Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049537/bq2036sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049537/bq2036Isup2.hkl |
CCDC reference: 667358
Gambogic acid (100 mg) dissolved in acetone (10 ml), anhydride K2CO3 (300 mg) and iodomethane (1 ml) was added and stirred at room temperature for a week. Inpoured the reagent into water (10 ml), and extracted with ether (60 ml) for 3 times. The ether layer was evaporated afrer being washed by water and dryed with anhydride Na2SO4. The residue was separated by silica chromatography, 6-methoxyl-methyl-gambogate (30 mg) was isolated as yellow needles. The title compound was dissolved in ethanol to get saturated solution, the cube crystals were obtained after a week's standing.
The positions of the H atoms of the hydroxyl groups were located initially in a difference Fourier map and then constrained to ride on the parent O atom with O—H = 0.82–0.85, Uiso(H) = 1.5Ueq(O). The methyl H atoms were constrained to an ideal geometry with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C), but were allowed to rotate freely about the C—C bonds. All remaining H atoms were placed in geometrically idealized positions (C—H = 0.93–0.97 Å) and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C). Friedel pairs were averaged before the final refinement as the absolute could not be determined unambiguously.
Garcinia L. Planch (e.g. Garcinia hanburyi Hook. and Garcinia morella Gesv.), is used in traditional Chinese medicine for detoxification, maintaining hemostasis, and as an anthelmintic. Gambogic acid (GBA), the primary component of Gamboge, is a prenylated xanthonoid that has the bridged structural moiety of tricyclo-4-oxa[4.3.1.0]decan-2-one. GBA is an effective telomerase inhibitor and displays potent anticancer activity both in vitro and in vivo. Moreover, GBA has been shown to induce apoptosis in a cell cycle independent manner. In order to study the structure–activity relationship of GBA, several derivates were synthesized and showed potential antitumor activity. The title compound, 6-methoxy-methyl-gambogate, is a derivative of them (Liu et al., 2004). We report here the crystal structure of (I).
The crystal structure of the title compound is shown in Fig. 1. The three fused rings A(O1/C1–C4/C9), B(C4–C9) and C(O2/C6/C7/C10–C12) is almost coplanar with mean deviation being 0.0670 (3) Å from their least square plane. Rings D(C10/C11/C13–C16), E(C13–C15/C17–C19) and G(C10/C13–C15/C18/C19) formed a conformation like triethylenediamine. Three chains including H(C34–C39/O7/O8), I(C27–C31) and J(C21–C26) exists in the compound. Chain H is almost planar indicated by the mean deviations being 0.0436 (2) Å from their least square plane, and it have a dihedral angle of 12.1 (6)° with the plane of the fused rings A, B and C. The double bond C35═C36 has a syn conformation with torision angle C38—C35—C36—C37 being -177.1 (5)°.
The title compound is assembled via hydrogen bonds C2—H2···O8i and C31—H31C···O6ii [Symmetry code: (i) 1 - x, 0.5 + y, 1 - z; (ii) 1 - x, 0.5 + y, -z] as shown in Fig. 2. Details of the hydrogen bonds geometry is shown in Table 1.
For related literature, see Liu et al. (2004).
Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000) and PLATON (Spek, 2003).
C40H48O8 | F(000) = 704 |
Mr = 656.78 | Dx = 1.232 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2245 reflections |
a = 7.865 (3) Å | θ = 2.4–21.5° |
