organic compounds
3,28-Diacetoxy-29-bromobetulin
aCollege of Life Sciences, Northeast Forestry University, Harbin 150040, People's Republic of China, and bSchool of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150080, People's Republic of China
*Correspondence e-mail: xiufeng.yan@126.com
In the title molecule, C34H53BrO4, all the cyclohexane rings adopt chair conformations, while the cyclopentane ring adopts an In the crystal, weak intermolecular C—H⋯O hydrogen bonds link the molecules into corrugated sheets parallel to the ab plane.
Related literature
For the anti-HIV and antitumor activities of betulin derivatives, see: Sun et al. (1998) and Kim et al. (1998), respectively. For a related structure, see Mohamed et al. (2006).
Experimental
Crystal data
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Data collection: RAPID-AUTO (Rigaku, 1998); cell RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536809027640/cv2584sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809027640/cv2584Isup2.hkl
Purified betulin (4.4 g, 10 mmol) was dissolved in dichloromethane (100 ml) and pyridine (0.5 ml) mixed solvent, followed by the addition of acetic anhydride (5 ml, 5.3 mmol). The reaction mixture was stirred for 24 h at room temperature. The solvent was removed by distillation under vacuum. The crude product was washed with a small quantity of benzene and then recrystallized from benzene (30 ml), 3.1 g diacetate-betulin was obtained.
The 3, 28-diacetate-betulin (1.0 g, 2 mmol), N-bromosuccinimide (0.35 g, 2 mmol) and benzoyl peroxide (0.05 g, 0.22 mmol) were dissolved in tetrachloromethane (50 ml). The reaction mixture was stirred for 6 h at reflux temperature. The solvent was removed by distillation under vacuum. The crude product was washed with a small quantity of ethanol and then recrystallized from petroleum ether (6 ml), 0.4 g suitable for X-ray diffraction test colourless block crystals of the titel compound was obtained.
C-bound H-atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.96-0.98 Å and Uiso(H) = 1.2-1.5Ueq(C).
Data collection: RAPID-AUTO (Rigaku, 1998); cell
RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C34H53BrO4 | F(000) = 1296 |
Mr = 605.67 | Dx = 1.261 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 15343 reflections |
a = 7.152 (3) Å | θ = 3.1–27.4° |
b = 14.946 (7) Å | µ = 1.32 mm−1 |
c = 29.837 (12) Å | T = 291 K |
V = 3189 (2) Å3 | Block, colourless |
Z = 4 | 0.40 × 0.38 × 0.37 mm |
Rigaku R-AXIS RAPID diffractometer | 5578 independent reflections |
Radiation source: fine-focus sealed tube | 3534 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.102 |
