Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041116/lh2479sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041116/lh2479Isup2.hkl |
CCDC reference: 660364
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.049
- wR factor = 0.096
- Data-to-parameter ratio = 12.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 41 Perc. PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Cragg et al. (1982); Gao et al. (2004); Gellert (1982); Nordlander & Njoroge (1987); Pausacker (1953); Ratnagiriswaran & Venkatachalam (1935); Staerk et al. (2000); Wu et al. (2002).
The title compound was synthesized by the route depicted in Fig. 3 (Pausacker, 1953; Cragg et al., 1982, Nordlander & Njoroge, 1987) and recrystallized from chloroform–anhydrous ethanol (1:3, v/v) to give 1.5 g (56.4%) of block-shaped light yellow crystals.
All H atoms were positioned geometrically and treated as riding (C—H = 0.96 Å for methyl; C—H = 0.93 Å for phenyl and C—H = 0.97 Å for methylene). Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms.
Phenanthroindolizidine alkaloids are extensively present in various plants of the Asclepiadaceae family (Gellert, 1982; Staerk et al., 2000). These natural products exhibit interesting biological properties, such as emetic and vesicant properties, unusual cardiovascular and immunological efects, nerve growth stimulation and probable anti-inflammatory, especially anti-tumor activity. Since the first isolation of (-)-tylophorine in 1935 (Ratnagiriswaran & Venkatachalam, 1935), phenanthroindolizidine alkaloids have engendered a great deal of synthetic work. To further evaluate the antitumor potential of these analogs (Gao et al., 2004; Wu et al., 2002), we plan to synthesize some tylophorine analogs that have a mode of action different from known antitumor drugs. 2,3-Dimethoxy-6,7-methylenedioxyphenanthrene is an important intermediate in the synthesis of phenanthroindolizidine alkaloid analogs. Here we report the synthesis and structure of the title compound. In the title molecule all non-hydrogen atoms are essentially coplanar, with the mean deviation of 0.0432 Å. The crystal structure is stabilized by weak intermolecular C—H···O hydrogen bonds.
For related literature, see: Cragg et al. (1982); Gao et al. (2004); Gellert (1982); Nordlander & Njoroge (1987); Pausacker (1953); Ratnagiriswaran & Venkatachalam (1935); Staerk et al. (2000); Wu et al. (2002).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
C17H14O4 | F(000) = 592 |
Mr = 282.28 | Dx = 1.416 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 476 reflections |
a = 7.370 (2) Å | θ = 2.4–19.8° |
b = 18.375 (5) Å | µ = 0.10 mm−1 |
c = 9.840 (3) Å | T = 293 K |
β = 96.363 (4)° | Block, yellow |
V = 1324.3 (6) Å3 | 0.20 × 0.15 × 0.06 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2452 independent reflections |