b = 17.017 (7) Å | µ = 0.09 mm−1 |
c = 13.711 (6) Å | T = 298 K |
β = 105.322 (6)° | Prism, colourless |
V = 1769.8 (13) Å3 | 0.54 × 0.40 × 0.27 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 3235 independent reflections |
Radiation source: fine-focus sealed tube | 2055 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
φ and ω scans | θmax = 25.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −9→8 |
Tmin = 0.955, Tmax = 0.977 | k = −20→17 |
8951 measured reflections | l = −14→16 |
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)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.153 | w = 1/[σ2(Fo2) + (0.0745P)2 + 0.3642P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
3235 reflections | Δρmax = 0.32 e Å−3 |
432 parameters | Δρmin = −0.48 e Å−3 |
125 restraints | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods |
C40H48O8 | V = 1769.8 (13) Å3 |
Mr = 656.78 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.865 (3) Å | µ = 0.09 mm−1 |
b = 17.017 (7) Å | T = 298 K |
c = 13.711 (6) Å | 0.54 × 0.40 × 0.27 mm |
β = 105.322 (6)° |
Bruker SMART CCD area-detector diffractometer | 3235 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2055 reflections with I > 2σ(I) |
Tmin = 0.955, Tmax = 0.977 | Rint = 0.045 |
8951 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 125 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.32 e Å−3 |
3235 reflections | Δρmin = −0.48 e Å−3 |
432 parameters | Absolute structure: Flack (1983), with how many Friedel pairs? |
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 | Occ. (<1) | |
O1 | 0.5187 (6) | 0.4902 (2) | 0.2713 (3) | 0.0607 (11) | |
O2 | 0.7046 (4) | 0.23511 (19) | 0.2426 (2) | 0.0438 (8) | |
O3 | 0.9237 (7) | 0.2103 (3) | 0.5463 (3) | 0.1002 (18) | |
O4 | 0.8083 (6) | 0.3577 (2) | 0.5729 (3) | 0.0662 (12) | |
O5 | 0.5472 (4) | 0.0946 (2) | 0.1436 (2) | 0.0484 (9) | |
O6 | 0.5658 (6) | −0.0343 (2) | 0.2965 (3) | 0.0706 (12) | |
O7 | 0.1983 (6) | 0.3344 (3) | 0.3839 (3) | 0.0737 (12) | |
O8 | 0.3480 (8) | 0.2268 (3) | 0.4380 (4) | 0.1069 (19) | |
C1 | 0.4618 (9) | 0.5561 (3) | 0.3239 (4) | 0.0602 (15) | |
C2 | 0.5470 (10) | 0.5550 (4) | 0.4337 (4) | 0.0739 (19) | |
H2 | 0.5404 | 0.5999 | 0.4712 | 0.089* | |
C3 | 0.6330 (9) | 0.4927 (4) | 0.4817 (4) | 0.0626 (17) | |
H3 | 0.6777 | 0.4939 | 0.5517 | 0.075* | |
C4 | 0.6574 (8) | 0.4233 (3) | 0.4258 (4) | 0.0478 (13) | |
C5 | 0.7372 (7) | 0.3556 (3) | 0.4701 (4) | 0.0462 (13) | |
C6 | 0.7569 (7) | 0.2895 (3) | 0.4128 (4) | 0.0433 (12) | |
C7 | 0.6901 (6) | 0.2951 (3) | 0.3070 (3) | 0.0383 (12) | |
C8 | 0.6127 (6) | 0.3626 (3) | 0.2596 (4) | 0.0389 (11) | |
C9 | 0.5938 (7) | 0.4244 (3) | 0.3201 (4) | 0.0433 (12) | |
C10 | 0.7517 (6) | 0.1570 (3) | 0.2772 (4) | 0.0413 (12) | |
C11 | 0.8407 (7) | 0.1514 (3) | 0.3876 (4) | 0.0504 (14) | |
C12 | 0.8475 (7) | 0.2180 (4) | 0.4566 (4) | 0.0592 (16) | |
C13 | 0.5929 (6) | 0.1014 (3) | 0.2509 (4) | 0.0422 (12) | |
C14 | 0.6617 (8) | 0.0210 (3) | 0.2962 (4) | 0.0512 (14) | |
C15 | 0.8607 (8) | 0.0173 (3) | 0.3400 (5) | 0.0608 (15) | |
H15 | 0.9021 | −0.0348 | 0.3664 | 0.073* | |
C16 | 0.8921 (8) | 0.0789 (3) | 0.4205 (5) | 0.0618 (16) | |
H16 | 0.9434 | 0.0677 | 0.4883 | 0.074* | |
C17 | 0.7047 (7) | 0.1018 (3) | 0.1087 (4) | 0.0498 (13) | |
C18 | 0.8537 (7) | 0.1191 (3) | 0.2049 (4) | 0.0496 (13) | |
H18 | 0.9377 | 0.1567 | 0.1900 | 0.060* | |
C19 | 0.9515 (7) | 0.0471 (4) | 0.2605 (5) | 0.0621 (16) | |
