotepoxide (Scheme I), which was first reported by Pancharoen et al. (1996). 3-Deacetylcrotepoxide (Scheme I) features a six-membered cyclohexane ring that adopts a twisted boat conformation owing to the presence of two adjacent epoxide attachements that tie up four of the six axial positions. The CH3CO2– and HO– substituents occupy regular equatorial positions as each is connected to a methine carbon atom (Fig. 1). However, the bond angles at the ring carbon connected to the C6H5CO2CH2– substituent deviate signifcantly from the idealized tetrahedral angles as the carbon atom is part of an epoxide ring [112.4 (2), 117.9 (2), 120.3 (3) °].

Experimental

Kaempferia rotunda rhizomes were purchased from a market in Kempas, Johor. The rhizomes were dried and then grounded. The grounded rhizomes were extracted with n-hexane (4.5 L), ethyl acetate (4.5 L) and methanol (4.5 L) in a soxhlet extractor for 16 h. The extracts were concentrated to give a dark brown semi-solid from the n-hexane extract (2.32 g), a dark brown oil from the ethyl acetate extract (6.80 g) and a dark brown viscous liquid from the methanol extract (15.27 g). The ethyl acetate extract (6.80 g) was fractionated by VLC (260 g, column size: 10 x 12 cm) by using petroleum ether, ether and ethyl acetate to afford four fractions, (0.02 g, 0.15 g, 2.70 g and 2.50 g. Evaporation of the solvent of the third fraction yielded 3-deacetylcrotepoxide (0.145 g, 2.13%) as colorless crystals.

The absolute configuration was assumed from that obtained from spectroscopic measurements (Pancharoen et al., 1996).

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95–0.99 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2–15U(C).

The hydroxy H-atom was located in a difference Fourier map, and was refined isotropically with the O–H distance restrained to 0.84±0.01 Å.

1374 Friedel pairs were merged.

Figures

Fig. 1.
Anisotropic displacement ellipsoid plot (Barbour, 2001) of C16H16O7 at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C16H16O7F(000) = 672
Mr = 320.29Dx = 1.445 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1788 reflections
a = 5.7451 (7) Åθ = 3.1–20.0°
b = 7.1746 (9) ŵ = 0.12 mm1
c = 35.708 (5) ÅT = 100 K
V = 1471.9 (3) Å3Prism, colorless
Z = 40.35 × 0.05 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer1730 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.073
graphiteθmax = 27.5°, θmin = 1.1°
ω scansh = −7→7
14228 measured reflectionsk = −9→9
2011 independent reflectionsl = −46→46

