Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801002215/cf6036sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801002215/cf6036Isup2.hkl |
CCDC reference: 159852
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.052
- wR factor = 0.158
- Data-to-parameter ratio = 9.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 70.01 From the CIF: _reflns_number_total 2865 Count of symmetry unique reflns 2867 Completeness (_total/calc) 99.93% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
The shade-dried and powdered whole plant (1.25 kg) of Adiantum Lunulatum was extracted with hexane (3 x 5L) followed by CH2Cl2:MeOH (1:1) (3 x 5L) at room temperature. The combined hexane extract was filtered and concentrated under pressure to obtain a greenish gummy residue (16.41 g). Silica gel column chromatography by gradient elution using hexane through hexane/benzene mixtures to benzene afforded the compound fern-9(11)-en-6α-ol (120 mg). Crystals of the title compound were then obtained from a solution in methanol by slow evaporation at room temperature. The extraction procedure is described by Niranjan Reddy et al. (2001).
Methyl and hydroxy H atoms were placed in ideal positions according to difference-map calculations and were allowed torsional freedom, with U(H) = 1.5Ueq(C or O). The remaining H atoms were included at geometrically calculated positions and allowed to ride on their parent atoms with U(H) = 1.2Ueq(C).
Data collection: local program (Belletti, 1992); cell refinement: local program; data reduction: local program; program(s) used to solve structure: SIR97 (Cascarano et al., 1996); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai & Huttner, 1994); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1983).
Fig. 1. The structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme. |
C30H49OH·CH4O | F(000) = 512 |
Mr = 458.74 | Dx = 1.083 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54178 Å |
a = 11.505 (3) Å | Cell parameters from 39 reflections |
b = 8.484 (2) Å | θ = 11.1–36.7° |
c = 14.616 (4) Å | µ = 0.49 mm−1 |
β = 99.42 (3)° | T = 293 K |
V = 1407.4 (6) Å3 | Plate, colourless |
Z = 2 | 0.19 × 0.14 × 0.11 mm |
Siemens AED single-crystal diffractometer | 2600 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.032 |
Graphite monochromator | θmax = 70.0°, θmin = 3.1° |
ω–2θ scans | h = −14→13 |
Absorption correction: part of the refinement model (ΔF) DIFABS (Walker & Stuart, 1983) and Gluzinski (1989) | k = −10→2 |
Tmin = 0.92, Tmax = 0.95 | l = 0→17 |
5337 measured reflections | 2 standard reflections every 100 reflections |
2865 independent reflections | intensity decay: none |
Refinement on F2 | Hydrogen site location: geom & circular difference map |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.052 | w = 1/[σ2(Fo2) + (0.1072P)2 + 0.1153P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.158 | (Δ/σ)max = 0.007 |
S = 1.12 | Δρmax = 0.18 e Å−3 |
2865 reflections | Δρmin = −0.18 e Å−3 |