H19A | 1.0726 | 0.0612 | 0.2934 | 0.074* | |
H19B | 0.9529 | 0.0057 | 0.2122 | 0.074* | |
C20 | 0.2619 (10) | 0.5505 (5) | 0.3030 (6) | 0.095 (2) | |
H20A | 0.2094 | 0.5530 | 0.2314 | 0.143* | |
H20B | 0.2194 | 0.5933 | 0.3356 | 0.143* | |
H20C | 0.2312 | 0.5016 | 0.3288 | 0.143* | |
C21 | 0.5154 (9) | 0.6285 (4) | 0.2739 (5) | 0.0726 (16) | |
H21A | 0.4726 | 0.6749 | 0.3011 | 0.087* | |
H21B | 0.4580 | 0.6266 | 0.2020 | 0.087* | |
C22 | 0.7133 (10) | 0.6369 (4) | 0.2884 (6) | 0.090 (2) | |
H22A | 0.7716 | 0.6362 | 0.3602 | 0.109* | |
H22B | 0.7554 | 0.5920 | 0.2579 | 0.109* | |
C23 | 0.7639 (11) | 0.7107 (5) | 0.2432 (6) | 0.101 (2) | |
H23 | 0.7458 | 0.7570 | 0.2752 | 0.121* | |
C24 | 0.8284 (12) | 0.7198 (6) | 0.1670 (7) | 0.1156 (18) | |
C25 | 0.8507 (13) | 0.6514 (6) | 0.1007 (7) | 0.1156 (18) | |
H25A | 0.9012 | 0.6698 | 0.0484 | 0.173* | |
H25B | 0.7378 | 0.6281 | 0.0706 | 0.173* | |
H25C | 0.9272 | 0.6128 | 0.1410 | 0.173* | |
C26 | 0.888 (2) | 0.7909 (10) | 0.1209 (14) | 0.111 (3) | 0.66 (2) |
H26A | 0.8023 | 0.8037 | 0.0588 | 0.166* | 0.66 (2) |
H26B | 0.9993 | 0.7803 | 0.1072 | 0.166* | 0.66 (2) |
H26C | 0.9003 | 0.8343 | 0.1669 | 0.166* | 0.66 (2) |
C26' | 0.858 (5) | 0.8123 (12) | 0.167 (3) | 0.111 (3) | 0.34 (2) |
H26D | 0.9077 | 0.8263 | 0.1127 | 0.166* | 0.34 (2) |
H26E | 0.9377 | 0.8278 | 0.2304 | 0.166* | 0.34 (2) |
H26F | 0.7475 | 0.8387 | 0.1590 | 0.166* | 0.34 (2) |
C27 | 0.5530 (7) | 0.3704 (3) | 0.1460 (3) | 0.0426 (12) | |
H27A | 0.4452 | 0.4010 | 0.1275 | 0.051* | |
H27B | 0.5273 | 0.3186 | 0.1162 | 0.051* | |
C28 | 0.6908 (7) | 0.4095 (3) | 0.1038 (4) | 0.0527 (14) | |
H28 | 0.7724 | 0.4406 | 0.1489 | 0.063* | |
C29 | 0.7106 (8) | 0.4053 (4) | 0.0109 (5) | 0.0641 (17) | |
C30 | 0.8509 (11) | 0.4509 (5) | −0.0172 (6) | 0.101 (3) | |
H30A | 0.9261 | 0.4746 | 0.0423 | 0.151* | |
H30B | 0.7984 | 0.4913 | −0.0646 | 0.151* | |
H30C | 0.9192 | 0.4165 | −0.0475 | 0.151* | |
C31 | 0.5965 (11) | 0.3570 (4) | −0.0713 (5) | 0.085 (2) | |
H31A | 0.4992 | 0.3365 | −0.0492 | 0.128* | |
H31B | 0.6640 | 0.3143 | −0.0875 | 0.128* | |
H31C | 0.5527 | 0.3891 | −0.1302 | 0.128* | |
C32 | 0.7212 (10) | 0.0255 (4) | 0.0523 (5) | 0.0759 (19) | |
H32A | 0.7303 | −0.0183 | 0.0975 | 0.114* | |
H32B | 0.8247 | 0.0279 | 0.0278 | 0.114* | |
H32C | 0.6190 | 0.0192 | −0.0037 | 0.114* | |
C33 | 0.6785 (9) | 0.1691 (4) | 0.0333 (4) | 0.0640 (16) | |
H33A | 0.5662 | 0.1636 | −0.0153 | 0.096* | |
H33B | 0.7705 | 0.1681 | −0.0008 | 0.096* | |
H33C | 0.6822 | 0.2182 | 0.0684 | 0.096* | |
C34 | 0.2699 (8) | 0.2663 (4) | 0.3681 (5) | 0.0580 (15) | |
C35 | 0.2475 (6) | 0.2510 (3) | 0.2599 (4) | 0.0500 (13) | |
C36 | 0.3255 (6) | 0.1904 (3) | 0.2271 (4) | 0.0493 (13) | |
H36 | 0.3111 | 0.1886 | 0.1576 | 0.059* | |
C37 | 0.4320 (7) | 0.1257 (3) | 0.2856 (4) | 0.0508 (13) | |
H37A | 0.3565 | 0.0801 | 0.2821 | 0.061* | |
H37B | 0.4710 | 0.1415 | 0.3560 | 0.061* | |
C38 | 0.1371 (8) | 0.3088 (4) | 0.1866 (4) | 0.0674 (17) | |
H38A | 0.1286 | 0.2921 | 0.1186 | 0.101* | |
H38B | 0.1912 | 0.3598 | 0.1974 | 0.101* | |
H38C | 0.0213 | 0.3115 | 0.1970 | 0.101* | |
C39 | 0.2139 (10) | 0.3574 (5) | 0.4855 (5) | 0.088 (2) | |
H39A | 0.1879 | 0.3133 | 0.5229 | 0.131* | |
H39B | 0.1325 | 0.3992 | 0.4865 | 0.131* | |
H39C | 0.3320 | 0.3751 | 0.5157 | 0.131* | |
C40 | 0.7167 (10) | 0.3145 (6) | 0.6312 (5) | 0.096 (3) | |
H40A | 0.6355 | 0.3485 | 0.6521 | 0.144* | |
H40B | 0.7994 | 0.2933 | 0.6898 | 0.144* | |