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117H atoms treated by a mixture of independent and constrained refinement
S = 1.12w = 1/[σ2(Fo2) + (0.0674P)2] where P = (Fo2 + 2Fc2)/3
2011 reflections(Δ/σ)max = 0.001
213 parametersΔρmax = 0.37 e Å3
1 restraintΔρmin = −0.33 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.4671 (3)0.4022 (3)0.89359 (5)0.0161 (4)
O20.1026 (4)0.3085 (3)0.88101 (5)0.0237 (5)
O30.5062 (3)0.3882 (3)0.78913 (5)0.0166 (4)
O40.1819 (4)0.5944 (3)0.74537 (5)0.0204 (5)
O50.4387 (4)0.9627 (3)0.80058 (6)0.0220 (5)
H50.541 (5)0.999 (5)0.7854 (8)0.032 (10)*
O60.6886 (3)0.7118 (3)0.84539 (5)0.0164 (4)
O70.5199 (4)0.8762 (3)0.89191 (6)0.0251 (5)
C10.1872 (5)0.4312 (4)0.94156 (7)0.0152 (6)
C20.3442 (5)0.5291 (4)0.96376 (8)0.0177 (6)
H20.48900.56840.95360.021*
C30.2893 (6)0.5693 (4)1.00069 (8)0.0208 (6)
H30.39630.63641.01580.025*
C40.0783 (6)0.5115 (4)1.01552 (8)0.0207 (6)
H40.04230.53641.04100.025*
C5−0.0805 (5)0.4172 (4)0.99317 (8)0.0203 (6)
H5A−0.22560.37891.00340.024*
C6−0.0289 (5)0.3787 (4)0.95618 (8)0.0183 (6)
H6−0.13950.31690.94080.022*
C70.2420 (5)0.3749 (4)0.90243 (7)0.0163 (6)
C80.5387 (5)0.3349 (4)0.85715 (7)0.0162 (6)
H8A0.48200.20580.85370.019*
H8B0.71080.33290.85580.019*
C90.4444 (5)0.4570 (4)0.82602 (7)0.0143 (6)
C100.2631 (5)0.3857 (4)0.80053 (7)0.0167 (6)
H100.19420.26150.80670.020*
C110.1072 (5)0.5236 (4)0.78182 (7)0.0177 (6)
H11−0.06400.50670.78560.021*
C120.1917 (5)0.7166 (4)0.77788 (7)0.0173 (6)
H120.06990.81600.77900.021*
C130.4278 (6)0.7684 (4)0.79357 (7)0.0170 (6)
H130.55300.73160.77560.020*
C140.4611 (5)0.6656 (4)0.83081 (7)0.0141 (6)
H140.33940.70780.84900.017*
C150.6928 (6)0.8232 (4)0.87612 (7)0.0183 (6)
C160.9378 (6)0.8664 (5)0.88744 (9)0.0274 (7)
H16A0.93660.95300.90870.041*
H16B1.02020.92350.86630.041*
H16C1.01690.75100.89470.041*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0167 (10)0.0203 (11)0.0112 (9)−0.0012 (9)0.0016 (8)0.0001 (8)
O20.0184 (11)0.0360 (13)0.0167 (10)−0.0048 (10)−0.0022 (9)−0.0016 (9)
O30.0193 (10)0.0184 (10)0.0120 (9)0.0009 (9)0.0021 (7)−0.0031 (8)
O40.0252 (11)0.0239 (11)0.0122 (9)−0.0022 (10)−0.0031 (8)0.0016 (8)
O50.0331 (13)0.0125 (10)0.0202 (10)−0.0010 (10)0.0035 (10)0.0003 (8)
O60.0171 (10)0.0177 (10)0.0146 (9)−0.0014 (9)0.0000 (8)−0.0013 (8)
O70.0250 (12)0.0321 (13)0.0182 (10)0.0011 (11)0.0004 (9)−0.0079 (9)
C10.0159 (13)0.0173 (14)0.0124 (12)0.0034 (12)0.0009 (11)0.0031 (10)
C20.0170 (14)0.0161 (14)0.0201 (13)−0.0001 (12)0.0029 (11)0.0032 (11)
C30.0270 (16)0.0167 (14)0.0189 (14)0.0011 (13)−0.0008 (12)−0.0014 (11)
C40.0282 (17)0.0182 (15)0.0158 (13)0.0065 (13)0.0048 (13)0.0011 (11)
C50.0178 (15)0.0201 (16)0.0229 (15)0.0016 (12)0.0029 (12)0.0044 (11)
C60.0152 (14)0.0208 (14)0.0190 (14)0.0000 (13)−0.0029 (11)0.0042 (12)
C70.0168 (14)0.0166 (14)0.0155 (13)−0.0006 (12)−0.0017 (11)0.0038 (11)
C80.0170 (14)0.0183 (14)0.0132 (12)0.0021 (12)0.0000 (11)0.0006 (10)
C90.0160 (13)0.0176 (14)0.0094 (12)0.0012 (12)0.0015 (10)−0.0011 (10)
C100.0178 (14)0.0186 (14)0.0137 (12)−0.0004 (12)0.0004 (11)−0.0015 (11)
C110.0171 (14)0.0237 (15)0.0122 (12)−0.0013 (12)−0.0012 (11)0.0001 (11)
C120.0207 (14)0.0203 (14)0.0110 (12)0.0057 (13)−0.0010 (11)0.0009 (11)
C130.0232 (15)0.0144 (14)0.0133 (12)−0.0008 (12)−0.0003 (12)−0.0007 (10)
C140.0131 (13)0.0173 (14)0.0120 (12)0.0001 (11)0.0017 (10)−0.0005 (10)
C150.0236 (15)0.0173 (15)0.0141 (13)0.0008 (13)−0.0023 (12)−0.0007 (11)
C160.0241 (16)0.0281 (17)0.0300 (16)−0.0003 (15)−0.0067 (14)−0.0071 (14)

Geometric parameters (Å, °)