Radiation source: fine-focus sealed tube | 1011 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.078 |
φ and ω scans | θmax = 25.5°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.980, Tmax = 0.994 | k = −22→22 |
8248 measured reflections | l = −11→11 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.0197P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2452 reflections | Δρmax = 0.15 e Å−3 |
193 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0039 (7) |
C17H14O4 | V = 1324.3 (6) Å3 |
Mr = 282.28 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.370 (2) Å | µ = 0.10 mm−1 |
b = 18.375 (5) Å | T = 293 K |
c = 9.840 (3) Å | 0.20 × 0.15 × 0.06 mm |
β = 96.363 (4)° |
Bruker SMART CCD area-detector diffractometer | 2452 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1011 reflections with I > 2σ(I) |
Tmin = 0.980, Tmax = 0.994 | Rint = 0.078 |
8248 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.15 e Å−3 |
2452 reflections | Δρmin = −0.21 e Å−3 |
193 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1 | 1.5050 (3) | 0.57314 (11) | 0.3802 (2) | 0.0700 (7) | |
O2 | 1.4596 (3) | 0.67949 (12) | 0.2522 (2) | 0.0791 (7) | |
O3 | 0.8424 (3) | 0.47117 (11) | 0.8618 (2) | 0.0606 (6) | |
O4 | 0.5699 (3) | 0.55533 (11) | 0.8808 (2) | 0.0654 (7) | |
C1 | 1.3541 (4) | 0.60954 (18) | 0.4156 (3) | 0.0528 (8) | |
C2 | 1.3279 (4) | 0.67320 (18) | 0.3401 (3) | 0.0568 (9) | |
C3 | 1.1868 (4) | 0.71875 (16) | 0.3549 (3) | 0.0610 (9) | |
H3 | 1.1713 | 0.7615 | 0.3045 | 0.073* | |
C4 | 1.0630 (4) | 0.69895 (17) | 0.4501 (3) | 0.0517 (9) | |
C5 | 0.9111 (4) | 0.74388 (16) | 0.4666 (3) | 0.0587 (9) | |
H5 | 0.8970 | 0.7872 | 0.4177 | 0.070* | |
C6 | 0.7854 (4) | 0.72569 (16) | 0.5513 (3) | 0.0561 (9) | |
H6 | 0.6867 | 0.7563 | 0.5592 | 0.067* | |
C7 | 0.8033 (4) | 0.65989 (16) | 0.6287 (3) | 0.0471 (8) | |
C8 | 0.6715 (4) | 0.64073 (16) | 0.7161 (3) | 0.0529 (9) | |
H8 | 0.5715 | 0.6710 | 0.7217 | 0.063* | |
C9 | 0.6883 (4) | 0.57893 (17) | 0.7920 (3) | 0.0513 (9) | |
C10 | 0.8390 (4) | 0.53238 (16) | 0.7810 (3) | 0.0489 (8) | |
C11 | 0.9687 (4) | 0.54971 (15) | 0.6972 (3) | 0.0499 (8) | |
H11 | 1.0676 | 0.5187 | 0.6924 | 0.060* | |
C12 | 0.9550 (4) | 0.61436 (16) | 0.6173 (3) | 0.0448 (8) | |
C13 | 1.0876 (4) | 0.63338 (16) | 0.5259 (3) | 0.0455 (8) | |
C14 | 1.2392 (4) | 0.58828 (15) | 0.5059 (3) | 0.0523 (8) | |
H14 | 1.2589 | 0.5449 | 0.5541 | 0.063* | |
C15 | 1.5719 (4) | 0.61577 (19) | 0.2752 (3) | 0.0749 (11) | |
H15A | 1.5682 | 0.5875 | 0.1916 | 0.090* | |
H15B | 1.6975 | 0.6299 | 0.3025 | 0.090* | |
C16 | 0.9977 (4) | 0.42465 (15) | 0.8652 (3) | 0.0643 (10) | |
H16A | 1.0101 | 0.4076 | 0.7745 | 0.096* | |
H16B | 0.9822 | 0.3839 | 0.9238 | 0.096* | |
