Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035325/xu2295sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035325/xu2295Isup2.hkl |
CCDC reference: 659098
The rhizome of Acorus calamus L. (15 kg) were collected in the Tibet Autonomous area of China. The ethanol extract (2 kg) was suspended in water (2 l) and partitioned successively with petroleum ether, EtOAc and n-butanol. The EtOAc extract (1 kg) was chromatographed over silica gel (160–200 mesh, 2.3 kg) column with eluents of increasing polarity [petroleum ether-acetone (20:1, 15:1, 10:1, 5:1, 2:1, 1:1)] to afford Fr. 1–7 according to TLC analysis. Fr.5 (200 g) was applied to a silica gel (200–300 mesh, 1.6 kg) column and eluted with petroleum ether-acetone (10:1, 5:1, 2:1, 1:1) to obtain the title compound. The isolated product was recrystallized from a methanol solution to afford single crystals (30 mg).
Hydroxy H atoms were located in a difference Fourier map and refined isotropically. Other H atoms were placed in calculated positions with C—H = 0.94–1.00 Å, and refined in riding mode with Uiso(H) = 1.2Ueq(C). As no significant anomalous scatters the absolute configuration could not be determined from the X-ray analysis, Friedel pairs were merged. We assigned the conformation by reference to the chiral molecule of known absolute configuration (Yamamura et al., 1971).
Acorus calamus L. is a traditional Chinese herb distributed widely in China. It is well known for its medicinal properties such as emetic stomach in dyspepsy, remittet fever, nerve tonic and expectorant (Robert & Henrey, 1983). As part of our investigation of the bioactive constituents of the rhizome of A. calamus, we recently isolated the title compound. Its structure was elucidated by spectroscopic analysis including two-dimensional NMR, and was confirmed by single-crystal X-ray diffraction analysis.
The molecule contains two trans fused six-membered rings (Fig. 1). In the crystal structure, the molecules are combined by intermolecular hydrogen bonding.
For general background, see: Robert & Henrey (1983). For a related structure, see: Yamamura et al. (1971).
Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1997); software used to prepare material for publication: SHELXTL.
Fig. 1. View of the molecule of (1) showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. |
C15H26O2 | Dx = 1.127 Mg m−3 |
Mr = 238.36 | Melting point = 443–444 K |
Orthorhombic, P21212 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2 2ab | Cell parameters from 13629 reflections |
a = 9.8941 (4) Å | θ = 3.0–27.5° |
b = 15.7201 (7) Å | µ = 0.07 mm−1 |
c = 9.0288 (4) Å | T = 153 K |
V = 1404.3 (1) Å3 | Block, colourless |
Z = 4 | 0.36 × 0.36 × 0.36 mm |