O1—C71.345 (3)C5—C61.382 (4)
O1—C81.448 (3)C5—H5A0.9500
O2—C71.206 (3)C6—H60.9500
O3—C91.451 (3)C8—C91.515 (4)
O3—C101.455 (3)C8—H8A0.9900
O4—C121.455 (3)C8—H8B0.9900
O4—C111.462 (3)C9—C101.475 (4)
O5—C131.418 (3)C9—C141.509 (4)
O5—H50.84 (3)C10—C111.492 (4)
O6—C151.358 (3)C10—H101.0000
O6—C141.445 (3)C11—C121.474 (4)
O7—C151.204 (4)C11—H111.0000
C1—C21.391 (4)C12—C131.514 (4)
C1—C61.398 (4)C12—H121.0000
C1—C71.488 (4)C13—C141.532 (4)
C2—C31.386 (4)C13—H131.0000
C2—H20.9500C14—H141.0000
C3—C41.387 (4)C15—C161.497 (4)
C3—H30.9500C16—H16A0.9800
C4—C51.388 (4)C16—H16B0.9800
C4—H40.9500C16—H16C0.9800
C7—O1—C8115.8 (2)O3—C10—C11116.3 (2)
C9—O3—C1061.00 (17)C9—C10—C11118.1 (3)
C12—O4—C1160.70 (18)O3—C10—H10116.9
C13—O5—H5103 (3)C9—C10—H10116.9
C15—O6—C14116.2 (2)C11—C10—H10116.9
C2—C1—C6119.9 (3)O4—C11—C1259.43 (17)
C2—C1—C7122.3 (3)O4—C11—C10116.9 (2)
C6—C1—C7117.7 (3)C12—C11—C10117.9 (3)
C3—C2—C1120.0 (3)O4—C11—H11116.7
C3—C2—H2120.0C12—C11—H11116.7
C1—C2—H2120.0C10—C11—H11116.7
C2—C3—C4120.0 (3)O4—C12—C1159.86 (18)
C2—C3—H3120.0O4—C12—C13118.5 (2)
C4—C3—H3120.0C11—C12—C13119.3 (2)
C3—C4—C5120.1 (3)O4—C12—H12115.9
C3—C4—H4120.0C11—C12—H12115.9
C5—C4—H4120.0C13—C12—H12115.9
C6—C5—C4120.4 (3)O5—C13—C12110.3 (3)
C6—C5—H5A119.8O5—C13—C14108.3 (2)
C4—C5—H5A119.8C12—C13—C14108.3 (2)
C5—C6—C1119.6 (3)O5—C13—H13110.0
C5—C6—H6120.2C12—C13—H13110.0
C1—C6—H6120.2C14—C13—H13110.0
O2—C7—O1123.2 (3)O6—C14—C9109.0 (2)
O2—C7—C1124.2 (3)O6—C14—C13108.4 (2)
O1—C7—C1112.6 (2)C9—C14—C13111.8 (2)
O1—C8—C9111.4 (2)O6—C14—H14109.2
O1—C8—H8A109.3C9—C14—H14109.2
C9—C8—H8A109.3C13—C14—H14109.2
O1—C8—H8B109.3O7—C15—O6123.3 (3)
C9—C8—H8B109.3O7—C15—C16125.7 (3)
H8A—C8—H8B108.0O6—C15—C16110.9 (3)
O3—C9—C1059.64 (16)C15—C16—H16A109.5
O3—C9—C14115.2 (2)C15—C16—H16B109.5
C10—C9—C14117.3 (3)H16A—C16—H16B109.5
O3—C9—C8112.4 (2)C15—C16—H16C109.5
C10—C9—C8120.3 (3)H16A—C16—H16C109.5
C14—C9—C8117.9 (2)H16B—C16—H16C109.5
O3—C10—C959.37 (17)
C6—C1—C2—C32.1 (4)O3—C10—C11—O423.0 (4)
C7—C1—C2—C3−176.5 (3)C9—C10—C11—O490.6 (3)
C1—C2—C3—C40.2 (4)O3—C10—C11—C12−44.9 (3)
C2—C3—C4—C5−1.5 (4)C9—C10—C11—C1222.7 (4)
C3—C4—C5—C60.6 (4)C11—O4—C12—C13109.2 (3)
C4—C5—C6—C11.6 (4)C10—C11—C12—O4106.4 (3)
C2—C1—C6—C5−2.9 (4)O4—C11—C12—C13−107.9 (3)
C7—C1—C6—C5175.7 (3)C10—C11—C12—C13−1.5 (4)
C8—O1—C7—O2−4.1 (4)O4—C12—C13—O5133.7 (2)
C8—O1—C7—C1174.5 (2)C11—C12—C13—O5−156.8 (2)
C2—C1—C7—O2−171.5 (3)O4—C12—C13—C14−107.9 (3)
C6—C1—C7—O29.9 (4)C11—C12—C13—C14−38.4 (3)
C2—C1—C7—O19.9 (4)C15—O6—C14—C9−128.9 (2)
C6—C1—C7—O1−168.7 (2)C15—O6—C14—C13109.2 (2)
C7—O1—C8—C972.9 (3)O3—C9—C14—O6−93.0 (3)
C10—O3—C9—C14−108.2 (3)C10—C9—C14—O6−160.3 (2)
C10—O3—C9—C8113.0 (3)C8—C9—C14—O643.4 (3)
O1—C8—C9—O3−177.7 (2)O3—C9—C14—C1326.7 (4)
O1—C8—C9—C10−110.8 (3)C10—C9—C14—C13−40.6 (4)
O1—C8—C9—C1444.7 (4)C8—C9—C14—C13163.2 (2)
C9—O3—C10—C11108.5 (3)O5—C13—C14—O6−61.7 (3)
C14—C9—C10—O3104.6 (3)C12—C13—C14—O6178.7 (2)
C8—C9—C10—O3−99.8 (3)O5—C13—C14—C9178.2 (3)
O3—C9—C10—C11−105.5 (3)C12—C13—C14—C958.6 (3)
C14—C9—C10—C11−0.9 (4)C14—O6—C15—O73.2 (4)
C8—C9—C10—C11154.7 (3)C14—O6—C15—C16−177.8 (2)
C12—O4—C11—C10−108.0 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O5—H5···O4i0.84 (3)2.05 (3)2.887 (3)172 (4)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT5386).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2009). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Pancharoen, O., Tuntiwachwuttikul, P. & Taylor, W. C. (1996). Phytochemistry, 43, 305–308.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). J. Appl. Cryst.43, 920–925.

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