H40C | 0.6529 | 0.2723 | 0.5912 | 0.144* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.096 (3) | 0.043 (2) | 0.043 (2) | 0.015 (2) | 0.019 (2) | 0.0018 (18) |
O2 | 0.054 (2) | 0.0374 (19) | 0.0374 (17) | 0.0000 (16) | 0.0084 (15) | −0.0019 (16) |
O3 | 0.127 (4) | 0.087 (4) | 0.054 (3) | 0.029 (3) | −0.035 (3) | −0.004 (2) |
O4 | 0.086 (3) | 0.068 (3) | 0.037 (2) | −0.010 (2) | 0.003 (2) | −0.0025 (18) |
O5 | 0.0404 (19) | 0.062 (2) | 0.046 (2) | −0.0083 (17) | 0.0171 (15) | −0.0095 (17) |
O6 | 0.079 (3) | 0.055 (2) | 0.084 (3) | −0.013 (2) | 0.031 (2) | 0.001 (2) |
O7 | 0.078 (3) | 0.076 (3) | 0.071 (3) | 0.014 (2) | 0.026 (2) | −0.014 (2) |
O8 | 0.179 (6) | 0.087 (3) | 0.061 (3) | 0.048 (4) | 0.045 (3) | 0.012 (3) |
C1 | 0.087 (5) | 0.041 (3) | 0.057 (4) | 0.007 (3) | 0.026 (3) | −0.002 (3) |
C2 | 0.128 (6) | 0.046 (4) | 0.053 (3) | 0.006 (4) | 0.033 (4) | −0.005 (3) |
C3 | 0.097 (5) | 0.052 (4) | 0.043 (3) | −0.010 (3) | 0.027 (3) | −0.009 (3) |
C4 | 0.061 (3) | 0.048 (3) | 0.034 (3) | −0.014 (3) | 0.012 (2) | −0.005 (2) |
C5 | 0.047 (3) | 0.053 (3) | 0.033 (3) | −0.013 (3) | 0.001 (2) | 0.000 (2) |
C6 | 0.045 (3) | 0.044 (3) | 0.036 (3) | −0.003 (2) | 0.001 (2) | 0.000 (2) |
C7 | 0.038 (3) | 0.037 (3) | 0.040 (3) | −0.008 (2) | 0.010 (2) | −0.004 (2) |
C8 | 0.042 (3) | 0.036 (3) | 0.038 (3) | −0.006 (2) | 0.010 (2) | 0.000 (2) |
C9 | 0.054 (3) | 0.040 (3) | 0.037 (3) | −0.004 (2) | 0.013 (2) | 0.003 (2) |
C10 | 0.038 (3) | 0.034 (3) | 0.050 (3) | 0.002 (2) | 0.008 (2) | 0.004 (2) |
C11 | 0.046 (3) | 0.050 (3) | 0.049 (3) | 0.002 (3) | 0.002 (3) | 0.005 (3) |
C12 | 0.060 (4) | 0.057 (4) | 0.051 (3) | 0.003 (3) | −0.004 (3) | 0.005 (3) |
C13 | 0.040 (3) | 0.045 (3) | 0.043 (3) | −0.006 (2) | 0.013 (2) | −0.004 (2) |
C14 | 0.062 (4) | 0.041 (3) | 0.057 (3) | −0.005 (3) | 0.028 (3) | −0.002 (3) |
C15 | 0.065 (4) | 0.050 (3) | 0.069 (4) | 0.011 (3) | 0.021 (3) | 0.006 (3) |
C16 | 0.057 (4) | 0.057 (4) | 0.062 (4) | 0.009 (3) | −0.001 (3) | 0.010 (3) |
C17 | 0.055 (3) | 0.049 (3) | 0.054 (3) | 0.002 (3) | 0.030 (3) | −0.005 (3) |
C18 | 0.038 (3) | 0.047 (3) | 0.071 (4) | 0.000 (2) | 0.027 (3) | 0.003 (3) |
C19 | 0.046 (3) | 0.062 (4) | 0.079 (4) | 0.009 (3) | 0.018 (3) | 0.004 (3) |
C20 | 0.098 (6) | 0.097 (6) | 0.101 (6) | 0.006 (5) | 0.044 (4) | −0.007 (5) |
C21 | 0.101 (4) | 0.055 (3) | 0.063 (3) | 0.005 (3) | 0.024 (3) | 0.005 (3) |
C22 | 0.107 (4) | 0.083 (4) | 0.079 (4) | −0.011 (4) | 0.020 (3) | 0.019 (3) |
C23 | 0.117 (4) | 0.096 (4) | 0.083 (4) | −0.012 (4) | 0.015 (4) | 0.014 (4) |
C24 | 0.113 (3) | 0.125 (4) | 0.102 (4) | 0.002 (3) | 0.016 (3) | 0.025 (3) |
C25 | 0.113 (3) | 0.125 (4) | 0.102 (4) | 0.002 (3) | 0.016 (3) | 0.025 (3) |
C26 | 0.120 (6) | 0.121 (6) | 0.094 (6) | −0.016 (5) | 0.035 (5) | 0.035 (5) |
C26' | 0.120 (6) | 0.121 (6) | 0.094 (6) | −0.016 (5) | 0.035 (5) | 0.035 (5) |
C27 | 0.049 (3) | 0.040 (3) | 0.038 (3) | 0.000 (2) | 0.010 (2) | 0.000 (2) |
C28 | 0.052 (3) | 0.055 (4) | 0.052 (3) | −0.003 (3) | 0.015 (3) | 0.005 (3) |
C29 | 0.070 (4) | 0.069 (4) | 0.062 (4) | 0.014 (3) | 0.032 (3) | 0.018 (3) |
C30 | 0.107 (6) | 0.108 (6) | 0.113 (6) | 0.002 (5) | 0.076 (5) | 0.024 (5) |
C31 | 0.116 (6) | 0.093 (5) | 0.049 (4) | 0.015 (5) | 0.026 (4) | 0.007 (4) |
C32 | 0.086 (5) | 0.064 (4) | 0.089 (5) | 0.006 (4) | 0.043 (4) | −0.015 (4) |
C33 | 0.080 (4) | 0.066 (4) | 0.053 (3) | −0.005 (3) | 0.030 (3) | 0.000 (3) |
C34 | 0.057 (4) | 0.056 (4) | 0.068 (4) | 0.002 (3) | 0.029 (3) | −0.006 (3) |
