In the title compound, 3,20-dihydroxycevan-6-one, C
27H
43NO
3, all the six-membered rings have normal chair conformations except ring
D, which exists in a twist-chair conformation. The five-membered ring
C adopts an envelope conformation. An O—H
O hydrogen bond connects the molecules into spirals, which run along the
b-axis direction.
Supporting information
CCDC reference: 159988
Dried bulbs (1 kg) of Fritillaria roylei Hooker were ground to a fine powder and
mixed with 5% sodium carbonate solution and dried at room temperature. The
powder was macerated with CH2Cl2 for three days, filtered and the solution
extracted with 1% hydrochloric acid. The pH of the solution was adjusted to 9
with potassium carbonate solution and extracted with diethyl ether. The
solution was condensed under reduced pressure to give a diethyl ether extract,
which was separated on an aluminium oxide column chromatography using acetyl
acetate: methanol: concentrated ammonia solution (20:1:1) as eluent to afford
sipeimine (30 mg). The product was dissolved with methanol and chloroform
(3:2) and stored at room temperature. Three days later, transparent prism
crystals were obtained.
H atoms were visible in difference maps allowed for as riding atoms with O—H
0.82 Å, C—H 0.96 to 0.98 Å. With no atoms having significant anomalous
dispersion contributions, Friedel reflections were merged before the final
refinement and the relative stereochemistry is shown in the scheme and
figures.
Data collection: SMART (Bruker, 1998a); cell refinement: SMART and SAINT (Bruker, 1998a); data reduction: XPREP in SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1998b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997).
3
β,20
β-dihydroxy-6-one-5
α-cevanine
top
Crystal data top
C27H43NO3 | F(000) = 472 |
Mr = 429.62 | Dx = 1.199 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.6185 (5) Å | Cell parameters from 3905 reflections |
b = 12.3948 (8) Å | θ = 1.4–26.0° |
c = 14.5069 (10) Å | µ = 0.08 mm−1 |
β = 90.822 (1)° | T = 293 K |
V = 1189.95 (14) Å3 | Prism, colourless |
Z = 2 | 0.52 × 0.35 × 0.20 mm |
Data collection top
Siemens SMART/CCD diffractometer | 1789 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.032 |
Graphite monochromator | θmax = 26.0°, θmin = 1.4° |
ω scans | h = −8→8 |
7280 measured reflections | k = −15→13 |
2455 independent reflections | l = −16→17 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0662P)2] where P = (Fo2 + 2Fc2)/3 |
2455 reflections | (Δ/σ)max < 0.001 |
285 parameters | Δρmax = 0.16 e Å−3 |
1 restraint | Δρmin = −0.18 e Å−3 |