310 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0116 (17) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.0 (4) |
C30H49OH·CH4O | V = 1407.4 (6) Å3 |
Mr = 458.74 | Z = 2 |
Monoclinic, P21 | Cu Kα radiation |
a = 11.505 (3) Å | µ = 0.49 mm−1 |
b = 8.484 (2) Å | T = 293 K |
c = 14.616 (4) Å | 0.19 × 0.14 × 0.11 mm |
β = 99.42 (3)° |
Siemens AED single-crystal diffractometer | 2600 reflections with I > 2σ(I) |
Absorption correction: part of the refinement model (ΔF) DIFABS (Walker & Stuart, 1983) and Gluzinski (1989) | Rint = 0.032 |
Tmin = 0.92, Tmax = 0.95 | 2 standard reflections every 100 reflections |
5337 measured reflections | intensity decay: none |
2865 independent reflections |
R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.158 | Δρmax = 0.18 e Å−3 |
S = 1.12 | Δρmin = −0.18 e Å−3 |
2865 reflections | Absolute structure: Flack (1983) |
310 parameters | Absolute structure parameter: 0.0 (4) |
1 restraint |
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 | ||
C1 | −0.3617 (3) | −0.1508 (5) | 0.7496 (3) | 0.0689 (9) | |
H1A | −0.3676 | −0.1309 | 0.8140 | 0.083* | |
H1B | −0.3653 | −0.0498 | 0.7181 | 0.083* | |
C2 | −0.4672 (3) | −0.2504 (6) | 0.7062 (3) | 0.0830 (12) | |
H2A | −0.4680 | −0.3485 | 0.7402 | 0.100* | |
H2B | −0.5397 | −0.1943 | 0.7101 | 0.100* | |
C3 | −0.4603 (3) | −0.2856 (6) | 0.6053 (3) | 0.0751 (9) | |
H3A | −0.4642 | −0.1871 | 0.5712 | 0.090* | |
H3B | −0.5280 | −0.3485 | 0.5791 | 0.090* | |
C4 | −0.3469 (3) | −0.3740 (4) | 0.5925 (2) | 0.0568 (7) | |
C5 | −0.2388 (2) | −0.2754 (3) | 0.64152 (17) | 0.0465 (5) | |
H5 | −0.2451 | −0.1748 | 0.6081 | 0.056* | |
C6 | −0.1190 (2) | −0.3430 (3) | 0.62643 (17) | 0.0461 (6) | |
H6 | −0.1232 | −0.4584 | 0.6258 | 0.055* | |
C7 | −0.0171 (2) | −0.2906 (3) | 0.69980 (18) | 0.0479 (6) | |
H7A | 0.0563 | −0.3008 | 0.6757 | 0.058* | |
H7B | −0.0126 | −0.3579 | 0.7539 | 0.058* | |
C8 | −0.0336 (2) | −0.1194 (3) | 0.72759 (17) | 0.0420 (5) | |
H8 | −0.0511 | −0.0588 | 0.6699 | 0.050* | |
C9 | −0.1417 (2) | −0.1077 (3) | 0.77483 (18) | 0.0476 (6) | |
C10 | −0.2414 (2) | −0.2283 (4) | 0.7448 (2) | 0.0509 (6) | |
C11 | −0.1469 (3) | −0.0013 (4) | 0.8409 (2) | 0.0584 (7) | |
H11 | −0.2151 | 0.0011 | 0.8674 | 0.070* | |
C12 | −0.0519 (3) | 0.1152 (4) | 0.87646 (19) | 0.0580 (7) | |
H12A | −0.0135 | 0.0830 | 0.9377 | 0.070* | |
H12B | −0.0872 | 0.2178 | 0.8822 | 0.070* | |
C13 | 0.0410 (2) | 0.1287 (3) | 0.81198 (16) | 0.0433 (5) | |
C14 | 0.0761 (2) | −0.0419 (3) | 0.78627 (16) | 0.0417 (5) | |
C15 | 0.1790 (2) | −0.0323 (3) | 0.73083 (19) | 0.0497 (6) | |
H15A | 0.2014 | −0.1384 | 0.7162 | 0.060* | |
H15B | 0.1519 | 0.0215 | 0.6727 | 0.060* | |
C16 | 0.2885 (2) | 0.0538 (3) | 0.7819 (2) | 0.0511 (6) | |
H16A | 0.3212 | −0.0062 | 0.8366 | 0.061* | |
H16B | 0.3476 | 0.0589 | 0.7417 | 0.061* | |
C17 | 0.2605 (2) | 0.2209 (3) | 0.81106 (15) | 0.0444 (5) | |
C18 | 0.1522 (2) | 0.2110 (3) | 0.86228 (16) | 0.0446 (5) | |
H18 | 0.1790 | 0.1430 | 0.9158 | 0.053* | |
C19 | 0.1457 (3) | 0.3761 (4) | 0.9047 (2) | 0.0566 (7) | |