F(000) = 528 |
Rigaku R-AXIS RAPID IP diffractometer | 1823 reflections with I > 2σ(I) |
Radiation source: Rotating Anode | Rint = 0.021 |
Graphite monochromator | θmax = 27.5°, θmin = 3.0° |
ω scans | h = −12→12 |
13880 measured reflections | k = −20→20 |
1860 independent reflections | l = −11→11 |
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)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.090 | w = 1/[σ2(Fo2) + (0.0656P)2 + 0.1876P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.001 |
1860 reflections | Δρmax = 0.31 e Å−3 |
174 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.033 (5) |
C15H26O2 | V = 1404.3 (1) Å3 |
Mr = 238.36 | Z = 4 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 9.8941 (4) Å | µ = 0.07 mm−1 |
b = 15.7201 (7) Å | T = 153 K |
c = 9.0288 (4) Å | 0.36 × 0.36 × 0.36 mm |
Rigaku R-AXIS RAPID IP diffractometer | 1823 reflections with I > 2σ(I) |
13880 measured reflections | Rint = 0.021 |
1860 independent reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.31 e Å−3 |
1860 reflections | Δρmin = −0.15 e Å−3 |
174 parameters |
Experimental. 13C NMR (600 MHz, CDCl3, δ, p.p.m.): 50.3(C1), 22.8(C2), 34.3(C3), 145.9(C4), 45.6(C5), 76.4(C6), 51.5(C7), 16.5(C8), 41.3(C9), 71.8(C10), 25.5(C11), 18.0(C12), 23.6(C13), 28.1(C14), 111.5(C15). |
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 | ||
O1 | 0.61793 (9) | 0.70501 (6) | 0.40440 (9) | 0.0191 (2) | |
O2 | 0.84327 (9) | 0.79719 (6) | 0.46991 (9) | 0.0219 (2) | |
C1 | 0.74027 (12) | 0.79747 (8) | 0.22996 (13) | 0.0169 (2) | |
H1 | 0.7625 | 0.8010 | 0.1221 | 0.020* | |
C2 | 0.64773 (13) | 0.87333 (8) | 0.26421 (16) | 0.0238 (3) | |
H2A | 0.6980 | 0.9270 | 0.2480 | 0.029* | |
H2B | 0.6201 | 0.8712 | 0.3695 | 0.029* | |
C3 | 0.52124 (14) | 0.87232 (9) | 0.16545 (18) | 0.0288 (3) | |
H3A | 0.4599 | 0.9190 | 0.1955 | 0.035* | |
H3B | 0.5479 | 0.8820 | 0.0611 | 0.035* | |
C4 | 0.44852 (13) | 0.78906 (9) | 0.17762 (14) | 0.0238 (3) | |
C5 | 0.53566 (12) | 0.71155 (8) | 0.15681 (14) | 0.0222 (3) | |
H5A | 0.5623 | 0.7076 | 0.0513 | 0.027* | |
H5B | 0.4818 | 0.6603 | 0.1809 | 0.027* | |
C6 | 0.66413 (11) | 0.71181 (7) | 0.25289 (12) | 0.0156 (2) | |
C7 | 0.75716 (12) | 0.63626 (7) | 0.21106 (14) | 0.0183 (2) | |
H7 | 0.7832 | 0.6457 | 0.1053 | 0.022* | |
C8 | 0.88917 (13) | 0.63991 (8) | 0.29947 (14) | 0.0211 (3) | |
H8A | 0.8690 | 0.6338 | 0.4063 | 0.025* | |
H8B | 0.9482 | 0.5920 | 0.2697 | 0.025* | |
C9 | 0.96268 (12) | 0.72341 (8) | 0.27323 (15) | 0.0213 (3) | |
H9A | 0.9885 | 0.7273 | 0.1675 | 0.026* | |
H9B | 1.0467 | 0.7242 | 0.3328 | 0.026* | |
C10 | 0.87654 (12) | 0.80067 (8) | 0.31411 (13) | 0.0187 (2) | |
C11 | 0.69087 (14) | 0.54676 (8) | 0.21637 (16) | 0.0251 (3) | |