Crystal data top
C27H43NO3 | V = 1189.95 (14) Å3 |
Mr = 429.62 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.6185 (5) Å | µ = 0.08 mm−1 |
b = 12.3948 (8) Å | T = 293 K |
c = 14.5069 (10) Å | 0.52 × 0.35 × 0.20 mm |
β = 90.822 (1)° | |
Data collection top
Siemens SMART/CCD diffractometer | 1789 reflections with I > 2σ(I) |
7280 measured reflections | Rint = 0.032 |
2455 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 1 restraint |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.16 e Å−3 |
2455 reflections | Δρmin = −0.18 e Å−3 |
285 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 | Uiso*/Ueq | |
O1 | 0.6837 (6) | 0.7650 (3) | 0.78059 (17) | 0.1145 (12) | |
H1 | 0.7191 | 0.8207 | 0.8067 | 0.172* | |
O2 | 0.0921 (5) | 0.9253 (2) | 0.59128 (19) | 0.1042 (10) | |
O3 | 0.1456 (4) | 0.40336 (18) | 0.09243 (16) | 0.0795 (7) | |
H3 | 0.2577 | 0.4221 | 0.0751 | 0.119* | |
N1 | 0.2739 (3) | 0.5855 (2) | 0.00561 (14) | 0.0462 (6) | |
C1 | 0.6414 (5) | 0.6826 (3) | 0.53240 (19) | 0.0614 (9) | |
H1A | 0.6618 | 0.6115 | 0.5063 | 0.074* | |
H1B | 0.7309 | 0.7323 | 0.5014 | 0.074* | |
C2 | 0.6965 (5) | 0.6798 (4) | 0.6355 (2) | 0.0740 (11) | |
H2A | 0.6187 | 0.6235 | 0.6650 | 0.089* | |
H2B | 0.8384 | 0.6616 | 0.6427 | 0.089* | |
C3 | 0.6575 (6) | 0.7854 (4) | 0.6835 (2) | 0.0823 (12) | |
H3A | 0.7572 | 0.8388 | 0.6639 | 0.099* | |
C4 | 0.4469 (6) | 0.8279 (3) | 0.6636 (2) | 0.0722 (10) | |
H4A | 0.4349 | 0.9002 | 0.6886 | 0.087* | |
H4B | 0.3489 | 0.7824 | 0.6939 | 0.087* | |
C5 | 0.3998 (5) | 0.8306 (3) | 0.5601 (2) | 0.0591 (8) | |
H5 | 0.5064 | 0.8749 | 0.5332 | 0.071* | |
C6 | 0.2024 (6) | 0.8869 (3) | 0.5342 (2) | 0.0725 (10) | |
C7 | 0.1509 (6) | 0.8910 (3) | 0.4326 (2) | 0.0749 (10) | |
H7A | 0.2422 | 0.9399 | 0.4017 | 0.090* | |
H7B | 0.0141 | 0.9175 | 0.4236 | 0.090* | |
C8 | 0.1696 (4) | 0.7782 (2) | 0.39169 (19) | 0.0501 (7) | |
H8 | 0.0740 | 0.7328 | 0.4251 | 0.060* | |
C9 | 0.3800 (4) | 0.7311 (2) | 0.41165 (17) | 0.0437 (6) | |
H9 | 0.4784 | 0.7835 | 0.3890 | 0.052* | |
C10 | 0.4213 (4) | 0.7175 (2) | 0.51475 (18) | 0.0458 (7) | |
C11 | 0.3838 (4) | 0.6352 (2) | 0.34595 (17) | 0.0442 (6) | |
H11A | 0.2967 | 0.5774 | 0.3668 | 0.053* | |
H11B | 0.5199 | 0.6076 | 0.3387 | 0.053* | |
C12 | 0.3029 (4) | 0.6862 (2) | 0.25628 (17) | 0.0438 (6) | |
H12 | 0.4087 | 0.7353 | 0.2351 | 0.053* | |
C13 | 0.2594 (4) | 0.6081 (2) | 0.17582 (16) | 0.0440 (6) | |
H13 | 0.3503 | 0.5463 | 0.1839 | 0.053* | |
C14 | 0.1264 (4) | 0.7587 (2) | 0.28844 (19) | 0.0503 (7) | |
H14 | 0.1306 | 0.8277 | 0.2555 | 0.060* | |