H19A | 0.1085 | 0.3722 | 0.9596 | 0.068* | |
H19B | 0.1023 | 0.4484 | 0.8603 | 0.068* | |
C20 | 0.2764 (3) | 0.4250 (4) | 0.9294 (2) | 0.0601 (7) | |
H20A | 0.2990 | 0.4339 | 0.9961 | 0.072* | |
H20B | 0.2889 | 0.5262 | 0.9017 | 0.072* | |
C21 | 0.3507 (2) | 0.2958 (3) | 0.89094 (18) | 0.0482 (6) | |
H21 | 0.3674 | 0.2154 | 0.9394 | 0.058* | |
C22 | −0.3514 (4) | −0.5441 (5) | 0.6266 (3) | 0.0721 (9) | |
H22A | −0.4111 | −0.6011 | 0.5861 | 0.108* | |
H22B | −0.3697 | −0.5444 | 0.6883 | 0.108* | |
H22C | −0.2763 | −0.5935 | 0.6266 | 0.108* | |
C23 | −0.3455 (3) | −0.3809 (6) | 0.4869 (2) | 0.0781 (11) | |
H23A | −0.2826 | −0.4484 | 0.4751 | 0.117* | |
H23B | −0.3338 | −0.2769 | 0.4643 | 0.117* | |
H23C | −0.4193 | −0.4219 | 0.4558 | 0.117* | |
C24 | −0.2246 (3) | −0.3676 (5) | 0.8148 (2) | 0.0692 (9) | |
H24A | −0.2043 | −0.3271 | 0.8767 | 0.104* | |
H24B | −0.1626 | −0.4350 | 0.8012 | 0.104* | |
H24C | −0.2965 | −0.4266 | 0.8097 | 0.104* | |
C25 | −0.0186 (3) | 0.2222 (4) | 0.7261 (2) | 0.0539 (6) | |
H25A | −0.0136 | 0.3330 | 0.7395 | 0.081* | |
H25B | −0.0998 | 0.1918 | 0.7111 | 0.081* | |
H25C | 0.0207 | 0.1999 | 0.6745 | 0.081* | |
C26 | 0.1145 (3) | −0.1457 (4) | 0.8732 (2) | 0.0565 (7) | |
H26A | 0.1482 | −0.2421 | 0.8552 | 0.085* | |
H26B | 0.0472 | −0.1691 | 0.9019 | 0.085* | |
H26C | 0.1720 | −0.0901 | 0.9164 | 0.085* | |
C27 | 0.2460 (3) | 0.3322 (4) | 0.7265 (2) | 0.0608 (7) | |
H27A | 0.3216 | 0.3511 | 0.7089 | 0.091* | |
H27B | 0.2128 | 0.4303 | 0.7423 | 0.091* | |
H27C | 0.1946 | 0.2843 | 0.6757 | 0.091* | |
C28 | 0.4705 (3) | 0.3566 (4) | 0.8728 (2) | 0.0579 (7) | |
H28 | 0.4567 | 0.4455 | 0.8296 | 0.069* | |
C29 | 0.5428 (3) | 0.2333 (5) | 0.8313 (3) | 0.0708 (9) | |
H29A | 0.5496 | 0.1403 | 0.8692 | 0.106* | |
H29B | 0.6198 | 0.2745 | 0.8287 | 0.106* | |
H29C | 0.5044 | 0.2073 | 0.7698 | 0.106* | |
C30 | 0.5420 (4) | 0.4158 (6) | 0.9631 (3) | 0.0868 (13) | |
H30A | 0.5418 | 0.3376 | 1.0106 | 0.130* | |
H30B | 0.5078 | 0.5116 | 0.9815 | 0.130* | |
H30C | 0.6216 | 0.4356 | 0.9543 | 0.130* | |
O1 | −0.09827 (17) | −0.2879 (3) | 0.53654 (13) | 0.0531 (5) | |
H1O1 | −0.0404 | −0.3328 | 0.5228 | 0.080* | |
O1S | −0.0913 (2) | 0.0284 (3) | 0.48765 (19) | 0.0713 (6) | |
H1OS | −0.0946 | −0.0624 | 0.5063 | 0.107* | |
C1S | −0.2020 (3) | 0.0982 (6) | 0.4806 (3) | 0.0792 (10) | |
H1CS | −0.2308 | 0.0865 | 0.5382 | 0.119* | |
H2CS | −0.2555 | 0.0481 | 0.4319 | 0.119* | |
H3CS | −0.1961 | 0.2083 | 0.4667 | 0.119* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0550 (15) | 0.070 (2) | 0.087 (2) | −0.0005 (16) | 0.0260 (15) | −0.0120 (19) |
C2 | 0.0519 (16) | 0.086 (3) | 0.117 (3) | −0.0080 (17) | 0.0305 (18) | −0.019 (2) |
C3 | 0.0469 (15) | 0.081 (2) | 0.095 (2) | −0.0022 (17) | 0.0061 (14) | −0.001 (2) |
C4 | 0.0508 (14) | 0.0614 (17) | 0.0573 (14) | −0.0064 (13) | 0.0057 (11) | −0.0006 (13) |
C5 | 0.0474 (12) | 0.0419 (12) | 0.0501 (12) | −0.0012 (11) | 0.0073 (10) | 0.0034 (11) |
C6 | 0.0530 (13) | 0.0348 (12) | 0.0502 (12) | 0.0011 (10) | 0.0076 (10) | −0.0026 (10) |