ω scans | θmax = 25.0°, θmin = 3.1° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −8→8 |
Tmin = 0.622, Tmax = 0.642 | k = −17→17 |
23319 measured reflections | l = −35→35 |
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)] = 0.057 | H-atom parameters constrained |
wR(F2) = 0.145 | w = 1/[σ2(Fo2) + (0.066P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.94 | (Δ/σ)max < 0.001 |
5578 reflections | Δρmax = 0.45 e Å−3 |
358 parameters | Δρmin = −0.58 e Å−3 |
18 restraints | Absolute structure: Flack (1983), 2346 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.024 (12) |
C34H53BrO4 | V = 3189 (2) Å3 |
Mr = 605.67 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.152 (3) Å | µ = 1.32 mm−1 |
b = 14.946 (7) Å | T = 291 K |
c = 29.837 (12) Å | 0.40 × 0.38 × 0.37 mm |
Rigaku R-AXIS RAPID diffractometer | 5578 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 3534 reflections with I > 2σ(I) |
Tmin = 0.622, Tmax = 0.642 | Rint = 0.102 |
23319 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | H-atom parameters constrained |
wR(F2) = 0.145 | Δρmax = 0.45 e Å−3 |
S = 0.94 | Δρmin = −0.58 e Å−3 |
5578 reflections | Absolute structure: Flack (1983), 2346 Friedel pairs |
358 parameters | Absolute structure parameter: 0.024 (12) |
18 restraints |
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 | ||
Br1 | 1.44746 (8) | −0.01367 (6) | 0.18762 (2) | 0.1130 (4) | |
C1 | 1.0979 (5) | 0.4597 (3) | 0.38899 (13) | 0.0394 (10) | |
H1A | 1.2251 | 0.4468 | 0.3798 | 0.047* | |
H1B | 1.0239 | 0.4685 | 0.3621 | 0.047* | |
C2 | 1.0967 (5) | 0.5466 (3) | 0.41652 (14) | 0.0419 (10) | |
H2A | 1.1780 | 0.5401 | 0.4423 | 0.050* | |
H2B | 1.1437 | 0.5955 | 0.3984 | 0.050* | |
C3 | 0.9011 (6) | 0.5672 (3) | 0.43183 (13) | 0.0384 (10) | |
H3 | 0.8215 | 0.5744 | 0.4053 | 0.046* | |
C4 | 0.8156 (5) | 0.4940 (3) | 0.46193 (12) | 0.0366 (9) | |
C5 | 0.8272 (5) | 0.4054 (3) | 0.43421 (12) | 0.0311 (9) | |
H5 | 0.7495 | 0.4169 | 0.4078 | 0.037* | |
C6 | 0.7341 (6) | 0.3239 (3) | 0.45702 (14) | 0.0430 (11) | |
H6A | 0.8162 | 0.3006 | 0.4801 | 0.052* | |
H6B | 0.6182 | 0.3424 | 0.4712 | 0.052* | |
C7 | 0.6935 (5) | 0.2506 (3) | 0.42254 (13) | 0.0380 (10) | |
H7A | 0.6044 | 0.2733 | 0.4008 | 0.046* | |
H7B | 0.6360 | 0.2002 | 0.4377 | 0.046* | |
C8 | 0.8677 (5) | 0.2177 (3) | 0.39760 (12) | 0.0308 (9) | |
C9 | 0.9820 (4) | 0.3005 (3) | 0.37983 (11) | 0.0294 (8) | |
H9 | 0.9009 | 0.3276 | 0.3571 | 0.035* | |
C10 | 1.0203 (4) | 0.3785 (3) | 0.41474 (11) | 0.0281 (8) | |
C11 | 1.1536 (5) | 0.2692 (3) | 0.35383 (13) | 0.0379 (10) | |
H11A | 1.2395 | 0.2404 | 0.3744 | 0.045* | |
H11B | 1.2164 | 0.3211 | 0.3413 | 0.045* | |