C15 | −0.0821 (4) | 0.7082 (3) | 0.2756 (2) | 0.0668 (9) | |
H15A | −0.1025 | 0.6555 | 0.3240 | 0.080* | |
H15B | −0.1838 | 0.7639 | 0.2822 | 0.080* | |
C16 | −0.1116 (5) | 0.6539 (3) | 0.1835 (2) | 0.0630 (9) | |
H16A | −0.0954 | 0.7063 | 0.1345 | 0.076* | |
H16B | −0.2471 | 0.6245 | 0.1789 | 0.076* | |
C17 | 0.0430 (4) | 0.5635 (2) | 0.17314 (18) | 0.0490 (7) | |
H17 | 0.0293 | 0.5160 | 0.2267 | 0.059* | |
C18 | 0.3075 (4) | 0.6586 (3) | 0.08329 (18) | 0.0501 (7) | |
H18A | 0.2242 | 0.7223 | 0.0746 | 0.060* | |
H18B | 0.4476 | 0.6816 | 0.0840 | 0.060* | |
C19 | 0.2773 (5) | 0.6351 (2) | 0.5569 (2) | 0.0544 (7) | |
H19A | 0.1406 | 0.6599 | 0.5495 | 0.082* | |
H19B | 0.3085 | 0.6269 | 0.6214 | 0.082* | |
H19C | 0.2924 | 0.5669 | 0.5264 | 0.082* | |
C20 | 0.0089 (5) | 0.4937 (2) | 0.0870 (2) | 0.0569 (8) | |
C21 | −0.2041 (7) | 0.4472 (4) | 0.0837 (3) | 0.0983 (15) | |
H21A | −0.2108 | 0.3902 | 0.0389 | 0.147* | |
H21B | −0.2984 | 0.5029 | 0.0668 | 0.147* | |
H21C | −0.2374 | 0.4191 | 0.1432 | 0.147* | |
C22 | 0.0597 (4) | 0.5548 (3) | −0.00137 (19) | 0.0490 (7) | |
H22 | −0.0224 | 0.6205 | −0.0045 | 0.059* | |
C23 | 0.0190 (5) | 0.4881 (3) | −0.0879 (2) | 0.0660 (9) | |
H23A | 0.0860 | 0.4188 | −0.0817 | 0.079* | |
H23B | −0.1250 | 0.4749 | −0.0940 | 0.079* | |
C24 | 0.0930 (5) | 0.5442 (3) | −0.17424 (19) | 0.0671 (9) | |
H24A | 0.0708 | 0.4977 | −0.2272 | 0.081* | |
H24B | 0.0168 | 0.6101 | −0.1841 | 0.081* | |
C25 | 0.3144 (6) | 0.5704 (3) | −0.1651 (2) | 0.0708 (10) | |
H25 | 0.3490 | 0.6163 | −0.2176 | 0.085* | |
C26 | 0.3466 (6) | 0.6372 (3) | −0.0786 (2) | 0.0745 (11) | |
H26A | 0.4898 | 0.6520 | −0.0712 | 0.089* | |
H26B | 0.2778 | 0.7058 | −0.0865 | 0.089* | |
C27 | 0.4472 (7) | 0.4725 (5) | −0.1692 (3) | 0.1074 (17) | |
H27A | 0.4263 | 0.4288 | −0.1155 | 0.161* | |
H27B | 0.5862 | 0.4945 | −0.1711 | 0.161* | |
H27C | 0.4142 | 0.4316 | −0.2235 | 0.161* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.158 (3) | 0.145 (3) | 0.0399 (14) | −0.073 (3) | −0.0098 (15) | −0.0106 (17) |
O2 | 0.140 (2) | 0.098 (2) | 0.0756 (19) | 0.0266 (19) | 0.0348 (16) | −0.0260 (16) |
O3 | 0.142 (2) | 0.0497 (13) | 0.0462 (13) | 0.0046 (15) | −0.0053 (14) | 0.0065 (11) |
N1 | 0.0510 (13) | 0.0560 (14) | 0.0315 (12) | −0.0114 (12) | 0.0010 (9) | −0.0005 (10) |
C1 | 0.0572 (18) | 0.091 (2) | 0.0366 (16) | −0.0072 (17) | 0.0049 (13) | −0.0103 (16) |
C2 | 0.063 (2) | 0.121 (3) | 0.0386 (17) | −0.013 (2) | −0.0052 (14) | −0.0098 (19) |
C3 | 0.101 (3) | 0.108 (3) | 0.0381 (18) | −0.053 (2) | −0.0003 (17) | −0.0101 (18) |
C4 | 0.110 (3) | 0.066 (2) | 0.0409 (18) | −0.029 (2) | 0.0179 (17) | −0.0216 (15) |