C7 | 0.0481 (12) | 0.0399 (13) | 0.0543 (13) | 0.0073 (11) | 0.0041 (10) | −0.0062 (11) |
C8 | 0.0460 (12) | 0.0373 (12) | 0.0423 (11) | 0.0063 (9) | 0.0063 (9) | −0.0016 (9) |
C9 | 0.0481 (12) | 0.0476 (14) | 0.0482 (12) | 0.0039 (11) | 0.0115 (10) | 0.0011 (11) |
C10 | 0.0516 (13) | 0.0481 (14) | 0.0557 (14) | 0.0006 (11) | 0.0162 (11) | 0.0026 (12) |
C11 | 0.0574 (15) | 0.0653 (19) | 0.0567 (14) | 0.0025 (14) | 0.0214 (12) | −0.0058 (14) |
C12 | 0.0629 (16) | 0.0605 (17) | 0.0540 (14) | 0.0017 (14) | 0.0192 (12) | −0.0147 (14) |
C13 | 0.0547 (13) | 0.0366 (12) | 0.0386 (11) | 0.0070 (10) | 0.0076 (9) | −0.0038 (9) |
C14 | 0.0484 (12) | 0.0363 (12) | 0.0400 (11) | 0.0064 (10) | 0.0060 (9) | 0.0002 (9) |
C15 | 0.0498 (13) | 0.0468 (14) | 0.0531 (13) | 0.0048 (11) | 0.0099 (10) | −0.0120 (11) |
C16 | 0.0503 (13) | 0.0444 (14) | 0.0588 (14) | 0.0019 (11) | 0.0097 (11) | −0.0094 (12) |
C17 | 0.0568 (13) | 0.0393 (12) | 0.0365 (10) | 0.0011 (11) | 0.0058 (9) | −0.0006 (10) |
C18 | 0.0551 (13) | 0.0379 (12) | 0.0401 (11) | 0.0053 (11) | 0.0062 (10) | −0.0007 (10) |
C19 | 0.0660 (16) | 0.0466 (15) | 0.0562 (15) | 0.0046 (13) | 0.0067 (12) | −0.0125 (13) |
C20 | 0.0722 (18) | 0.0480 (16) | 0.0595 (15) | 0.0003 (14) | 0.0088 (13) | −0.0126 (13) |
C21 | 0.0579 (14) | 0.0405 (13) | 0.0449 (12) | −0.0023 (12) | 0.0047 (10) | −0.0029 (10) |
C22 | 0.080 (2) | 0.0569 (19) | 0.079 (2) | −0.0194 (17) | 0.0111 (17) | −0.0040 (17) |
C23 | 0.0718 (19) | 0.101 (3) | 0.0572 (16) | −0.025 (2) | −0.0027 (14) | −0.0012 (18) |
C24 | 0.089 (2) | 0.0635 (19) | 0.0564 (16) | −0.0136 (18) | 0.0163 (15) | 0.0111 (15) |
C25 | 0.0592 (14) | 0.0413 (13) | 0.0569 (14) | 0.0096 (12) | −0.0034 (11) | 0.0018 (12) |
C26 | 0.0673 (16) | 0.0434 (14) | 0.0535 (15) | 0.0005 (13) | −0.0060 (12) | 0.0073 (12) |
C27 | 0.0758 (18) | 0.0571 (17) | 0.0489 (14) | −0.0038 (15) | 0.0080 (13) | 0.0061 (14) |
C28 | 0.0672 (16) | 0.0490 (15) | 0.0572 (15) | −0.0097 (14) | 0.0095 (12) | −0.0025 (13) |
C29 | 0.0656 (18) | 0.064 (2) | 0.086 (2) | −0.0092 (16) | 0.0228 (16) | −0.0096 (18) |
C30 | 0.077 (2) | 0.099 (3) | 0.082 (2) | −0.028 (2) | 0.0068 (18) | −0.030 (2) |
O1 | 0.0544 (10) | 0.0558 (11) | 0.0504 (9) | 0.0038 (9) | 0.0124 (7) | −0.0020 (9) |
O1S | 0.0659 (12) | 0.0654 (14) | 0.0843 (15) | −0.0051 (11) | 0.0171 (10) | 0.0182 (13) |
C1S | 0.084 (2) | 0.072 (2) | 0.085 (2) | 0.009 (2) | 0.0213 (18) | 0.008 (2) |
C1—C2 | 1.529 (5) | C17—C18 | 1.558 (3) |
C1—C10 | 1.545 (4) | C17—C21 | 1.564 (3) |
C1—H1A | 0.970 | C18—C19 | 1.539 (4) |
C1—H1B | 0.970 | C18—H18 | 0.980 |
C2—C3 | 1.519 (6) | C19—C20 | 1.545 (4) |
C2—H2A | 0.970 | C19—H19A | 0.970 |
C2—H2B | 0.970 | C19—H19B | 0.970 |
C3—C4 | 1.544 (5) | C20—C21 | 1.551 (4) |
C3—H3A | 0.970 | C20—H20A | 0.970 |
C3—H3B | 0.970 | C20—H20B | 0.970 |
C4—C22 | 1.531 (5) | C21—C28 | 1.535 (4) |
C4—C23 | 1.547 (4) | C21—H21 | 0.980 |
C4—C5 | 1.571 (4) | C22—H22A | 0.960 |
C5—C6 | 1.541 (4) | C22—H22B | 0.960 |
C5—C10 | 1.567 (4) | C22—H22C | 0.960 |
C5—H5 | 0.980 | C23—H23A | 0.960 |