H11 | 0.5945 | 0.5535 | 0.1852 | 0.030* | |
C12 | 0.6908 (2) | 0.50475 (10) | 0.36807 (18) | 0.0434 (4) | |
H12A | 0.6393 | 0.4516 | 0.3636 | 0.052* | |
H12B | 0.6491 | 0.5431 | 0.4404 | 0.052* | |
H12C | 0.7840 | 0.4925 | 0.3980 | 0.052* | |
C13 | 0.75947 (19) | 0.48835 (9) | 0.1035 (2) | 0.0398 (4) | |
H13A | 0.8562 | 0.4845 | 0.1258 | 0.048* | |
H13B | 0.7472 | 0.5116 | 0.0037 | 0.048* | |
H13C | 0.7190 | 0.4315 | 0.1087 | 0.048* | |
C14 | 0.95452 (14) | 0.88257 (9) | 0.28216 (18) | 0.0277 (3) | |
H14A | 0.9036 | 0.9314 | 0.3203 | 0.033* | |
H14B | 0.9669 | 0.8888 | 0.1750 | 0.033* | |
H14C | 1.0430 | 0.8801 | 0.3307 | 0.033* | |
C15 | 0.31656 (14) | 0.78297 (11) | 0.20471 (19) | 0.0336 (3) | |
H15A | 0.274 (2) | 0.7267 (13) | 0.214 (2) | 0.040 (5)* | |
H15B | 0.263 (2) | 0.8316 (14) | 0.223 (2) | 0.046 (6)* | |
H1O | 0.688 (3) | 0.7229 (15) | 0.460 (3) | 0.062 (7)* | |
H2O | 0.918 (2) | 0.7915 (13) | 0.518 (2) | 0.045 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0174 (4) | 0.0239 (4) | 0.0159 (4) | 0.0001 (4) | 0.0043 (3) | 0.0028 (4) |
O2 | 0.0207 (4) | 0.0292 (4) | 0.0160 (4) | 0.0001 (4) | −0.0021 (3) | −0.0034 (4) |
C1 | 0.0172 (5) | 0.0171 (5) | 0.0165 (5) | −0.0021 (4) | 0.0004 (4) | 0.0021 (4) |
C2 | 0.0238 (6) | 0.0174 (5) | 0.0301 (7) | 0.0009 (5) | −0.0020 (5) | 0.0013 (5) |
C3 | 0.0242 (6) | 0.0253 (6) | 0.0370 (7) | 0.0027 (5) | −0.0041 (6) | 0.0092 (6) |
C4 | 0.0201 (6) | 0.0293 (6) | 0.0220 (6) | 0.0001 (5) | −0.0051 (5) | 0.0077 (5) |
C5 | 0.0181 (5) | 0.0253 (6) | 0.0231 (6) | −0.0038 (5) | −0.0047 (5) | 0.0024 (5) |
C6 | 0.0152 (5) | 0.0173 (5) | 0.0144 (5) | −0.0020 (4) | 0.0009 (4) | 0.0021 (4) |
C7 | 0.0187 (5) | 0.0174 (5) | 0.0186 (5) | −0.0020 (4) | 0.0032 (5) | −0.0007 (4) |
C8 | 0.0194 (5) | 0.0208 (5) | 0.0232 (6) | 0.0036 (5) | 0.0015 (5) | −0.0012 (5) |
C9 | 0.0144 (5) | 0.0267 (6) | 0.0228 (6) | −0.0008 (4) | 0.0013 (4) | −0.0032 (5) |
C10 | 0.0173 (5) | 0.0214 (5) | 0.0173 (5) | −0.0026 (5) | 0.0003 (4) | −0.0013 (5) |
C11 | 0.0251 (6) | 0.0180 (5) | 0.0322 (7) | −0.0036 (5) | 0.0052 (6) | −0.0010 (5) |
C12 | 0.0644 (11) | 0.0240 (6) | 0.0417 (8) | −0.0068 (7) | 0.0146 (9) | 0.0073 (7) |
C13 | 0.0463 (9) | 0.0239 (7) | 0.0491 (9) | −0.0067 (6) | 0.0125 (8) | −0.0134 (7) |
C14 | 0.0237 (6) | 0.0261 (6) | 0.0332 (7) | −0.0090 (5) | −0.0006 (6) | −0.0006 (6) |
C15 | 0.0211 (6) | 0.0432 (8) | 0.0367 (8) | 0.0028 (6) | −0.0012 (6) | 0.0089 (7) |
O1—C6 | 1.4462 (13) | C7—H7 | 1.0000 |
O1—H1O | 0.90 (3) | C8—C9 | 1.5193 (16) |
O2—C10 | 1.4457 (14) | C8—H8A | 0.9900 |
O2—H2O | 0.86 (2) | C8—H8B | 0.9900 |
C1—C2 | 1.5350 (17) | C9—C10 | 1.5290 (17) |
C1—C10 | 1.5484 (16) | C9—H9A | 0.9900 |
C1—C6 | 1.5568 (15) | C9—H9B | 0.9900 |