C5 | 0.084 (2) | 0.0530 (18) | 0.0411 (16) | −0.0164 (17) | 0.0158 (14) | −0.0134 (14) |
C6 | 0.107 (3) | 0.0494 (19) | 0.062 (2) | −0.0023 (19) | 0.0224 (19) | −0.0194 (17) |
C7 | 0.101 (3) | 0.064 (2) | 0.060 (2) | 0.022 (2) | 0.0052 (18) | −0.0133 (17) |
C8 | 0.0536 (16) | 0.0511 (17) | 0.0458 (16) | 0.0029 (14) | 0.0109 (13) | −0.0032 (13) |
C9 | 0.0501 (15) | 0.0467 (16) | 0.0345 (14) | −0.0063 (13) | 0.0094 (11) | −0.0036 (12) |
C10 | 0.0513 (16) | 0.0522 (17) | 0.0341 (14) | −0.0082 (13) | 0.0094 (11) | −0.0108 (12) |
C11 | 0.0452 (14) | 0.0539 (16) | 0.0334 (14) | 0.0051 (13) | 0.0006 (11) | −0.0073 (12) |
C12 | 0.0443 (15) | 0.0511 (16) | 0.0360 (15) | −0.0011 (12) | 0.0040 (11) | −0.0030 (12) |
C13 | 0.0464 (15) | 0.0529 (16) | 0.0327 (14) | 0.0042 (13) | 0.0003 (11) | −0.0007 (12) |
C14 | 0.0561 (17) | 0.0524 (17) | 0.0424 (16) | 0.0087 (14) | 0.0063 (12) | 0.0011 (13) |
C15 | 0.0457 (16) | 0.099 (3) | 0.056 (2) | 0.0103 (17) | 0.0044 (14) | −0.0094 (19) |
C16 | 0.0432 (16) | 0.089 (2) | 0.0571 (19) | 0.0029 (16) | 0.0008 (13) | −0.0058 (18) |
C17 | 0.0590 (17) | 0.0563 (18) | 0.0318 (14) | −0.0117 (14) | 0.0021 (12) | 0.0044 (12) |
C18 | 0.0523 (16) | 0.0623 (18) | 0.0357 (15) | −0.0129 (14) | 0.0031 (12) | −0.0056 (13) |
C19 | 0.0650 (18) | 0.0594 (18) | 0.0390 (15) | −0.0132 (15) | 0.0070 (13) | −0.0051 (13) |
C20 | 0.074 (2) | 0.0506 (19) | 0.0458 (17) | −0.0174 (16) | −0.0009 (14) | 0.0041 (14) |
C21 | 0.111 (3) | 0.118 (4) | 0.067 (3) | −0.069 (3) | 0.018 (2) | −0.016 (2) |
C22 | 0.0548 (17) | 0.0547 (17) | 0.0375 (15) | −0.0056 (13) | −0.0064 (12) | 0.0027 (12) |
C23 | 0.069 (2) | 0.083 (2) | 0.0463 (18) | −0.0199 (19) | −0.0107 (15) | −0.0088 (17) |
C24 | 0.091 (2) | 0.079 (2) | 0.0308 (16) | 0.0031 (19) | −0.0131 (15) | −0.0005 (15) |
C25 | 0.094 (3) | 0.086 (3) | 0.0327 (16) | −0.026 (2) | 0.0056 (15) | −0.0043 (16) |
C26 | 0.107 (3) | 0.080 (2) | 0.0372 (17) | −0.038 (2) | 0.0121 (16) | −0.0059 (16) |
C27 | 0.089 (3) | 0.154 (5) | 0.079 (3) | 0.014 (3) | −0.002 (2) | −0.047 (3) |
Geometric parameters (Å, º) top
O1—C3 | 1.439 (4) | C13—C18 | 1.519 (4) |
O1—H1 | 0.8200 | C13—C17 | 1.535 (4) |
O2—C6 | 1.209 (4) | C13—H13 | 0.9800 |
O3—C20 | 1.441 (4) | C14—C15 | 1.524 (4) |
O3—H3 | 0.8200 | C14—H14 | 0.9800 |
N1—C18 | 1.461 (4) | C15—C16 | 1.506 (4) |
N1—C26 | 1.467 (4) | C15—H15A | 0.9700 |
N1—C22 | 1.470 (3) | C15—H15B | 0.9700 |
C1—C2 | 1.536 (4) | C16—C17 | 1.526 (4) |
C1—C10 | 1.537 (4) | C16—H16A | 0.9700 |
C1—H1A | 0.9700 | C16—H16B | 0.9700 |
C1—H1B | 0.9700 | C17—C20 | 1.534 (4) |