C6—O1 | 1.451 (3) | C23—H23B | 0.960 |
C6—C7 | 1.521 (3) | C23—H23C | 0.960 |
C6—H6 | 0.980 | C24—H24A | 0.960 |
C7—C8 | 1.528 (4) | C24—H24B | 0.960 |
C7—H7A | 0.970 | C24—H24C | 0.960 |
C7—H7B | 0.970 | C25—H25A | 0.960 |
C8—C9 | 1.522 (3) | C25—H25B | 0.960 |
C8—C14 | 1.551 (3) | C25—H25C | 0.960 |
C8—H8 | 0.980 | C26—H26A | 0.960 |
C9—C11 | 1.331 (4) | C26—H26B | 0.960 |
C9—C10 | 1.545 (4) | C26—H26C | 0.960 |
C10—C24 | 1.554 (4) | C27—H27A | 0.960 |
C11—C12 | 1.502 (5) | C27—H27B | 0.960 |
C11—H11 | 0.930 | C27—H27C | 0.960 |
C12—C13 | 1.540 (4) | C28—C29 | 1.522 (5) |
C12—H12A | 0.970 | C28—C30 | 1.522 (5) |
C12—H12B | 0.970 | C28—H28 | 0.980 |
C13—C18 | 1.535 (4) | C29—H29A | 0.960 |
C13—C25 | 1.547 (4) | C29—H29B | 0.960 |
C13—C14 | 1.565 (3) | C29—H29C | 0.960 |
C14—C15 | 1.542 (4) | C30—H30A | 0.960 |
C14—C26 | 1.550 (3) | C30—H30B | 0.960 |
C15—C16 | 1.539 (4) | C30—H30C | 0.960 |
C15—H15A | 0.970 | O1—H1O1 | 0.820 |
C15—H15B | 0.970 | O1S—C1S | 1.393 (5) |
C16—C17 | 1.530 (4) | O1S—H1OS | 0.820 |
C16—H16A | 0.970 | C1S—H1CS | 0.960 |
C16—H16B | 0.970 | C1S—H2CS | 0.960 |
C17—C27 | 1.542 (4) | C1S—H3CS | 0.960 |
C2—C1—C10 | 113.7 (3) | C16—C17—C18 | 107.7 (2) |
C2—C1—H1A | 108.8 | C27—C17—C18 | 115.3 (2) |
C10—C1—H1A | 108.8 | C16—C17—C21 | 116.1 (2) |
C2—C1—H1B | 108.8 | C27—C17—C21 | 108.7 (2) |
C10—C1—H1B | 108.8 | C18—C17—C21 | 98.54 (18) |
H1A—C1—H1B | 107.7 | C13—C18—C19 | 121.0 (2) |
C3—C2—C1 | 110.3 (3) | C13—C18—C17 | 117.7 (2) |
C3—C2—H2A | 109.6 | C19—C18—C17 | 103.9 (2) |
C1—C2—H2A | 109.6 | C13—C18—H18 | 104.1 |
C3—C2—H2B | 109.6 | C19—C18—H18 | 104.1 |
C1—C2—H2B | 109.6 | C17—C18—H18 | 104.1 |
H2A—C2—H2B | 108.1 | C18—C19—C20 | 103.2 (2) |
C2—C3—C4 | 113.1 (3) | C18—C19—H19A | 111.1 |
C2—C3—H3A | 109.0 | C20—C19—H19A | 111.1 |
C4—C3—H3A | 109.0 | C18—C19—H19B | 111.1 |
C2—C3—H3B | 109.0 | C20—C19—H19B | 111.1 |
C4—C3—H3B | 109.0 | H19A—C19—H19B | 109.1 |
H3A—C3—H3B | 107.8 | C19—C20—C21 | 107.4 (2) |
C22—C4—C3 | 110.1 (3) | C19—C20—H20A | 110.2 |
C22—C4—C23 | 107.2 (3) | C21—C20—H20A | 110.2 |
C3—C4—C23 | 106.6 (3) | C19—C20—H20B | 110.2 |
C22—C4—C5 | 114.9 (3) | C21—C20—H20B | 110.2 |
C3—C4—C5 | 107.9 (3) | H20A—C20—H20B | 108.5 |
C23—C4—C5 | 109.8 (3) | C28—C21—C20 | 112.9 (2) |
C6—C5—C10 | 113.0 (2) | C28—C21—C17 | 120.8 (2) |
C6—C5—C4 | 113.3 (2) | C20—C21—C17 | 102.7 (2) |
C10—C5—C4 | 115.9 (2) | C28—C21—H21 | 106.5 |
C6—C5—H5 | 104.3 | C20—C21—H21 | 106.5 |
C10—C5—H5 | 104.3 | C17—C21—H21 | 106.5 |
C4—C5—H5 | 104.3 | C4—C22—H22A | 109.5 |
O1—C6—C7 | 108.8 (2) | C4—C22—H22B | 109.5 |
O1—C6—C5 | 107.0 (2) | H22A—C22—H22B | 109.5 |
C7—C6—C5 | 113.2 (2) | C4—C22—H22C | 109.5 |
O1—C6—H6 | 109.2 | H22A—C22—H22C | 109.5 |
C7—C6—H6 | 109.2 | H22B—C22—H22C | 109.5 |
C5—C6—H6 | 109.2 | C4—C23—H23A | 109.5 |
C6—C7—C8 | 110.5 (2) | C4—C23—H23B | 109.5 |
C6—C7—H7A | 109.5 | H23A—C23—H23B | 109.5 |
C8—C7—H7A | 109.5 | C4—C23—H23C | 109.5 |
C6—C7—H7B | 109.5 | H23A—C23—H23C | 109.5 |
C8—C7—H7B | 109.5 | H23B—C23—H23C | 109.5 |
H7A—C7—H7B | 108.1 | C10—C24—H24A | 109.5 |