H16C | 1.1053 | 0.4512 | 0.8996 | 0.096* | |
C17 | 0.4168 (4) | 0.60052 (16) | 0.8973 (3) | 0.0728 (10) | |
H17A | 0.4587 | 0.6467 | 0.9339 | 0.109* | |
H17B | 0.3421 | 0.5776 | 0.9589 | 0.109* | |
H17C | 0.3466 | 0.6077 | 0.8101 | 0.109* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0601 (15) | 0.0798 (17) | 0.0734 (17) | 0.0039 (13) | 0.0226 (13) | 0.0136 (13) |
O2 | 0.0748 (18) | 0.0823 (18) | 0.0852 (18) | −0.0120 (15) | 0.0314 (14) | 0.0148 (14) |
O3 | 0.0691 (15) | 0.0549 (14) | 0.0609 (15) | 0.0081 (12) | 0.0219 (11) | 0.0117 (12) |
O4 | 0.0588 (15) | 0.0665 (15) | 0.0747 (17) | 0.0039 (12) | 0.0239 (13) | 0.0043 (12) |
C1 | 0.048 (2) | 0.056 (2) | 0.053 (2) | 0.0010 (18) | 0.0043 (18) | −0.0028 (18) |
C2 | 0.056 (2) | 0.058 (2) | 0.056 (2) | −0.012 (2) | 0.0074 (19) | 0.0065 (19) |
C3 | 0.071 (3) | 0.045 (2) | 0.066 (3) | −0.0108 (19) | 0.002 (2) | 0.0063 (17) |
C4 | 0.059 (2) | 0.045 (2) | 0.052 (2) | −0.0040 (18) | 0.0047 (18) | 0.0012 (17) |
C5 | 0.074 (3) | 0.045 (2) | 0.056 (2) | 0.0018 (19) | 0.002 (2) | 0.0056 (17) |
C6 | 0.069 (2) | 0.045 (2) | 0.053 (2) | 0.0078 (18) | 0.0018 (19) | −0.0018 (17) |
C7 | 0.052 (2) | 0.043 (2) | 0.045 (2) | −0.0002 (17) | −0.0004 (17) | −0.0057 (16) |
C8 | 0.054 (2) | 0.054 (2) | 0.051 (2) | 0.0064 (17) | 0.0051 (18) | −0.0061 (17) |
C9 | 0.047 (2) | 0.056 (2) | 0.051 (2) | −0.0041 (19) | 0.0080 (18) | −0.0055 (18) |
C10 | 0.053 (2) | 0.044 (2) | 0.048 (2) | −0.0002 (18) | 0.0027 (17) | 0.0017 (17) |
C11 | 0.051 (2) | 0.044 (2) | 0.055 (2) | −0.0008 (16) | 0.0060 (17) | −0.0027 (17) |
C12 | 0.050 (2) | 0.042 (2) | 0.042 (2) | 0.0026 (16) | 0.0017 (16) | −0.0026 (16) |
C13 | 0.052 (2) | 0.044 (2) | 0.041 (2) | −0.0021 (16) | 0.0037 (16) | −0.0045 (16) |
C14 | 0.057 (2) | 0.048 (2) | 0.053 (2) | 0.0011 (17) | 0.0072 (18) | 0.0035 (16) |
C15 | 0.070 (3) | 0.083 (3) | 0.075 (3) | −0.010 (2) | 0.023 (2) | 0.002 (2) |
C16 | 0.072 (2) | 0.053 (2) | 0.069 (2) | 0.0160 (19) | 0.0116 (19) | 0.0119 (17) |
C17 | 0.057 (2) | 0.088 (3) | 0.075 (3) | 0.008 (2) | 0.0192 (19) | −0.009 (2) |
O1—C1 | 1.375 (3) | C7—C12 | 1.410 (3) |
O1—C15 | 1.428 (3) | C7—C8 | 1.411 (4) |
O2—C2 | 1.375 (3) | C8—C9 | 1.357 (3) |
O2—C15 | 1.437 (3) | C8—H8 | 0.9300 |
O3—C10 | 1.376 (3) | C9—C10 | 1.416 (4) |
O3—C16 | 1.426 (3) | C10—C11 | 1.367 (3) |
O4—C9 | 1.372 (3) | C11—C12 | 1.422 (3) |
O4—C17 | 1.424 (3) | C11—H11 | 0.9300 |
C1—C14 | 1.351 (4) | C12—C13 | 1.443 (4) |
C1—C2 | 1.387 (4) | C13—C14 | 1.422 (3) |
C2—C3 | 1.355 (4) | C14—H14 | 0.9300 |
C3—C4 | 1.426 (4) | C15—H15A | 0.9700 |
C3—H3 | 0.9300 | C15—H15B | 0.9700 |
C4—C5 | 1.415 (4) | C16—H16A | 0.9600 |
C4—C13 | 1.418 (4) | C16—H16B | 0.9600 |
C5—C6 | 1.355 (4) | C16—H16C | 0.9600 |
C5—H5 | 0.9300 | C17—H17A | 0.9600 |
C6—C7 | 1.427 (3) | C17—H17B | 0.9600 |