C2—C3 | 1.506 (6) | C17—H17 | 0.9800 |
C2—H2A | 0.9700 | C18—H18A | 0.9700 |
C2—H2B | 0.9700 | C18—H18B | 0.9700 |
C3—C4 | 1.514 (5) | C19—H19A | 0.9600 |
C3—H3A | 0.9800 | C19—H19B | 0.9600 |
C4—C5 | 1.529 (4) | C19—H19C | 0.9600 |
C4—H4A | 0.9700 | C20—C21 | 1.524 (5) |
C4—H4B | 0.9700 | C20—C22 | 1.530 (4) |
C5—C6 | 1.523 (5) | C21—H21A | 0.9600 |
C5—C10 | 1.557 (4) | C21—H21B | 0.9600 |
C5—H5 | 0.9800 | C21—H21C | 0.9600 |
C6—C7 | 1.510 (5) | C22—C23 | 1.523 (4) |
C7—C8 | 1.524 (5) | C22—H22 | 0.9800 |
C7—H7A | 0.9700 | C23—C24 | 1.520 (5) |
C7—H7B | 0.9700 | C23—H23A | 0.9700 |
C8—C9 | 1.534 (4) | C23—H23B | 0.9700 |
C8—C14 | 1.540 (4) | C24—C25 | 1.505 (5) |
C8—H8 | 0.9800 | C24—H24A | 0.9700 |
C9—C11 | 1.524 (4) | C24—H24B | 0.9700 |
C9—C10 | 1.526 (3) | C25—C27 | 1.500 (6) |
C9—H9 | 0.9800 | C25—C26 | 1.515 (4) |
C10—C19 | 1.530 (4) | C25—H25 | 0.9800 |
C11—C12 | 1.536 (4) | C26—H26A | 0.9700 |
C11—H11A | 0.9700 | C26—H26B | 0.9700 |
C11—H11B | 0.9700 | C27—H27A | 0.9600 |
C12—C13 | 1.540 (4) | C27—H27B | 0.9600 |
C12—C14 | 1.551 (4) | C27—H27C | 0.9600 |
C12—H12 | 0.9800 | | |
| | | |
C3—O1—H1 | 109.5 | C8—C14—C12 | 104.7 (2) |
C20—O3—H3 | 109.5 | C15—C14—H14 | 109.4 |
C18—N1—C26 | 108.9 (2) | C8—C14—H14 | 109.4 |
C18—N1—C22 | 110.5 (2) | C12—C14—H14 | 109.4 |
C26—N1—C22 | 112.5 (2) | C16—C15—C14 | 113.4 (2) |
C2—C1—C10 | 112.3 (3) | C16—C15—H15A | 108.9 |
C2—C1—H1A | 109.1 | C14—C15—H15A | 108.9 |
C10—C1—H1A | 109.1 | C16—C15—H15B | 108.9 |
C2—C1—H1B | 109.1 | C14—C15—H15B | 108.9 |
C10—C1—H1B | 109.1 | H15A—C15—H15B | 107.7 |
H1A—C1—H1B | 107.9 | C15—C16—C17 | 109.7 (2) |
C3—C2—C1 | 113.0 (3) | C15—C16—H16A | 109.7 |
C3—C2—H2A | 109.0 | C17—C16—H16A | 109.7 |
C1—C2—H2A | 109.0 | C15—C16—H16B | 109.7 |
C3—C2—H2B | 109.0 | C17—C16—H16B | 109.7 |
C1—C2—H2B | 109.0 | H16A—C16—H16B | 108.2 |
H2A—C2—H2B | 107.8 | C16—C17—C20 | 113.8 (2) |
O1—C3—C2 | 106.3 (4) | C16—C17—C13 | 111.1 (2) |
O1—C3—C4 | 110.2 (3) | C20—C17—C13 | 110.5 (2) |
C2—C3—C4 | 112.2 (3) | C16—C17—H17 | 107.0 |
O1—C3—H3A | 109.4 | C20—C17—H17 | 107.0 |
C2—C3—H3A | 109.4 | C13—C17—H17 | 107.0 |
C4—C3—H3A | 109.4 | N1—C18—C13 | 113.2 (2) |
C3—C4—C5 | 111.7 (3) | N1—C18—H18A | 108.9 |
C3—C4—H4A | 109.3 | C13—C18—H18A | 108.9 |
C5—C4—H4A | 109.3 | N1—C18—H18B | 108.9 |
C3—C4—H4B | 109.3 | C13—C18—H18B | 108.9 |
C5—C4—H4B | 109.3 | H18A—C18—H18B | 107.7 |
H4A—C4—H4B | 107.9 | C10—C19—H19A | 109.5 |
C6—C5—C4 | 114.4 (3) | C10—C19—H19B | 109.5 |
C6—C5—C10 | 113.1 (3) | H19A—C19—H19B | 109.5 |
C4—C5—C10 | 112.1 (3) | C10—C19—H19C | 109.5 |