C9—C8—C7 | 109.2 (2) | C10—C24—H24B | 109.5 |
C9—C8—C14 | 111.9 (2) | H24A—C24—H24B | 109.5 |
C7—C8—C14 | 115.1 (2) | C10—C24—H24C | 109.5 |
C9—C8—H8 | 106.7 | H24A—C24—H24C | 109.5 |
C7—C8—H8 | 106.7 | H24B—C24—H24C | 109.5 |
C14—C8—H8 | 106.7 | C13—C25—H25A | 109.5 |
C11—C9—C8 | 120.7 (2) | C13—C25—H25B | 109.5 |
C11—C9—C10 | 122.4 (2) | H25A—C25—H25B | 109.5 |
C8—C9—C10 | 116.9 (2) | C13—C25—H25C | 109.5 |
C1—C10—C9 | 109.5 (3) | H25A—C25—H25C | 109.5 |
C1—C10—C24 | 108.1 (3) | H25B—C25—H25C | 109.5 |
C9—C10—C24 | 108.1 (2) | C14—C26—H26A | 109.5 |
C1—C10—C5 | 108.1 (2) | C14—C26—H26B | 109.5 |
C9—C10—C5 | 108.2 (2) | H26A—C26—H26B | 109.5 |
C24—C10—C5 | 114.9 (3) | C14—C26—H26C | 109.5 |
C9—C11—C12 | 125.5 (2) | H26A—C26—H26C | 109.5 |
C9—C11—H11 | 117.2 | H26B—C26—H26C | 109.5 |
C12—C11—H11 | 117.2 | C17—C27—H27A | 109.5 |
C11—C12—C13 | 112.1 (2) | C17—C27—H27B | 109.5 |
C11—C12—H12A | 109.2 | H27A—C27—H27B | 109.5 |
C13—C12—H12A | 109.2 | C17—C27—H27C | 109.5 |
C11—C12—H12B | 109.2 | H27A—C27—H27C | 109.5 |
C13—C12—H12B | 109.2 | H27B—C27—H27C | 109.5 |
H12A—C12—H12B | 107.9 | C29—C28—C30 | 108.7 (3) |
C18—C13—C12 | 110.4 (2) | C29—C28—C21 | 113.7 (3) |
C18—C13—C25 | 112.3 (2) | C30—C28—C21 | 109.5 (3) |
C12—C13—C25 | 106.0 (2) | C29—C28—H28 | 108.3 |
C18—C13—C14 | 107.93 (19) | C30—C28—H28 | 108.3 |
C12—C13—C14 | 108.1 (2) | C21—C28—H28 | 108.3 |
C25—C13—C14 | 112.2 (2) | C28—C29—H29A | 109.5 |
C15—C14—C26 | 108.7 (2) | C28—C29—H29B | 109.5 |
C15—C14—C8 | 110.91 (19) | H29A—C29—H29B | 109.5 |
C26—C14—C8 | 108.0 (2) | C28—C29—H29C | 109.5 |
C15—C14—C13 | 109.1 (2) | H29A—C29—H29C | 109.5 |
C26—C14—C13 | 112.3 (2) | H29B—C29—H29C | 109.5 |
C8—C14—C13 | 107.84 (19) | C28—C30—H30A | 109.5 |
C16—C15—C14 | 114.1 (2) | C28—C30—H30B | 109.5 |
C16—C15—H15A | 108.7 | H30A—C30—H30B | 109.5 |
C14—C15—H15A | 108.7 | C28—C30—H30C | 109.5 |
C16—C15—H15B | 108.7 | H30A—C30—H30C | 109.5 |
C14—C15—H15B | 108.7 | H30B—C30—H30C | 109.5 |
H15A—C15—H15B | 107.6 | C6—O1—H1O1 | 109.5 |
C17—C16—C15 | 112.5 (2) | C1S—O1S—H1OS | 109.5 |
C17—C16—H16A | 109.1 | O1S—C1S—H1CS | 109.5 |
C15—C16—H16A | 109.1 | O1S—C1S—H2CS | 109.5 |
C17—C16—H16B | 109.1 | H1CS—C1S—H2CS | 109.5 |
C15—C16—H16B | 109.1 | O1S—C1S—H3CS | 109.5 |
H16A—C16—H16B | 107.8 | H1CS—C1S—H3CS | 109.5 |
C16—C17—C27 | 110.1 (2) | H2CS—C1S—H3CS | 109.5 |
C10—C1—C2—C3 | −57.9 (5) | C7—C8—C14—C26 | −55.7 (3) |
C1—C2—C3—C4 | 58.8 (5) | C9—C8—C14—C13 | −51.8 (3) |
C2—C3—C4—C22 | 71.3 (4) | C7—C8—C14—C13 | −177.3 (2) |
C2—C3—C4—C23 | −172.7 (4) | C18—C13—C14—C15 | −54.3 (2) |
C2—C3—C4—C5 | −54.7 (4) | C12—C13—C14—C15 | −173.7 (2) |
C22—C4—C5—C6 | 62.0 (3) | C25—C13—C14—C15 | 69.9 (3) |
C3—C4—C5—C6 | −174.8 (3) | C18—C13—C14—C26 | 66.3 (3) |
C23—C4—C5—C6 | −58.9 (4) | C12—C13—C14—C26 | −53.1 (3) |
C22—C4—C5—C10 | −71.1 (3) | C25—C13—C14—C26 | −169.5 (2) |
C3—C4—C5—C10 | 52.2 (3) | C18—C13—C14—C8 | −174.86 (19) |
C23—C4—C5—C10 | 168.0 (3) | C12—C13—C14—C8 | 65.8 (2) |
C10—C5—C6—O1 | −143.6 (2) | C25—C13—C14—C8 | −50.7 (3) |