C12 | 1.1069 (5) | 0.2039 (3) | 0.31566 (13) | 0.0367 (9) | |
H12A | 1.0373 | 0.2354 | 0.2926 | 0.044* | |
H12B | 1.2223 | 0.1825 | 0.3024 | 0.044* | |
C13 | 0.9924 (5) | 0.1240 (3) | 0.33177 (12) | 0.0310 (9) | |
H13 | 1.0681 | 0.0934 | 0.3544 | 0.037* | |
C14 | 0.8095 (5) | 0.1562 (3) | 0.35600 (12) | 0.0324 (9) | |
C15 | 0.6922 (6) | 0.0744 (3) | 0.37207 (14) | 0.0445 (11) | |
H15A | 0.7519 | 0.0492 | 0.3984 | 0.053* | |
H15B | 0.5695 | 0.0955 | 0.3810 | 0.053* | |
C16 | 0.6672 (6) | −0.0005 (3) | 0.33708 (15) | 0.0503 (11) | |
H16A | 0.6061 | −0.0512 | 0.3511 | 0.060* | |
H16B | 0.5865 | 0.0208 | 0.3132 | 0.060* | |
C17 | 0.8514 (6) | −0.0310 (3) | 0.31707 (13) | 0.0423 (10) | |
C18 | 0.9435 (5) | 0.0536 (3) | 0.29593 (12) | 0.0341 (9) | |
H18 | 0.8472 | 0.0810 | 0.2770 | 0.041* | |
C19 | 1.0936 (5) | 0.0189 (3) | 0.26382 (12) | 0.0395 (9) | |
H19 | 1.2080 | 0.0073 | 0.2809 | 0.047* | |
C20 | 1.1404 (6) | 0.0818 (3) | 0.22529 (15) | 0.0500 (12) | |
C21 | 1.0121 (7) | −0.0725 (3) | 0.24745 (15) | 0.0582 (13) | |
H21A | 0.9779 | −0.0688 | 0.2160 | 0.070* | |
H21B | 1.1044 | −0.1195 | 0.2509 | 0.070* | |
C22 | 0.8384 (7) | −0.0930 (3) | 0.27615 (16) | 0.0549 (12) | |
H22A | 0.7249 | −0.0811 | 0.2594 | 0.066* | |
H22B | 0.8381 | −0.1552 | 0.2854 | 0.066* | |
C23 | 0.6078 (6) | 0.5185 (3) | 0.46879 (16) | 0.0609 (14) | |
H23A | 0.5525 | 0.4779 | 0.4899 | 0.091* | |
H23B | 0.5431 | 0.5144 | 0.4407 | 0.091* | |
H23C | 0.5987 | 0.5785 | 0.4801 | 0.091* | |
C24 | 0.9094 (6) | 0.4905 (3) | 0.50812 (12) | 0.0520 (11) | |
H24A | 1.0428 | 0.4891 | 0.5045 | 0.078* | |
H24B | 0.8693 | 0.4377 | 0.5237 | 0.078* | |
H24C | 0.8749 | 0.5426 | 0.5251 | 0.078* | |
C25 | 1.1663 (5) | 0.3518 (3) | 0.45069 (14) | 0.0448 (11) | |
H25A | 1.2627 | 0.3163 | 0.4371 | 0.067* | |
H25B | 1.1063 | 0.3177 | 0.4739 | 0.067* | |
H25C | 1.2205 | 0.4048 | 0.4634 | 0.067* | |
C26 | 0.9830 (6) | 0.1609 (3) | 0.43158 (12) | 0.0464 (11) | |
H26A | 0.9780 | 0.1885 | 0.4606 | 0.070* | |
H26B | 1.1106 | 0.1575 | 0.4218 | 0.070* | |
H26C | 0.9314 | 0.1017 | 0.4333 | 0.070* | |
C27 | 0.6862 (5) | 0.2109 (3) | 0.32242 (13) | 0.0416 (10) | |
H27A | 0.6494 | 0.1730 | 0.2980 | 0.062* | |
H27B | 0.7568 | 0.2606 | 0.3111 | 0.062* | |
H27C | 0.5768 | 0.2325 | 0.3376 | 0.062* | |
C28 | 0.9630 (7) | −0.0780 (3) | 0.35488 (15) | 0.0532 (12) | |
H28A | 1.0021 | −0.0341 | 0.3769 | 0.064* | |
H28B | 0.8833 | −0.1213 | 0.3698 | 0.064* | |
C29 | 1.3386 (8) | 0.0938 (4) | 0.21333 (19) | 0.0841 (19) | |
H29A | 1.4084 | 0.1103 | 0.2399 | 0.101* | |
H29B | 1.3494 | 0.1424 | 0.1919 | 0.101* | |
C30 | 1.0135 (8) | 0.1247 (4) | 0.20139 (15) | 0.0696 (16) | |
H30A | 1.0504 | 0.1613 | 0.1778 | 0.084* | |