C6—C5—H5 | 105.4 | H19A—C19—H19C | 109.5 |
C4—C5—H5 | 105.4 | H19B—C19—H19C | 109.5 |
C10—C5—H5 | 105.4 | O3—C20—C21 | 106.7 (3) |
O2—C6—C7 | 121.7 (4) | O3—C20—C22 | 106.5 (2) |
O2—C6—C5 | 122.4 (4) | C21—C20—C22 | 112.0 (3) |
C7—C6—C5 | 115.9 (3) | O3—C20—C17 | 108.0 (2) |
C6—C7—C8 | 109.3 (3) | C21—C20—C17 | 111.4 (3) |
C6—C7—H7A | 109.8 | C22—C20—C17 | 111.8 (2) |
C8—C7—H7A | 109.8 | C20—C21—H21A | 109.5 |
C6—C7—H7B | 109.8 | C20—C21—H21B | 109.5 |
C8—C7—H7B | 109.8 | H21A—C21—H21B | 109.5 |
H7A—C7—H7B | 108.3 | C20—C21—H21C | 109.5 |
C7—C8—C9 | 110.7 (3) | H21A—C21—H21C | 109.5 |
C7—C8—C14 | 120.5 (3) | H21B—C21—H21C | 109.5 |
C9—C8—C14 | 106.2 (2) | N1—C22—C23 | 110.9 (2) |
C7—C8—H8 | 106.2 | N1—C22—C20 | 107.1 (2) |
C9—C8—H8 | 106.2 | C23—C22—C20 | 112.5 (2) |
C14—C8—H8 | 106.2 | N1—C22—H22 | 108.8 |
C11—C9—C10 | 121.5 (2) | C23—C22—H22 | 108.8 |
C11—C9—C8 | 101.7 (2) | C20—C22—H22 | 108.8 |
C10—C9—C8 | 112.1 (2) | C24—C23—C22 | 112.0 (3) |
C11—C9—H9 | 106.9 | C24—C23—H23A | 109.2 |
C10—C9—H9 | 106.9 | C22—C23—H23A | 109.2 |
C8—C9—H9 | 106.9 | C24—C23—H23B | 109.2 |
C9—C10—C19 | 111.2 (2) | C22—C23—H23B | 109.2 |
C9—C10—C1 | 110.5 (2) | H23A—C23—H23B | 107.9 |
C19—C10—C1 | 109.9 (3) | C25—C24—C23 | 110.5 (2) |
C9—C10—C5 | 107.4 (2) | C25—C24—H24A | 109.5 |
C19—C10—C5 | 111.7 (2) | C23—C24—H24A | 109.5 |
C1—C10—C5 | 106.0 (2) | C25—C24—H24B | 109.5 |
C9—C11—C12 | 101.5 (2) | C23—C24—H24B | 109.5 |
C9—C11—H11A | 111.5 | H24A—C24—H24B | 108.1 |
C12—C11—H11A | 111.5 | C27—C25—C24 | 113.1 (3) |
C9—C11—H11B | 111.5 | C27—C25—C26 | 113.5 (3) |
C12—C11—H11B | 111.5 | C24—C25—C26 | 108.4 (3) |
H11A—C11—H11B | 109.3 | C27—C25—H25 | 107.1 |
C11—C12—C13 | 116.2 (2) | C24—C25—H25 | 107.1 |
C11—C12—C14 | 103.8 (2) | C26—C25—H25 | 107.1 |
C13—C12—C14 | 117.3 (2) | N1—C26—C25 | 114.0 (3) |
C11—C12—H12 | 106.2 | N1—C26—H26A | 108.7 |
C13—C12—H12 | 106.2 | C25—C26—H26A | 108.7 |
C14—C12—H12 | 106.2 | N1—C26—H26B | 108.7 |
C18—C13—C17 | 109.5 (2) | C25—C26—H26B | 108.7 |
C18—C13—C12 | 111.8 (2) | H26A—C26—H26B | 107.6 |
C17—C13—C12 | 114.2 (2) | C25—C27—H27A | 109.5 |
C18—C13—H13 | 107.0 | C25—C27—H27B | 109.5 |
C17—C13—H13 | 107.0 | H27A—C27—H27B | 109.5 |
C12—C13—H13 | 107.0 | C25—C27—H27C | 109.5 |
C15—C14—C8 | 109.8 (2) | H27A—C27—H27C | 109.5 |
C15—C14—C12 | 114.2 (3) | H27B—C27—H27C | 109.5 |
| | | |
C10—C1—C2—C3 | −55.3 (4) | C7—C8—C14—C12 | 134.6 (3) |
C1—C2—C3—O1 | 170.6 (3) | C9—C8—C14—C12 | 7.8 (3) |
C1—C2—C3—C4 | 50.1 (4) | C11—C12—C14—C15 | −99.1 (3) |
O1—C3—C4—C5 | −169.3 (3) | C13—C12—C14—C15 | 30.6 (3) |
C2—C3—C4—C5 | −51.1 (4) | C11—C12—C14—C8 | 21.0 (3) |