C35 | 0.030 (3) | 0.061 (4) | 0.058 (3) | −0.002 (3) | 0.011 (2) | 0.001 (3) |
C36 | 0.035 (3) | 0.063 (4) | 0.047 (3) | −0.004 (3) | 0.007 (2) | −0.002 (3) |
C37 | 0.045 (3) | 0.056 (3) | 0.058 (3) | −0.001 (3) | 0.026 (3) | 0.004 (3) |
C38 | 0.057 (4) | 0.075 (4) | 0.072 (4) | 0.017 (3) | 0.018 (3) | 0.007 (3) |
C39 | 0.091 (5) | 0.100 (6) | 0.086 (5) | 0.001 (4) | 0.046 (4) | −0.035 (4) |
C40 | 0.094 (6) | 0.149 (8) | 0.044 (3) | −0.008 (5) | 0.019 (3) | 0.020 (4) |
O1—C9 | 1.357 (6) | C22—C23 | 1.499 (11) |
O1—C1 | 1.467 (7) | C22—H22A | 0.9700 |
O2—C7 | 1.374 (6) | C22—H22B | 0.9700 |
O2—C10 | 1.427 (6) | C23—C24 | 1.286 (10) |
O3—C12 | 1.225 (6) | C23—H23 | 0.9300 |
O4—C5 | 1.372 (6) | C24—C26 | 1.497 (13) |
O4—C40 | 1.416 (8) | C24—C25 | 1.516 (11) |
O5—C13 | 1.424 (6) | C24—C26' | 1.592 (18) |
O5—C17 | 1.446 (6) | C25—H25A | 0.9600 |
O6—C14 | 1.207 (6) | C25—H25B | 0.9600 |
O7—C34 | 1.332 (7) | C25—H25C | 0.9600 |
O7—C39 | 1.421 (8) | C26—H26A | 0.9600 |
O8—C34 | 1.198 (7) | C26—H26B | 0.9600 |
C1—C2 | 1.478 (8) | C26—H26C | 0.9600 |
C1—C21 | 1.522 (9) | C26'—H26D | 0.9600 |
C1—C20 | 1.524 (10) | C26'—H26E | 0.9600 |
C2—C3 | 1.333 (8) | C26'—H26F | 0.9600 |
C2—H2 | 0.9300 | C27—C28 | 1.512 (8) |
C3—C4 | 1.448 (8) | C27—H27A | 0.9700 |
C3—H3 | 0.9300 | C27—H27B | 0.9700 |
C4—C5 | 1.374 (7) | C28—C29 | 1.326 (8) |
C4—C9 | 1.403 (7) | C28—H28 | 0.9300 |
C5—C6 | 1.404 (7) | C29—C30 | 1.481 (10) |
C6—C7 | 1.410 (6) | C29—C31 | 1.488 (9) |
C6—C12 | 1.457 (7) | C30—H30A | 0.9600 |
C7—C8 | 1.379 (6) | C30—H30B | 0.9600 |
C8—C9 | 1.372 (7) | C30—H30C | 0.9600 |
C8—C27 | 1.508 (7) | C31—H31A | 0.9600 |
C10—C11 | 1.493 (7) | C31—H31B | 0.9600 |
C10—C13 | 1.532 (7) | C31—H31C | 0.9600 |
C10—C18 | 1.570 (7) | C32—H32A | 0.9600 |
C11—C16 | 1.338 (7) | C32—H32B | 0.9600 |
C11—C12 | 1.468 (8) | C32—H32C | 0.9600 |
C13—C37 | 1.522 (7) | C33—H33A | 0.9600 |
C13—C14 | 1.541 (8) | C33—H33B | 0.9600 |
C14—C15 | 1.523 (8) | C33—H33C | 0.9600 |
C15—C16 | 1.494 (8) | C34—C35 | 1.470 (8) |
C15—C19 | 1.539 (9) | C35—C36 | 1.337 (7) |
C15—H15 | 0.9800 | C35—C38 | 1.508 (8) |
C16—H16 | 0.9300 | C36—C37 | 1.484 (7) |
C17—C33 | 1.521 (8) | C36—H36 | 0.9300 |
C17—C32 | 1.534 (8) | C37—H37A | 0.9700 |
C17—C18 | 1.543 (8) | C37—H37B | 0.9700 |
C18—C19 | 1.537 (8) | C38—H38A | 0.9600 |
C18—H18 | 0.9800 | C38—H38B | 0.9600 |
C19—H19A | 0.9700 | C38—H38C | 0.9600 |
C19—H19B | 0.9700 | C39—H39A | 0.9600 |
C20—H20A | 0.9600 | C39—H39B | 0.9600 |
C20—H20B | 0.9600 | C39—H39C | 0.9600 |
C20—H20C | 0.9600 | C40—H40A | 0.9600 |
C21—C22 | 1.524 (10) | C40—H40B | 0.9600 |
C21—H21A | 0.9700 | C40—H40C | 0.9600 |
C21—H21B | 0.9700 | ||
C9—O1—C1 | 122.6 (4) | C21—C22—H22A | 108.9 |
C7—O2—C10 | 122.5 (3) | C23—C22—H22B | 108.9 |
C5—O4—C40 | 115.9 (5) | C21—C22—H22B | 108.9 |
C13—O5—C17 | 109.3 (4) | H22A—C22—H22B | 107.7 |
C34—O7—C39 | 117.9 (5) | C24—C23—C22 | 129.9 (9) |
O1—C1—C2 | 112.1 (5) | C24—C23—H23 | 115.1 |
O1—C1—C21 | 104.0 (5) | C22—C23—H23 | 115.1 |
C2—C1—C21 | 111.4 (5) | C23—C24—C26 | 132.5 (13) |
O1—C1—C20 | 107.0 (5) | C23—C24—C25 | 121.9 (9) |
C2—C1—C20 | 111.0 (6) | C26—C24—C25 | 105.6 (12) |
C21—C1—C20 | 111.2 (6) | C23—C24—C26' | 101.9 (16) |
C3—C2—C1 | 123.2 (5) | C26—C24—C26' | 30.6 (11) |
C3—C2—H2 | 118.4 | C25—C24—C26' | 136.1 (17) |
C1—C2—H2 | 118.4 | C24—C25—H25A | 109.5 |
C2—C3—C4 | 120.5 (5) | C24—C25—H25B | 109.5 |
C2—C3—H3 | 119.7 | H25A—C25—H25B | 109.5 |