H30B | 0.8873 | 0.1184 | 0.2082 | 0.084* | |
C31 | 1.2306 (8) | −0.1665 (4) | 0.3652 (2) | 0.0732 (16) | |
C32 | 1.3789 (7) | −0.2221 (4) | 0.3428 (2) | 0.094 (2) | |
H32A | 1.4944 | −0.2161 | 0.3589 | 0.141* | |
H32B | 1.3957 | −0.2019 | 0.3126 | 0.141* | |
H32C | 1.3411 | −0.2837 | 0.3427 | 0.141* | |
C33 | 0.8263 (7) | 0.7245 (3) | 0.43739 (18) | 0.0534 (12) | |
C34 | 0.8185 (9) | 0.8011 (3) | 0.46859 (19) | 0.0819 (18) | |
H34A | 0.9413 | 0.8261 | 0.4719 | 0.123* | |
H34B | 0.7738 | 0.7812 | 0.4972 | 0.123* | |
H34C | 0.7354 | 0.8458 | 0.4569 | 0.123* | |
O1 | 1.1239 (5) | −0.1224 (2) | 0.33705 (11) | 0.0625 (9) | |
O2 | 1.2042 (7) | −0.1640 (4) | 0.40533 (18) | 0.1280 (19) | |
O3 | 0.8996 (4) | 0.65128 (19) | 0.45704 (10) | 0.0473 (7) | |
O4 | 0.7726 (6) | 0.7259 (2) | 0.39882 (13) | 0.0783 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0718 (4) | 0.1855 (9) | 0.0816 (4) | 0.0435 (5) | 0.0114 (3) | −0.0252 (5) |
C1 | 0.039 (2) | 0.044 (3) | 0.035 (2) | −0.0083 (19) | 0.0101 (17) | −0.0059 (19) |
C2 | 0.047 (2) | 0.037 (3) | 0.042 (2) | −0.010 (2) | 0.0035 (19) | −0.0031 (19) |
C3 | 0.050 (2) | 0.032 (2) | 0.033 (2) | 0.0026 (19) | −0.0026 (18) | −0.0114 (18) |
C4 | 0.0410 (19) | 0.038 (2) | 0.0307 (19) | 0.001 (2) | 0.0084 (16) | −0.0040 (19) |
C5 | 0.0329 (19) | 0.032 (2) | 0.029 (2) | −0.0004 (17) | 0.0074 (16) | 0.0006 (17) |
C6 | 0.046 (2) | 0.042 (3) | 0.041 (2) | −0.008 (2) | 0.0186 (19) | −0.001 (2) |
C7 | 0.044 (2) | 0.033 (2) | 0.038 (2) | −0.0085 (19) | 0.0154 (18) | 0.0018 (19) |
C8 | 0.0327 (18) | 0.031 (2) | 0.0285 (19) | −0.0018 (17) | 0.0032 (16) | 0.0014 (17) |
C9 | 0.0260 (17) | 0.036 (2) | 0.0257 (18) | 0.0005 (16) | 0.0028 (14) | 0.0018 (16) |
C10 | 0.0263 (18) | 0.033 (2) | 0.0250 (18) | −0.0032 (16) | −0.0006 (15) | 0.0006 (17) |
C11 | 0.0321 (19) | 0.038 (2) | 0.044 (2) | −0.0041 (19) | 0.0077 (17) | −0.0048 (19) |
C12 | 0.0346 (19) | 0.034 (2) | 0.041 (2) | −0.0028 (17) | 0.0098 (18) | −0.0103 (19) |
C13 | 0.0304 (18) | 0.031 (2) | 0.032 (2) | 0.0034 (16) | −0.0028 (15) | 0.0021 (17) |
C14 | 0.0334 (18) | 0.031 (2) | 0.032 (2) | −0.0026 (18) | 0.0030 (16) | −0.0023 (17) |
C15 | 0.046 (2) | 0.039 (3) | 0.048 (3) | −0.005 (2) | 0.013 (2) | −0.006 (2) |
C16 | 0.056 (2) | 0.037 (3) | 0.058 (3) | −0.016 (2) | 0.008 (2) | −0.008 (2) |
C17 | 0.055 (2) | 0.031 (2) | 0.041 (2) | −0.002 (2) | 0.0046 (19) | −0.004 (2) |
C18 | 0.0378 (18) | 0.034 (2) | 0.0303 (18) | 0.0008 (18) | −0.0003 (16) | −0.0001 (17) |
C19 | 0.050 (2) | 0.037 (2) | 0.0312 (19) | 0.004 (2) | 0.0009 (16) | −0.0066 (18) |
C20 | 0.060 (3) | 0.049 (3) | 0.041 (2) | −0.003 (2) | 0.010 (2) | −0.012 (2) |