C3—C4—C5—C6 | −171.9 (3) | C13—C12—C14—C8 | 150.7 (2) |
C3—C4—C5—C10 | 57.6 (4) | C8—C14—C15—C16 | −161.4 (3) |
C4—C5—C6—O2 | −0.5 (5) | C12—C14—C15—C16 | −44.3 (4) |
C10—C5—C6—O2 | 129.5 (3) | C14—C15—C16—C17 | 60.4 (4) |
C4—C5—C6—C7 | −180.0 (3) | C15—C16—C17—C20 | 172.6 (3) |
C10—C5—C6—C7 | −50.0 (4) | C15—C16—C17—C13 | −61.9 (3) |
O2—C6—C7—C8 | −129.2 (4) | C18—C13—C17—C16 | −77.8 (3) |
C5—C6—C7—C8 | 50.3 (4) | C12—C13—C17—C16 | 48.4 (3) |
C6—C7—C8—C9 | −55.0 (4) | C18—C13—C17—C20 | 49.5 (3) |
C6—C7—C8—C14 | −179.8 (3) | C12—C13—C17—C20 | 175.7 (2) |
C7—C8—C9—C11 | −166.2 (3) | C26—N1—C18—C13 | −173.5 (3) |
C14—C8—C9—C11 | −33.7 (3) | C22—N1—C18—C13 | 62.5 (3) |
C7—C8—C9—C10 | 62.6 (3) | C17—C13—C18—N1 | −54.3 (3) |
C14—C8—C9—C10 | −164.9 (2) | C12—C13—C18—N1 | 178.2 (2) |
C11—C9—C10—C19 | −56.1 (3) | C16—C17—C20—O3 | −172.0 (2) |
C8—C9—C10—C19 | 64.2 (3) | C13—C17—C20—O3 | 62.3 (3) |
C11—C9—C10—C1 | 66.2 (3) | C16—C17—C20—C21 | −55.1 (4) |
C8—C9—C10—C1 | −173.5 (2) | C13—C17—C20—C21 | 179.1 (3) |
C11—C9—C10—C5 | −178.7 (3) | C16—C17—C20—C22 | 71.1 (3) |
C8—C9—C10—C5 | −58.3 (3) | C13—C17—C20—C22 | −54.7 (3) |
C2—C1—C10—C9 | 173.8 (3) | C18—N1—C22—C23 | 174.1 (2) |
C2—C1—C10—C19 | −63.1 (3) | C26—N1—C22—C23 | 52.1 (3) |
C2—C1—C10—C5 | 57.8 (4) | C18—N1—C22—C20 | −62.8 (3) |
C6—C5—C10—C9 | 51.2 (3) | C26—N1—C22—C20 | 175.3 (3) |
C4—C5—C10—C9 | −177.6 (2) | O3—C20—C22—N1 | −57.7 (3) |
C6—C5—C10—C19 | −71.0 (3) | C21—C20—C22—N1 | −174.0 (3) |
C4—C5—C10—C19 | 60.2 (3) | C17—C20—C22—N1 | 60.1 (3) |
C6—C5—C10—C1 | 169.4 (3) | O3—C20—C22—C23 | 64.4 (3) |
C4—C5—C10—C1 | −59.5 (3) | C21—C20—C22—C23 | −51.9 (4) |
C10—C9—C11—C12 | 171.7 (2) | C17—C20—C22—C23 | −177.8 (2) |
C8—C9—C11—C12 | 46.4 (3) | N1—C22—C23—C24 | −53.3 (4) |
C9—C11—C12—C13 | −172.4 (2) | C20—C22—C23—C24 | −173.2 (2) |
C9—C11—C12—C14 | −42.0 (3) | C22—C23—C24—C25 | 56.3 (4) |
C11—C12—C13—C18 | −144.6 (2) | C23—C24—C25—C27 | 71.1 (4) |
C14—C12—C13—C18 | 91.7 (3) | C23—C24—C25—C26 | −55.7 (4) |
C11—C12—C13—C17 | 90.4 (3) | C18—N1—C26—C25 | −178.3 (3) |
C14—C12—C13—C17 | −33.2 (3) | C22—N1—C26—C25 | −55.4 (4) |
C7—C8—C14—C15 | −102.4 (3) | C27—C25—C26—N1 | −70.2 (4) |
C9—C8—C14—C15 | 130.7 (3) | C24—C25—C26—N1 | 56.4 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.82 | 1.99 | 2.748 (3) | 154 |
O3—H3···N1 | 0.82 | 2.27 | 2.727 (3) | 116 |
Symmetry code: (i) −x+1, y+1/2, −z+1. |
Experimental details
Crystal data |
Chemical formula | C27H43NO3 |
Mr | 429.62 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 6.6185 (5), 12.3948 (8), 14.5069 (10) |