C1—H1 | 1.0000 | C10—C14 | 1.5284 (17) |
C2—C3 | 1.5367 (19) | C11—C12 | 1.521 (2) |
C2—H2A | 0.9900 | C11—C13 | 1.530 (2) |
C2—H2B | 0.9900 | C11—H11 | 1.0000 |
C3—C4 | 1.4976 (19) | C12—H12A | 0.9800 |
C3—H3A | 0.9900 | C12—H12B | 0.9800 |
C3—H3B | 0.9900 | C12—H12C | 0.9800 |
C4—C15 | 1.332 (2) | C13—H13A | 0.9800 |
C4—C5 | 1.5044 (18) | C13—H13B | 0.9800 |
C5—C6 | 1.5389 (16) | C13—H13C | 0.9800 |
C5—H5A | 0.9900 | C14—H14A | 0.9800 |
C5—H5B | 0.9900 | C14—H14B | 0.9800 |
C6—C7 | 1.5493 (16) | C14—H14C | 0.9800 |
C7—C8 | 1.5318 (17) | C15—H15A | 0.98 (2) |
C7—C11 | 1.5531 (16) | C15—H15B | 0.94 (2) |
C6—O1—H1O | 105.3 (17) | C7—C8—H8A | 109.4 |
C10—O2—H2O | 107.7 (14) | C9—C8—H8B | 109.4 |
C2—C1—C10 | 113.29 (10) | C7—C8—H8B | 109.4 |
C2—C1—C6 | 110.89 (9) | H8A—C8—H8B | 108.0 |
C10—C1—C6 | 112.60 (9) | C8—C9—C10 | 112.45 (9) |
C2—C1—H1 | 106.5 | C8—C9—H9A | 109.1 |
C10—C1—H1 | 106.5 | C10—C9—H9A | 109.1 |
C6—C1—H1 | 106.5 | C8—C9—H9B | 109.1 |
C1—C2—C3 | 111.16 (11) | C10—C9—H9B | 109.1 |
C1—C2—H2A | 109.4 | H9A—C9—H9B | 107.8 |
C3—C2—H2A | 109.4 | O2—C10—C14 | 109.30 (11) |
C1—C2—H2B | 109.4 | O2—C10—C9 | 109.37 (10) |
C3—C2—H2B | 109.4 | C14—C10—C9 | 110.01 (10) |
H2A—C2—H2B | 108.0 | O2—C10—C1 | 106.14 (9) |
C4—C3—C2 | 110.96 (10) | C14—C10—C1 | 111.99 (10) |
C4—C3—H3A | 109.4 | C9—C10—C1 | 109.94 (10) |
C2—C3—H3A | 109.4 | C12—C11—C13 | 109.84 (12) |
C4—C3—H3B | 109.4 | C12—C11—C7 | 114.92 (12) |
C2—C3—H3B | 109.4 | C13—C11—C7 | 109.61 (11) |
H3A—C3—H3B | 108.0 | C12—C11—H11 | 107.4 |
C15—C4—C3 | 123.18 (14) | C13—C11—H11 | 107.4 |
C15—C4—C5 | 121.77 (13) | C7—C11—H11 | 107.4 |
C3—C4—C5 | 115.05 (11) | C11—C12—H12A | 109.5 |
C4—C5—C6 | 113.62 (10) | C11—C12—H12B | 109.5 |
C4—C5—H5A | 108.8 | H12A—C12—H12B | 109.5 |
C6—C5—H5A | 108.8 | C11—C12—H12C | 109.5 |
C4—C5—H5B | 108.8 | H12A—C12—H12C | 109.5 |
C6—C5—H5B | 108.8 | H12B—C12—H12C | 109.5 |
H5A—C5—H5B | 107.7 | C11—C13—H13A | 109.5 |
O1—C6—C5 | 105.78 (9) | C11—C13—H13B | 109.5 |
O1—C6—C7 | 111.20 (9) | H13A—C13—H13B | 109.5 |
C5—C6—C7 | 110.57 (9) | C11—C13—H13C | 109.5 |
O1—C6—C1 | 110.04 (9) | H13A—C13—H13C | 109.5 |
C5—C6—C1 | 109.09 (9) | H13B—C13—H13C | 109.5 |
C7—C6—C1 | 110.07 (9) | C10—C14—H14A | 109.5 |
C8—C7—C6 | 110.54 (9) | C10—C14—H14B | 109.5 |
C8—C7—C11 | 112.21 (10) | H14A—C14—H14B | 109.5 |
C6—C7—C11 | 115.85 (9) | C10—C14—H14C | 109.5 |
C8—C7—H7 | 105.8 | H14A—C14—H14C | 109.5 |
C6—C7—H7 | 105.8 | H14B—C14—H14C | 109.5 |
C11—C7—H7 | 105.8 | C4—C15—H15A | 119.8 (12) |
C9—C8—C7 | 111.05 (10) | C4—C15—H15B | 121.4 (14) |
C9—C8—H8A | 109.4 | H15A—C15—H15B | 118.7 (18) |
C10—C1—C2—C3 | 173.71 (10) | O1—C6—C7—C11 | 62.51 (13) |
C6—C1—C2—C3 | −58.55 (13) | C5—C6—C7—C11 | −54.69 (13) |