C21 | 0.083 (3) | 0.045 (3) | 0.047 (3) | −0.004 (3) | 0.009 (2) | −0.012 (2) |
C22 | 0.069 (3) | 0.038 (3) | 0.058 (3) | −0.007 (2) | 0.001 (2) | −0.007 (2) |
C23 | 0.049 (2) | 0.052 (3) | 0.082 (3) | −0.001 (2) | 0.024 (2) | −0.021 (3) |
C24 | 0.078 (3) | 0.049 (3) | 0.029 (2) | −0.007 (3) | 0.0065 (19) | −0.004 (2) |
C25 | 0.042 (2) | 0.047 (3) | 0.045 (2) | 0.006 (2) | −0.0109 (19) | −0.005 (2) |
C26 | 0.066 (3) | 0.041 (3) | 0.033 (2) | 0.001 (2) | −0.008 (2) | 0.007 (2) |
C27 | 0.0335 (19) | 0.051 (3) | 0.041 (2) | 0.0097 (19) | −0.0099 (17) | −0.004 (2) |
C28 | 0.072 (3) | 0.036 (3) | 0.052 (3) | 0.003 (3) | 0.003 (2) | 0.007 (2) |
C29 | 0.075 (3) | 0.115 (5) | 0.062 (3) | −0.033 (4) | 0.011 (3) | −0.009 (4) |
C30 | 0.089 (4) | 0.078 (4) | 0.041 (3) | 0.016 (3) | 0.004 (3) | 0.008 (3) |
C31 | 0.066 (3) | 0.074 (4) | 0.079 (4) | −0.009 (3) | −0.014 (3) | 0.001 (4) |
C32 | 0.065 (3) | 0.064 (4) | 0.153 (6) | 0.014 (3) | −0.022 (4) | −0.005 (4) |
C33 | 0.056 (3) | 0.040 (3) | 0.064 (3) | −0.004 (2) | 0.006 (2) | −0.006 (3) |
C34 | 0.107 (4) | 0.046 (3) | 0.093 (4) | −0.001 (3) | 0.018 (4) | −0.025 (3) |
O1 | 0.078 (2) | 0.054 (2) | 0.055 (2) | 0.0185 (19) | −0.0040 (17) | 0.0052 (17) |
O2 | 0.109 (3) | 0.179 (5) | 0.097 (3) | 0.039 (3) | −0.026 (3) | 0.022 (3) |
O3 | 0.0630 (18) | 0.0353 (18) | 0.0435 (16) | 0.0022 (15) | −0.0035 (14) | −0.0104 (14) |
O4 | 0.108 (3) | 0.049 (2) | 0.078 (3) | 0.013 (2) | −0.027 (2) | 0.005 (2) |
Br1—C29 | 1.943 (6) | C17—C28 | 1.550 (6) |
C1—C2 | 1.537 (5) | C17—C18 | 1.559 (5) |
C1—C10 | 1.539 (5) | C18—C19 | 1.530 (5) |
C1—H1A | 0.9700 | C18—H18 | 0.9800 |
C1—H1B | 0.9700 | C19—C20 | 1.522 (6) |
C2—C3 | 1.504 (6) | C19—C21 | 1.563 (6) |
C2—H2A | 0.9700 | C19—H19 | 0.9800 |
C2—H2B | 0.9700 | C20—C30 | 1.320 (6) |
C3—O3 | 1.464 (5) | C20—C29 | 1.473 (7) |
C3—C4 | 1.542 (6) | C21—C22 | 1.540 (7) |
C3—H3 | 0.9800 | C21—H21A | 0.9700 |
C4—C24 | 1.534 (5) | C21—H21B | 0.9700 |
C4—C23 | 1.544 (5) | C22—H22A | 0.9700 |
C4—C5 | 1.563 (5) | C22—H22B | 0.9700 |
C5—C6 | 1.546 (5) | C23—H23A | 0.9600 |
C5—C10 | 1.551 (5) | C23—H23B | 0.9600 |
C5—H5 | 0.9800 | C23—H23C | 0.9600 |
C6—C7 | 1.531 (6) | C24—H24A | 0.9600 |
C6—H6A | 0.9700 | C24—H24B | 0.9600 |
C6—H6B | 0.9700 | C24—H24C | 0.9600 |
C7—C8 | 1.532 (5) | C25—H25A | 0.9600 |
C7—H7A | 0.9700 | C25—H25B | 0.9600 |
C7—H7B | 0.9700 | C25—H25C | 0.9600 |
C8—C26 | 1.559 (5) | C26—H26A | 0.9600 |
C8—C9 | 1.574 (5) | C26—H26B | 0.9600 |
C8—C14 | 1.600 (5) | C26—H26C | 0.9600 |
C9—C11 | 1.525 (5) | C27—H27A | 0.9600 |
C9—C10 | 1.588 (5) | C27—H27B | 0.9600 |
C9—H9 | 0.9800 | C27—H27C | 0.9600 |
C10—C25 | 1.550 (5) | C28—O1 | 1.431 (5) |
C11—C12 | 1.537 (5) | C28—H28A | 0.9700 |