C4—C3—H3 | 119.7 | C24—C25—H25C | 109.5 |
C5—C4—C9 | 117.7 (5) | H25A—C25—H25C | 109.5 |
C5—C4—C3 | 124.0 (5) | H25B—C25—H25C | 109.5 |
C9—C4—C3 | 118.3 (5) | C24—C26—H26A | 109.5 |
O4—C5—C4 | 116.6 (5) | C24—C26—H26B | 109.5 |
O4—C5—C6 | 121.3 (5) | C24—C26—H26C | 109.5 |
C4—C5—C6 | 122.0 (4) | C24—C26'—H26D | 109.5 |
C5—C6—C7 | 117.1 (4) | C24—C26'—H26E | 109.5 |
C5—C6—C12 | 123.6 (4) | H26D—C26'—H26E | 109.5 |
C7—C6—C12 | 119.2 (5) | C24—C26'—H26F | 109.5 |
O2—C7—C8 | 114.6 (4) | H26D—C26'—H26F | 109.5 |
O2—C7—C6 | 122.7 (4) | H26E—C26'—H26F | 109.5 |
C8—C7—C6 | 122.6 (4) | C8—C27—C28 | 112.0 (4) |
C9—C8—C7 | 117.2 (4) | C8—C27—H27A | 109.2 |
C9—C8—C27 | 120.2 (4) | C28—C27—H27A | 109.2 |
C7—C8—C27 | 122.6 (4) | C8—C27—H27B | 109.2 |
O1—C9—C8 | 115.9 (4) | C28—C27—H27B | 109.2 |
O1—C9—C4 | 120.7 (5) | H27A—C27—H27B | 107.9 |
C8—C9—C4 | 123.3 (5) | C29—C28—C27 | 128.5 (5) |
O2—C10—C11 | 114.1 (4) | C29—C28—H28 | 115.7 |
O2—C10—C13 | 111.9 (4) | C27—C28—H28 | 115.7 |
C11—C10—C13 | 109.5 (4) | C28—C29—C30 | 120.4 (7) |
O2—C10—C18 | 107.7 (4) | C28—C29—C31 | 123.8 (6) |
C11—C10—C18 | 115.6 (4) | C30—C29—C31 | 115.7 (6) |
C13—C10—C18 | 96.8 (4) | C29—C30—H30A | 109.5 |
C16—C11—C12 | 122.6 (5) | C29—C30—H30B | 109.5 |
C16—C11—C10 | 114.8 (5) | H30A—C30—H30B | 109.5 |
C12—C11—C10 | 122.0 (5) | C29—C30—H30C | 109.5 |
O3—C12—C6 | 123.9 (5) | H30A—C30—H30C | 109.5 |
O3—C12—C11 | 119.3 (5) | H30B—C30—H30C | 109.5 |
C6—C12—C11 | 116.7 (4) | C29—C31—H31A | 109.5 |
O5—C13—C37 | 110.0 (4) | C29—C31—H31B | 109.5 |
O5—C13—C10 | 105.1 (4) | H31A—C31—H31B | 109.5 |
C37—C13—C10 | 116.9 (4) | C29—C31—H31C | 109.5 |
O5—C13—C14 | 108.1 (4) | H31A—C31—H31C | 109.5 |
C37—C13—C14 | 110.3 (4) | H31B—C31—H31C | 109.5 |
C10—C13—C14 | 106.0 (4) | C17—C32—H32A | 109.5 |
O6—C14—C15 | 123.0 (5) | C17—C32—H32B | 109.5 |
O6—C14—C13 | 122.8 (5) | H32A—C32—H32B | 109.5 |
C15—C14—C13 | 114.3 (5) | C17—C32—H32C | 109.5 |
C16—C15—C14 | 102.4 (5) | H32A—C32—H32C | 109.5 |
C16—C15—C19 | 105.9 (5) | H32B—C32—H32C | 109.5 |
C14—C15—C19 | 109.1 (5) | C17—C33—H33A | 109.5 |
C16—C15—H15 | 112.9 | C17—C33—H33B | 109.5 |
C14—C15—H15 | 112.9 | H33A—C33—H33B | 109.5 |
C19—C15—H15 | 112.9 | C17—C33—H33C | 109.5 |
C11—C16—C15 | 115.0 (5) | H33A—C33—H33C | 109.5 |
C11—C16—H16 | 122.5 | H33B—C33—H33C | 109.5 |
C15—C16—H16 | 122.5 | O8—C34—O7 | 120.5 (6) |
O5—C17—C33 | 108.3 (4) | O8—C34—C35 | 127.4 (6) |
O5—C17—C32 | 106.8 (5) | O7—C34—C35 | 112.0 (6) |
C33—C17—C32 | 108.0 (5) | C36—C35—C34 | 122.2 (5) |
O5—C17—C18 | 104.9 (4) | C36—C35—C38 | 120.9 (5) |
C33—C17—C18 | 111.9 (5) | C34—C35—C38 | 116.9 (5) |
C32—C17—C18 | 116.5 (5) | C35—C36—C37 | 129.3 (5) |
C19—C18—C17 | 116.1 (5) | C35—C36—H36 | 115.3 |
C19—C18—C10 | 106.6 (4) | C37—C36—H36 | 115.3 |
C17—C18—C10 | 102.6 (4) | C36—C37—C13 | 115.4 (4) |
C19—C18—H18 | 110.4 | C36—C37—H37A | 108.4 |
C17—C18—H18 | 110.4 | C13—C37—H37A | 108.4 |
C10—C18—H18 | 110.4 | C36—C37—H37B | 108.4 |
C18—C19—C15 | 110.4 (5) | C13—C37—H37B | 108.4 |
C18—C19—H19A | 109.6 | H37A—C37—H37B | 107.5 |
C15—C19—H19A | 109.6 | C35—C38—H38A | 109.5 |
C18—C19—H19B | 109.6 | C35—C38—H38B | 109.5 |
C15—C19—H19B | 109.6 | H38A—C38—H38B | 109.5 |
H19A—C19—H19B | 108.1 | C35—C38—H38C | 109.5 |
C1—C20—H20A | 109.5 | H38A—C38—H38C | 109.5 |
C1—C20—H20B | 109.5 | H38B—C38—H38C | 109.5 |
H20A—C20—H20B | 109.5 | O7—C39—H39A | 109.5 |
C1—C20—H20C | 109.5 | O7—C39—H39B | 109.5 |
H20A—C20—H20C | 109.5 | H39A—C39—H39B | 109.5 |