C1—C2—C3—C4 | 54.42 (15) | C1—C6—C7—C11 | −175.28 (11) |
C2—C3—C4—C15 | 129.47 (15) | C6—C7—C8—C9 | −57.77 (13) |
C2—C3—C4—C5 | −50.57 (16) | C11—C7—C8—C9 | 171.24 (10) |
C15—C4—C5—C6 | −129.50 (14) | C7—C8—C9—C10 | 58.00 (13) |
C3—C4—C5—C6 | 50.54 (15) | C8—C9—C10—O2 | 61.20 (13) |
C4—C5—C6—O1 | 66.73 (12) | C8—C9—C10—C14 | −178.75 (12) |
C4—C5—C6—C7 | −172.78 (10) | C8—C9—C10—C1 | −54.97 (13) |
C4—C5—C6—C1 | −51.61 (13) | C2—C1—C10—O2 | 62.15 (13) |
C2—C1—C6—O1 | −59.63 (12) | C6—C1—C10—O2 | −64.69 (12) |
C10—C1—C6—O1 | 68.48 (12) | C2—C1—C10—C14 | −57.05 (14) |
C2—C1—C6—C5 | 56.00 (12) | C6—C1—C10—C14 | 176.11 (10) |
C10—C1—C6—C5 | −175.89 (9) | C2—C1—C10—C9 | −179.67 (10) |
C2—C1—C6—C7 | 177.48 (10) | C6—C1—C10—C9 | 53.49 (12) |
C10—C1—C6—C7 | −54.41 (12) | C8—C7—C11—C12 | 43.20 (16) |
O1—C6—C7—C8 | −66.54 (12) | C6—C7—C11—C12 | −85.04 (15) |
C5—C6—C7—C8 | 176.26 (9) | C8—C7—C11—C13 | −81.05 (14) |
C1—C6—C7—C8 | 55.66 (12) | C6—C7—C11—C13 | 150.71 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O2 | 0.90 (3) | 1.94 (3) | 2.7240 (13) | 146 (2) |
O2—H2O···O1i | 0.86 (2) | 2.10 (2) | 2.9452 (13) | 167 (2) |
Symmetry code: (i) x+1/2, −y+3/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C15H26O2 |
Mr | 238.36 |
Crystal system, space group | Orthorhombic, P21212 |
Temperature (K) | 153 |
a, b, c (Å) | 9.8941 (4), 15.7201 (7), 9.0288 (4) |
V (Å3) | 1404.3 (1) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.36 × 0.36 × 0.36 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID IP |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13880, 1860, 1823 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.090, 1.00 |
No. of reflections | 1860 |
No. of parameters | 174 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.15 |
Computer programs: RAPID-AUTO (Rigaku, 2004), RAPID-AUTO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O2 | 0.90 (3) | 1.94 (3) | 2.7240 (13) | 146 (2) |
O2—H2O···O1i | 0.86 (2) | 2.10 (2) | 2.9452 (13) | 167 (2) |
Symmetry code: (i) x+1/2, −y+3/2, −z+1. |
Acorus calamus L. is a traditional Chinese herb distributed widely in China. It is well known for its medicinal properties such as emetic stomach in dyspepsy, remittet fever, nerve tonic and expectorant (Robert & Henrey, 1983). As part of our investigation of the bioactive constituents of the rhizome of A. calamus, we recently isolated the title compound. Its structure was elucidated by spectroscopic analysis including two-dimensional NMR, and was confirmed by single-crystal X-ray diffraction analysis.
The molecule contains two trans fused six-membered rings (Fig. 1). In the crystal structure, the molecules are combined by intermolecular hydrogen bonding.