C11—H11A | 0.9700 | C28—H28B | 0.9700 |
C11—H11B | 0.9700 | C29—H29A | 0.9700 |
C12—C13 | 1.526 (5) | C29—H29B | 0.9700 |
C12—H12A | 0.9700 | C30—H30A | 0.9300 |
C12—H12B | 0.9700 | C30—H30B | 0.9300 |
C13—C18 | 1.540 (5) | C31—O2 | 1.211 (7) |
C13—C14 | 1.570 (5) | C31—O1 | 1.313 (6) |
C13—H13 | 0.9800 | C31—C32 | 1.504 (8) |
C14—C15 | 1.558 (5) | C32—H32A | 0.9600 |
C14—C27 | 1.565 (5) | C32—H32B | 0.9600 |
C15—C16 | 1.541 (5) | C32—H32C | 0.9600 |
C15—H15A | 0.9700 | C33—O4 | 1.213 (6) |
C15—H15B | 0.9700 | C33—O3 | 1.348 (6) |
C16—C17 | 1.516 (6) | C33—C34 | 1.477 (7) |
C16—H16A | 0.9700 | C34—H34A | 0.9600 |
C16—H16B | 0.9700 | C34—H34B | 0.9600 |
C17—C22 | 1.536 (6) | C34—H34C | 0.9600 |
C2—C1—C10 | 113.4 (3) | C16—C17—C28 | 107.3 (4) |
C2—C1—H1A | 108.9 | C22—C17—C28 | 109.6 (4) |
C10—C1—H1A | 108.9 | C16—C17—C18 | 106.4 (3) |
C2—C1—H1B | 108.9 | C22—C17—C18 | 101.1 (3) |
C10—C1—H1B | 108.9 | C28—C17—C18 | 116.4 (3) |
H1A—C1—H1B | 107.7 | C19—C18—C13 | 120.5 (3) |
C3—C2—C1 | 109.9 (3) | C19—C18—C17 | 106.0 (3) |
C3—C2—H2A | 109.7 | C13—C18—C17 | 111.6 (3) |
C1—C2—H2A | 109.7 | C19—C18—H18 | 105.9 |
C3—C2—H2B | 109.7 | C13—C18—H18 | 105.9 |
C1—C2—H2B | 109.7 | C17—C18—H18 | 105.9 |
H2A—C2—H2B | 108.2 | C20—C19—C18 | 114.7 (3) |
O3—C3—C2 | 109.8 (3) | C20—C19—C21 | 112.7 (3) |
O3—C3—C4 | 107.9 (3) | C18—C19—C21 | 103.3 (3) |
C2—C3—C4 | 113.6 (3) | C20—C19—H19 | 108.6 |
O3—C3—H3 | 108.5 | C18—C19—H19 | 108.6 |
C2—C3—H3 | 108.5 | C21—C19—H19 | 108.6 |
C4—C3—H3 | 108.5 | C30—C20—C29 | 118.1 (5) |
C24—C4—C3 | 112.0 (3) | C30—C20—C19 | 123.9 (4) |
C24—C4—C23 | 108.1 (3) | C29—C20—C19 | 118.0 (5) |
C3—C4—C23 | 106.9 (3) | C22—C21—C19 | 107.5 (4) |
C24—C4—C5 | 115.1 (3) | C22—C21—H21A | 110.2 |
C3—C4—C5 | 105.8 (3) | C19—C21—H21A | 110.2 |
C23—C4—C5 | 108.8 (3) | C22—C21—H21B | 110.2 |
C6—C5—C10 | 110.1 (3) | C19—C21—H21B | 110.2 |
C6—C5—C4 | 114.3 (3) | H21A—C21—H21B | 108.5 |
C10—C5—C4 | 117.7 (3) | C17—C22—C21 | 105.9 (4) |
C6—C5—H5 | 104.4 | C17—C22—H22A | 110.6 |
C10—C5—H5 | 104.4 | C21—C22—H22A | 110.6 |
C4—C5—H5 | 104.4 | C17—C22—H22B | 110.6 |
C7—C6—C5 | 110.5 (3) | C21—C22—H22B | 110.6 |
C7—C6—H6A | 109.6 | H22A—C22—H22B | 108.7 |
C5—C6—H6A | 109.6 | C4—C23—H23A | 109.5 |
C7—C6—H6B | 109.6 | C4—C23—H23B | 109.5 |
C5—C6—H6B | 109.6 | H23A—C23—H23B | 109.5 |
H6A—C6—H6B | 108.1 | C4—C23—H23C | 109.5 |
C6—C7—C8 | 113.7 (3) | H23A—C23—H23C | 109.5 |
C6—C7—H7A | 108.8 | H23B—C23—H23C | 109.5 |
C8—C7—H7A | 108.8 | C4—C24—H24A | 109.5 |
C6—C7—H7B | 108.8 | C4—C24—H24B | 109.5 |
C8—C7—H7B | 108.8 | H24A—C24—H24B | 109.5 |
H7A—C7—H7B | 107.7 | C4—C24—H24C | 109.5 |
C7—C8—C26 | 106.8 (3) | H24A—C24—H24C | 109.5 |