H20B—C20—H20C | 109.5 | O7—C39—H39C | 109.5 |
C1—C21—C22 | 114.3 (6) | H39A—C39—H39C | 109.5 |
C1—C21—H21A | 108.7 | H39B—C39—H39C | 109.5 |
C22—C21—H21A | 108.7 | O4—C40—H40A | 109.5 |
C1—C21—H21B | 108.7 | O4—C40—H40B | 109.5 |
C22—C21—H21B | 108.7 | H40A—C40—H40B | 109.5 |
H21A—C21—H21B | 107.6 | O4—C40—H40C | 109.5 |
C23—C22—C21 | 113.5 (6) | H40A—C40—H40C | 109.5 |
C23—C22—H22A | 108.9 | H40B—C40—H40C | 109.5 |
C9—O1—C1—C2 | 19.3 (8) | C11—C10—C13—C37 | 73.1 (5) |
C9—O1—C1—C21 | 139.7 (5) | C18—C10—C13—C37 | −166.6 (4) |
C9—O1—C1—C20 | −102.6 (6) | O2—C10—C13—C14 | −177.8 (4) |
O1—C1—C2—C3 | −14.1 (9) | C11—C10—C13—C14 | −50.3 (5) |
C21—C1—C2—C3 | −130.0 (7) | C18—C10—C13—C14 | 70.0 (4) |
C20—C1—C2—C3 | 105.5 (8) | O5—C13—C14—O6 | −74.4 (6) |
C1—C2—C3—C4 | 4.2 (10) | C37—C13—C14—O6 | 45.8 (7) |
C2—C3—C4—C5 | −176.9 (6) | C10—C13—C14—O6 | 173.3 (5) |
C2—C3—C4—C9 | 2.2 (9) | O5—C13—C14—C15 | 105.3 (5) |
C40—O4—C5—C4 | 108.0 (6) | C37—C13—C14—C15 | −134.4 (5) |
C40—O4—C5—C6 | −76.5 (7) | C10—C13—C14—C15 | −6.9 (6) |
C9—C4—C5—O4 | 176.0 (5) | O6—C14—C15—C16 | −120.0 (6) |
C3—C4—C5—O4 | −5.0 (8) | C13—C14—C15—C16 | 60.2 (6) |
C9—C4—C5—C6 | 0.5 (8) | O6—C14—C15—C19 | 128.1 (6) |
C3—C4—C5—C6 | 179.6 (5) | C13—C14—C15—C19 | −51.7 (6) |
O4—C5—C6—C7 | −175.6 (5) | C12—C11—C16—C15 | 174.8 (5) |
C4—C5—C6—C7 | −0.3 (8) | C10—C11—C16—C15 | 3.4 (8) |
O4—C5—C6—C12 | 2.0 (8) | C14—C15—C16—C11 | −59.6 (7) |
C4—C5—C6—C12 | 177.2 (5) | C19—C15—C16—C11 | 54.7 (7) |
C10—O2—C7—C8 | −168.6 (4) | C13—O5—C17—C33 | −123.1 (5) |
C10—O2—C7—C6 | 14.4 (7) | C13—O5—C17—C32 | 120.8 (5) |
C5—C6—C7—O2 | 178.6 (5) | C13—O5—C17—C18 | −3.4 (5) |
C12—C6—C7—O2 | 0.9 (7) | O5—C17—C18—C19 | 91.1 (5) |
C5—C6—C7—C8 | 1.8 (7) | C33—C17—C18—C19 | −151.7 (5) |
C12—C6—C7—C8 | −175.9 (5) | C32—C17—C18—C19 | −26.8 (7) |
O2—C7—C8—C9 | 179.7 (4) | O5—C17—C18—C10 | −24.8 (5) |
C6—C7—C8—C9 | −3.3 (7) | C33—C17—C18—C10 | 92.4 (5) |
O2—C7—C8—C27 | −1.5 (7) | C32—C17—C18—C10 | −142.7 (5) |
C6—C7—C8—C27 | 175.6 (5) | O2—C10—C18—C19 | 162.8 (4) |
C1—O1—C9—C8 | 169.3 (5) | C11—C10—C18—C19 | 33.8 (6) |
C1—O1—C9—C4 | −14.7 (8) | C13—C10—C18—C19 | −81.6 (5) |
C7—C8—C9—O1 | 179.4 (4) | O2—C10—C18—C17 | −74.7 (5) |
C27—C8—C9—O1 | 0.5 (7) | C11—C10—C18—C17 | 156.4 (4) |
C7—C8—C9—C4 | 3.5 (8) | C13—C10—C18—C17 | 40.9 (4) |
C27—C8—C9—C4 | −175.4 (5) | C17—C18—C19—C15 | −89.9 (6) |
C5—C4—C9—O1 | −177.9 (5) | C10—C18—C19—C15 | 23.7 (6) |
C3—C4—C9—O1 | 3.0 (8) | C16—C15—C19—C18 | −68.9 (6) |
C5—C4—C9—C8 | −2.2 (8) | C14—C15—C19—C18 | 40.7 (6) |
C3—C4—C9—C8 | 178.7 (5) | O1—C1—C21—C22 | −63.2 (7) |
C7—O2—C10—C11 | −19.5 (6) | C2—C1—C21—C22 | 57.6 (8) |
C7—O2—C10—C13 | 105.5 (5) | C20—C1—C21—C22 | −178.1 (6) |
C7—O2—C10—C18 | −149.3 (4) | C1—C21—C22—C23 | −177.0 (6) |
O2—C10—C11—C16 | −177.5 (5) | C21—C22—C23—C24 | −111.6 (10) |
C13—C10—C11—C16 | 56.3 (6) | C22—C23—C24—C26 | −177.2 (11) |
C18—C10—C11—C16 | −51.7 (7) | C22—C23—C24—C25 | 5.6 (15) |
O2—C10—C11—C12 | 11.1 (7) | C22—C23—C24—C26' | −176.9 (15) |
C13—C10—C11—C12 | −115.1 (5) | C9—C8—C27—C28 | 83.4 (6) |
C18—C10—C11—C12 | 136.8 (5) | C7—C8—C27—C28 | −95.4 (6) |
C5—C6—C12—O3 | −4.4 (9) | C8—C27—C28—C29 | 157.5 (6) |
C7—C6—C12—O3 | 173.1 (6) | C27—C28—C29—C30 | 177.5 (6) |
C5—C6—C12—C11 | 173.9 (5) | C27—C28—C29—C31 | −1.7 (10) |
C7—C6—C12—C11 | −8.6 (7) | C39—O7—C34—O8 | −1.5 (9) |
C16—C11—C12—O3 | 9.9 (9) | C39—O7—C34—C35 | −178.6 (5) |
C10—C11—C12—O3 | −179.3 (6) | O8—C34—C35—C36 | −4.4 (10) |