C4—C5—C6—O1 | 82.0 (3) | C26—C14—C15—C16 | −65.4 (3) |
C10—C5—C6—C7 | −23.7 (3) | C8—C14—C15—C16 | 176.0 (2) |
C4—C5—C6—C7 | −158.1 (2) | C13—C14—C15—C16 | 57.3 (3) |
O1—C6—C7—C8 | 81.4 (3) | C14—C15—C16—C17 | −56.3 (3) |
C5—C6—C7—C8 | −37.5 (3) | C15—C16—C17—C27 | −76.5 (3) |
C6—C7—C8—C9 | 65.3 (3) | C15—C16—C17—C18 | 50.1 (3) |
C6—C7—C8—C14 | −167.9 (2) | C15—C16—C17—C21 | 159.4 (2) |
C7—C8—C9—C11 | 148.4 (3) | C12—C13—C18—C19 | −56.6 (3) |
C14—C8—C9—C11 | 19.8 (4) | C25—C13—C18—C19 | 61.4 (3) |
C7—C8—C9—C10 | −29.4 (3) | C14—C13—C18—C19 | −174.5 (2) |
C14—C8—C9—C10 | −158.0 (2) | C12—C13—C18—C17 | 174.3 (2) |
C2—C1—C10—C9 | 170.4 (3) | C25—C13—C18—C17 | −67.7 (3) |
C2—C1—C10—C24 | −72.1 (4) | C14—C13—C18—C17 | 56.4 (3) |
C2—C1—C10—C5 | 52.8 (4) | C16—C17—C18—C13 | −53.7 (3) |
C11—C9—C10—C1 | 35.6 (4) | C27—C17—C18—C13 | 69.8 (3) |
C8—C9—C10—C1 | −146.7 (3) | C21—C17—C18—C13 | −174.7 (2) |
C11—C9—C10—C24 | −81.9 (4) | C16—C17—C18—C19 | 169.5 (2) |
C8—C9—C10—C24 | 95.8 (3) | C27—C17—C18—C19 | −67.0 (3) |
C11—C9—C10—C5 | 153.1 (3) | C21—C17—C18—C19 | 48.5 (2) |
C8—C9—C10—C5 | −29.1 (3) | C13—C18—C19—C20 | −169.1 (2) |
C6—C5—C10—C1 | 175.7 (2) | C17—C18—C19—C20 | −34.1 (3) |
C4—C5—C10—C1 | −51.1 (3) | C18—C19—C20—C21 | 5.9 (3) |
C6—C5—C10—C9 | 57.2 (3) | C19—C20—C21—C28 | 155.7 (2) |
C4—C5—C10—C9 | −169.6 (2) | C19—C20—C21—C17 | 24.0 (3) |
C6—C5—C10—C24 | −63.6 (3) | C16—C17—C21—C28 | 75.1 (3) |
C4—C5—C10—C24 | 69.6 (3) | C27—C17—C21—C28 | −49.7 (3) |
C8—C9—C11—C12 | −0.2 (5) | C18—C17—C21—C28 | −170.2 (3) |
C10—C9—C11—C12 | 177.4 (3) | C16—C17—C21—C20 | −158.1 (2) |
C9—C11—C12—C13 | 14.5 (5) | C27—C17—C21—C20 | 77.1 (3) |
C11—C12—C13—C18 | −164.3 (3) | C18—C17—C21—C20 | −43.5 (3) |
C11—C12—C13—C25 | 73.9 (3) | C20—C21—C28—C29 | −177.6 (3) |
C11—C12—C13—C14 | −46.5 (3) | C17—C21—C28—C29 | −55.6 (4) |
C9—C8—C14—C15 | −171.3 (2) | C20—C21—C28—C30 | 60.6 (4) |
C7—C8—C14—C15 | 63.3 (3) | C17—C21—C28—C30 | −177.4 (3) |
C9—C8—C14—C26 | 69.7 (3) |
Experimental details
Crystal data | |
Chemical formula | C30H49OH·CH4O |
Mr | 458.74 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 11.505 (3), 8.484 (2), 14.616 (4) |
β (°) | 99.42 (3) |
V (Å3) | 1407.4 (6) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 0.49 |
Crystal size (mm) | 0.19 × 0.14 × 0.11 |
Data collection | |
Diffractometer | Siemens AED single-crystal diffractometer |
Absorption correction | Part of the refinement model (ΔF) DIFABS (Walker & Stuart, 1983) and Gluzinski (1989) |
Tmin, Tmax | 0.92, 0.95 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5337, 2865, 2600 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.158, 1.12 |
No. of reflections | 2865 |
No. of parameters | 310 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.18 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.0 (4) |
Computer programs: local program (Belletti, 1992), local program, SIR97 (Cascarano et al., 1996), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai & Huttner, 1994), SHELXL97 and PARST (Nardelli, 1983).