C7—C8—C9 | 109.5 (3) | H24B—C24—H24C | 109.5 |
C26—C8—C9 | 111.9 (3) | C10—C25—H25A | 109.5 |
C7—C8—C14 | 110.5 (3) | C10—C25—H25B | 109.5 |
C26—C8—C14 | 109.2 (3) | H25A—C25—H25B | 109.5 |
C9—C8—C14 | 109.0 (3) | C10—C25—H25C | 109.5 |
C11—C9—C8 | 110.4 (3) | H25A—C25—H25C | 109.5 |
C11—C9—C10 | 114.8 (3) | H25B—C25—H25C | 109.5 |
C8—C9—C10 | 116.5 (3) | C8—C26—H26A | 109.5 |
C11—C9—H9 | 104.5 | C8—C26—H26B | 109.5 |
C8—C9—H9 | 104.5 | H26A—C26—H26B | 109.5 |
C10—C9—H9 | 104.5 | C8—C26—H26C | 109.5 |
C1—C10—C25 | 107.8 (3) | H26A—C26—H26C | 109.5 |
C1—C10—C5 | 107.7 (3) | H26B—C26—H26C | 109.5 |
C25—C10—C5 | 114.1 (3) | C14—C27—H27A | 109.5 |
C1—C10—C9 | 108.3 (3) | C14—C27—H27B | 109.5 |
C25—C10—C9 | 112.4 (3) | H27A—C27—H27B | 109.5 |
C5—C10—C9 | 106.4 (3) | C14—C27—H27C | 109.5 |
C9—C11—C12 | 113.4 (3) | H27A—C27—H27C | 109.5 |
C9—C11—H11A | 108.9 | H27B—C27—H27C | 109.5 |
C12—C11—H11A | 108.9 | O1—C28—C17 | 110.7 (3) |
C9—C11—H11B | 108.9 | O1—C28—H28A | 109.5 |
C12—C11—H11B | 108.9 | C17—C28—H28A | 109.5 |
H11A—C11—H11B | 107.7 | O1—C28—H28B | 109.5 |
C13—C12—C11 | 112.4 (3) | C17—C28—H28B | 109.5 |
C13—C12—H12A | 109.1 | H28A—C28—H28B | 108.1 |
C11—C12—H12A | 109.1 | C20—C29—Br1 | 112.4 (4) |
C13—C12—H12B | 109.1 | C20—C29—H29A | 109.1 |
C11—C12—H12B | 109.1 | Br1—C29—H29A | 109.1 |
H12A—C12—H12B | 107.9 | C20—C29—H29B | 109.1 |
C12—C13—C18 | 116.0 (3) | Br1—C29—H29B | 109.1 |
C12—C13—C14 | 110.6 (3) | H29A—C29—H29B | 107.9 |
C18—C13—C14 | 109.9 (3) | C20—C30—H30A | 120.0 |
C12—C13—H13 | 106.6 | C20—C30—H30B | 120.0 |
C18—C13—H13 | 106.6 | H30A—C30—H30B | 120.0 |
C14—C13—H13 | 106.6 | O2—C31—O1 | 121.8 (6) |
C15—C14—C27 | 107.6 (3) | O2—C31—C32 | 124.4 (6) |
C15—C14—C13 | 110.5 (3) | O1—C31—C32 | 113.7 (6) |
C27—C14—C13 | 109.6 (3) | C31—C32—H32A | 109.5 |
C15—C14—C8 | 110.6 (3) | C31—C32—H32B | 109.5 |
C27—C14—C8 | 110.1 (3) | H32A—C32—H32B | 109.5 |
C13—C14—C8 | 108.5 (3) | C31—C32—H32C | 109.5 |
C16—C15—C14 | 115.1 (3) | H32A—C32—H32C | 109.5 |
C16—C15—H15A | 108.5 | H32B—C32—H32C | 109.5 |
C14—C15—H15A | 108.5 | O4—C33—O3 | 123.4 (4) |
C16—C15—H15B | 108.5 | O4—C33—C34 | 124.9 (5) |
C14—C15—H15B | 108.5 | O3—C33—C34 | 111.7 (5) |
H15A—C15—H15B | 107.5 | C33—C34—H34A | 109.5 |
C17—C16—C15 | 112.6 (3) | C33—C34—H34B | 109.5 |
C17—C16—H16A | 109.1 | H34A—C34—H34B | 109.5 |
C15—C16—H16A | 109.1 | C33—C34—H34C | 109.5 |
C17—C16—H16B | 109.1 | H34A—C34—H34C | 109.5 |
C15—C16—H16B | 109.1 | H34B—C34—H34C | 109.5 |
H16A—C16—H16B | 107.8 | C31—O1—C28 | 117.5 (4) |
C16—C17—C22 | 116.2 (3) | C33—O3—C3 | 118.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C32—H32A···O4i | 0.96 | 2.48 | 3.365 (7) | 154 |
C28—H28B···O4ii | 0.97 | 2.57 | 3.487 (6) | 158 |