C16—C11—C12—C6 | −168.5 (6) | O7—C34—C35—C36 | 172.5 (5) |
C10—C11—C12—C6 | 2.3 (8) | O8—C34—C35—C38 | 177.9 (6) |
C17—O5—C13—C37 | 158.2 (4) | O7—C34—C35—C38 | −5.2 (7) |
C17—O5—C13—C10 | 31.5 (5) | C34—C35—C36—C37 | 5.3 (8) |
C17—O5—C13—C14 | −81.3 (5) | C38—C35—C36—C37 | −177.1 (5) |
O2—C10—C13—O5 | 67.9 (5) | C35—C36—C37—C13 | −140.1 (6) |
C11—C10—C13—O5 | −164.6 (4) | O5—C13—C37—C36 | −45.3 (6) |
C18—C10—C13—O5 | −44.3 (4) | C10—C13—C37—C36 | 74.4 (6) |
O2—C10—C13—C37 | −54.4 (6) | C14—C13—C37—C36 | −164.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O8i | 0.93 | 2.53 | 3.400 (8) | 156 |
C31—H31C···O6ii | 0.96 | 2.58 | 3.535 (8) | 176 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+1, y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C40H48O8 |
Mr | 656.78 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 298 |
a, b, c (Å) | 7.865 (3), 17.017 (7), 13.711 (6) |
β (°) | 105.322 (6) |
V (Å3) | 1769.8 (13) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.54 × 0.40 × 0.27 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.955, 0.977 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8951, 3235, 2055 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.153, 1.05 |
No. of reflections | 3235 |
No. of parameters | 432 |
No. of restraints | 125 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.48 |
Absolute structure | Flack (1983), with how many Friedel pairs? |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000) and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O8i | 0.93 | 2.53 | 3.400 (8) | 155.5 |
C31—H31C···O6ii | 0.96 | 2.58 | 3.535 (8) | 175.6 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+1, y+1/2, −z. |
Garcinia L. Planch (e.g. Garcinia hanburyi Hook. and Garcinia morella Gesv.), is used in traditional Chinese medicine for detoxification, maintaining hemostasis, and as an anthelmintic. Gambogic acid (GBA), the primary component of Gamboge, is a prenylated xanthonoid that has the bridged structural moiety of tricyclo-4-oxa[4.3.1.0]decan-2-one. GBA is an effective telomerase inhibitor and displays potent anticancer activity both in vitro and in vivo. Moreover, GBA has been shown to induce apoptosis in a cell cycle independent manner. In order to study the structure–activity relationship of GBA, several derivates were synthesized and showed potential antitumor activity. The title compound, 6-methoxy-methyl-gambogate, is a derivative of them (Liu et al., 2004). We report here the crystal structure of (I).
The crystal structure of the title compound is shown in Fig. 1. The three fused rings A(O1/C1–C4/C9), B(C4–C9) and C(O2/C6/C7/C10–C12) is almost coplanar with mean deviation being 0.0670 (3) Å from their least square plane. Rings D(C10/C11/C13–C16), E(C13–C15/C17–C19) and G(C10/C13–C15/C18/C19) formed a conformation like triethylenediamine. Three chains including H(C34–C39/O7/O8), I(C27–C31) and J(C21–C26) exists in the compound. Chain H is almost planar indicated by the mean deviations being 0.0436 (2) Å from their least square plane, and it have a dihedral angle of 12.1 (6)° with the plane of the fused rings A, B and C. The double bond C35═C36 has a syn conformation with torision angle C38—C35—C36—C37 being -177.1 (5)°.
The title compound is assembled via hydrogen bonds C2—H2···O8i and C31—H31C···O6ii [Symmetry code: (i) 1 - x, 0.5 + y, 1 - z; (ii) 1 - x, 0.5 + y, -z] as shown in Fig. 2. Details of the hydrogen bonds geometry is shown in Table 1.