β (°) | 90.822 (1) |
V (Å3) | 1189.95 (14) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.52 × 0.35 × 0.20 |
|
Data collection |
Diffractometer | Siemens SMART/CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7280, 2455, 1789 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.111, 0.99 |
No. of reflections | 2455 |
No. of parameters | 285 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.18 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.82 | 1.99 | 2.748 (3) | 154 |
O3—H3···N1 | 0.82 | 2.27 | 2.727 (3) | 116 |
Symmetry code: (i) −x+1, y+1/2, −z+1. |
The title compound, (I), was first isolated from Fritillaria imperialis L. (Liliaceae). It has since been extracted from several other species of Fritillaria (Xu et al., 1990; Hu et al., 1993) and also named imperialine and kashmirine. The structure and relative stereochemistry have been established by spectroscopy. In the course of systematic screening for anti-cough agents, sipeimine was isolated from Fritillaria roylei Hooker. The present study reports the crystal structure of sipeimine. The relative stereochemistry and conformation of all the rings in the molecule and the hydrogen-bonding scheme are now clearly defined.
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The molecule (Fig. 1) is composed of five six-membered rings and one five-membered ring. The stereochemistry of the ring juncture is A/B trans, B/C trans, C/D cis, D/E cis and E/F trans. The configurations at the other chiral centres are: C3—OH and C20—Me are equatorial; C10—Me, C20—OH and C22—Me are axial. Molecular dimensions are unexceptional. The cyclohexane rings A, B, E and F have normal chair conformations with mean values of the torsion angles: 55 (4), 55 (5), 57 (5) and 54.9 (16)°, respectively (the torsion angle of the normal chair form of cyclohexane is 56°). Ring D exists in a twist chair form owing to the cis fusion with ring C and ring E. This is also indicated by the smaller torsion angle C13—C12—C14—C15 30.6 (3)° and C12—C14—C15—C16 - 44.3 (4)°. The five-membered ring C adopts an envelope conformation with C11 displaced by 0.683 (4) Å from the mean plane of the remaining four atoms. The model also reveals that the skeleton is twisted strongly at the D ring because of the presence of cis H-atoms H12,H14 and H13,H17; this results in an interplanar angle of 79.9 (1)° between the planes of the A,B,C and E,F ring atoms.
Details of hydrogen bonding are in Table 1. Molecules are linked into spirals along the b-direction (Fig. 2). There is also an intramolecular O—H···N hydrogen bond.