Symmetry codes: (i) x+1, y−1, z; (ii) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C34H53BrO4 |
Mr | 605.67 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 291 |
a, b, c (Å) | 7.152 (3), 14.946 (7), 29.837 (12) |
V (Å3) | 3189 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.32 |
Crystal size (mm) | 0.40 × 0.38 × 0.37 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.622, 0.642 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23319, 5578, 3534 |
Rint | 0.102 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.145, 0.94 |
No. of reflections | 5578 |
No. of parameters | 358 |
No. of restraints | 18 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.58 |
Absolute structure | Flack (1983), 2346 Friedel pairs |
Absolute structure parameter | 0.024 (12) |
Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C32—H32A···O4i | 0.96 | 2.48 | 3.365 (7) | 154.2 |
C28—H28B···O4ii | 0.97 | 2.57 | 3.487 (6) | 158.3 |
Symmetry codes: (i) x+1, y−1, z; (ii) x, y−1, z. |
Acknowledgements
The authors thank the `948' Project of State Forestry Administration (2006–4-119) and the Innovation Fund for Outstanding Young Teachers of Northeast Forestry University for supporting of this study.
References
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Kim, D. S., Pezzuto, J. M. & Pisha, E. (1998). Bioorg. Med. Chem. Lett. 8, 1707–1712. Web of Science CrossRef CAS PubMed Google Scholar
Mohamed, I. E., Choudhary, M. I., Ali, S., Anjum, S. & Atta-ur-Rahman (2006). Acta Cryst. E62, o1352–o1354. Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, C.-I., Wang, H.-K., Kashiwada, Y., Shen, J.-K., Cosentino, L.-M., Chen, C.-H., Yang, L.-M. & Lee, K.-H. (1998). J. Med. Chem. 41, 4648–4657. Web of Science CrossRef CAS PubMed Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Betulin and its derivatives have been attracting extensive interests, owing to their anti-HIV and antitumor activites (Sun et al., 1998; Kim et al., 1998). The crystal structure of the diacetylation of betulin has been reported, considering the significance of its stereochemistry study. (Mohamed et al., 2006). We report here the synthesis and the crystal structure of the title compound (I) - a new betulin derivative.
In (I) (Fig. 1), the cyclopentane ring adopts a twisted envelope conformation and all cyclohexane rings adopt chair conformations. The bond distances and angles are all within the expected ranges and agree with those in the similar compound reported previously (Mohamed et al., 2006).
In the crystal, weak intermolecular C—H···O hydrogen bonds (Table 1) link the molecules into corrugated sheets parallel to ab plane.