C6—O1 | 1.451 (3) | C9—C11 | 1.331 (4) |
O1—C6—C7 | 108.8 (2) | C8—C9—C10 | 116.9 (2) |
O1—C6—C5 | 107.0 (2) | C9—C11—C12 | 125.5 (2) |
C11—C9—C8 | 120.7 (2) | C18—C13—C25 | 112.3 (2) |
C11—C9—C10 | 122.4 (2) | C27—C17—C18 | 115.3 (2) |
C10—C5—C6—O1 | −143.6 (2) | C8—C9—C11—C12 | −0.2 (5) |
O1—C6—C7—C8 | 81.4 (3) | C10—C9—C11—C12 | 177.4 (3) |
Ring | q2 | q3 | QT | θ |
A | 0.037 (4) | 0.562 (4) | 0.563 (4) | 3.7 (4) |
B | 0.758 (3) | -0.027 (3) | 0.758 (3) | 92.0 (2) |
C | 0.417 (3) | -0.355 (3) | 0.548 (3) | 130.4 (3) |
D | 0.038 (3) | 0.563 (3) | 0.564 (3) | 3.9 (3) |
E | 0.490 (3) |
The title compound, (I), has been isolated from the whole plant of Adiantum lunuatum L. (Adiantaceae) which is a common fern and used as an ornamental plant in Japan, Europe and widely distributed in India. The dried whole plant has been used as a medicine for bronchitis and cough (Hashimoto & Nishimoto, 1996). Isolation of this compound has also been reported by another group (Sunder et al., 1976). Spectroscopic analysis suggest that the compound is closely related to a derivative of fern-9(11)-ene, but there is an ambiguity regarding the position of the hydroxyl group which is located at C6. So to establish the structure unequivocally the present X-ray structural analysis of the title compound has been undertaken, which confirms the structure obtained by chemical and spectroscopic studies.
The data set does not contain any Friedel opposites, and the value of the Flack (1983) parameter obtained is inadequate to indicate the absolute configuration. However, the absolute stereochemistry of a related triterpenoid has been established by Oh & Maslen (1966) by a direct method of anomalous dispersion phasing and the present structure is in accord with this. Hence the present enantiomer has been retained.
The molecule is composed of five fused rings, four of which are six-membered and one is five-membered. Rings A (C1–C5/C10) and D (C13–C18) adopt a chair conformation (see Table 2), ring B (C5–C9/C10) is in a twist boat conformation, ring C (C8–C14) containing a double bond is in a distorted chair conformation and the five-membered ring E (C17–C21) adopts an envelope conformation. The conformation of a chair in ring A followed by a boat in ring B is unusual but also observed in the pentacyclo triterpenoid (Parvez et al., 1999). This configuration seems to have arisen from the coplanarity of atoms C8–C12 due to the double bond at C9═C11. The relevant torsion angles are C8—C9—-C11–C12 - 0.3 (5)° and C10—C9—C11—C12 177.4 (3)°. In ring C, atoms C8, C9, C13 and C14 are only approximately coplanar, with deviations of up to 0.238 (3) Å from their mean plane. Atom C8 is 0.526 (3) Å above this plane and atom C12 is 0.481 (3) Å below it. Hence it is inferred that the conformation of ring C is intermediate between a chair and a twist boat, with a ring puckering parameter ϕ = 95.1 (4)°. The ring-puckering parameters (Table 2) were calculated using the method of Cremer & Pople (1975). The hydroxyl group at C6 is twisted from the plane of the ring B. The associated torsion angles are C10—C5—C6—O1 - 143.6 (2)° and C8—C7—C6—O1 81.4 (3)°.
The Csp3—Csp3 bond lengths lie between 1.519 (6) and 1.571 (4) Å. The variation in bond length indicates that the structure is subject to certain strain which mainly arises from the repulsion of the methyl groups at C25 and C27 and also from the constraint placed on C8–C12 to lie in one plane due to the presence of a double bond at C9═C11. Repulsion between two methyl groups C25 and C27 is evident in that the angles C18—C13—C25 112.3 (2)° and C18—C17—C27 115.3 (2)° are much larger than the normal tetrahedral value of 109.5° formed by pairs of Csp3—Csp3 bonds. Csp3—Csp2 bond lengths lie between 1.502 (5) and 1.546 (3) Å. In the molecule (Fig. 1), there is one endocyclic double bond C9═C11 and one Csp3—O bond, indicated by the bond lengths 1.331 (4) and 1.451 (3) Å, respectively. All these values are within expected ranges.
The O1S atom of the methanol solvent molecule is connected to the main molecule through a hydrogen bond with the O atom of the hydroxyl group: O1S—H1OS····O1, with O1S···O1 2.781 (4) Å and O1S—H1OS···O1 173.2 (2)°. There are no other intermolecular hydrogen bonds and the structure is stabilized by van der Waals interactions.