C6—H6 | 0.9300 | C17—H17C | 0.9600 |
C1—O1—C15 | 105.7 (2) | C11—C10—C9 | 120.8 (3) |
C2—O2—C15 | 105.5 (2) | O3—C10—C9 | 114.5 (3) |
C10—O3—C16 | 117.8 (2) | C10—C11—C12 | 121.1 (3) |
C9—O4—C17 | 117.1 (2) | C10—C11—H11 | 119.5 |
C14—C1—O1 | 127.5 (3) | C12—C11—H11 | 119.5 |
C14—C1—C2 | 122.4 (3) | C7—C12—C11 | 117.4 (3) |
O1—C1—C2 | 110.1 (3) | C7—C12—C13 | 120.2 (3) |
C3—C2—O2 | 128.2 (3) | C11—C12—C13 | 122.4 (3) |
C3—C2—C1 | 121.8 (3) | C4—C13—C14 | 118.6 (3) |
O2—C2—C1 | 110.0 (3) | C4—C13—C12 | 118.6 (3) |
C2—C3—C4 | 117.9 (3) | C14—C13—C12 | 122.8 (3) |
C2—C3—H3 | 121.1 | C1—C14—C13 | 118.8 (3) |
C4—C3—H3 | 121.1 | C1—C14—H14 | 120.6 |
C5—C4—C13 | 119.5 (3) | C13—C14—H14 | 120.6 |
C5—C4—C3 | 119.9 (3) | O1—C15—O2 | 108.8 (2) |
C13—C4—C3 | 120.6 (3) | O1—C15—H15A | 109.9 |
C6—C5—C4 | 122.0 (3) | O2—C15—H15A | 109.9 |
C6—C5—H5 | 119.0 | O1—C15—H15B | 109.9 |
C4—C5—H5 | 119.0 | O2—C15—H15B | 109.9 |
C5—C6—C7 | 120.5 (3) | H15A—C15—H15B | 108.3 |
C5—C6—H6 | 119.7 | O3—C16—H16A | 109.5 |
C7—C6—H6 | 119.7 | O3—C16—H16B | 109.5 |
C12—C7—C8 | 120.3 (3) | H16A—C16—H16B | 109.5 |
C12—C7—C6 | 119.2 (3) | O3—C16—H16C | 109.5 |
C8—C7—C6 | 120.5 (3) | H16A—C16—H16C | 109.5 |
C9—C8—C7 | 121.1 (3) | H16B—C16—H16C | 109.5 |
C9—C8—H8 | 119.4 | O4—C17—H17A | 109.5 |
C7—C8—H8 | 119.4 | O4—C17—H17B | 109.5 |
C8—C9—O4 | 126.1 (3) | H17A—C17—H17B | 109.5 |
C8—C9—C10 | 119.2 (3) | O4—C17—H17C | 109.5 |
O4—C9—C10 | 114.7 (3) | H17A—C17—H17C | 109.5 |
C11—C10—O3 | 124.7 (3) | H17B—C17—H17C | 109.5 |
C15—O1—C1—C14 | 176.3 (3) | O4—C9—C10—C11 | −179.3 (2) |
C15—O1—C1—C2 | −1.5 (3) | C8—C9—C10—O3 | −179.7 (2) |
C15—O2—C2—C3 | −178.2 (3) | O4—C9—C10—O3 | −0.3 (4) |
C15—O2—C2—C1 | 0.3 (3) | O3—C10—C11—C12 | −179.8 (2) |
C14—C1—C2—C3 | 1.4 (5) | C9—C10—C11—C12 | −0.9 (4) |
O1—C1—C2—C3 | 179.4 (3) | C8—C7—C12—C11 | −0.3 (4) |
C14—C1—C2—O2 | −177.2 (3) | C6—C7—C12—C11 | 179.3 (2) |
O1—C1—C2—O2 | 0.8 (4) | C8—C7—C12—C13 | 178.8 (3) |
O2—C2—C3—C4 | 177.6 (3) | C6—C7—C12—C13 | −1.6 (4) |
C1—C2—C3—C4 | −0.7 (5) | C10—C11—C12—C7 | 0.4 (4) |
C2—C3—C4—C5 | −178.5 (3) | C10—C11—C12—C13 | −178.7 (3) |
C2—C3—C4—C13 | −0.3 (4) | C5—C4—C13—C14 | 178.8 (3) |
C13—C4—C5—C6 | −1.1 (4) | C3—C4—C13—C14 | 0.6 (4) |
C3—C4—C5—C6 | 177.1 (3) | C5—C4—C13—C12 | 0.4 (4) |
C4—C5—C6—C7 | 0.5 (5) | C3—C4—C13—C12 | −177.8 (3) |
C5—C6—C7—C12 | 0.9 (4) | C7—C12—C13—C4 | 0.9 (4) |
C5—C6—C7—C8 | −179.5 (3) | C11—C12—C13—C4 | 180.0 (3) |
C12—C7—C8—C9 | 0.8 (4) | C7—C12—C13—C14 | −177.4 (3) |
C6—C7—C8—C9 | −178.9 (3) | C11—C12—C13—C14 | 1.6 (4) |
C7—C8—C9—O4 | 179.4 (3) | O1—C1—C14—C13 | −178.6 (3) |
C7—C8—C9—C10 | −1.2 (4) | C2—C1—C14—C13 | −1.0 (4) |
C17—O4—C9—C8 | −1.4 (4) | C4—C13—C14—C1 | 0.0 (4) |
C17—O4—C9—C10 | 179.2 (2) | C12—C13—C14—C1 | 178.4 (3) |
C16—O3—C10—C11 | 4.1 (4) | C1—O1—C15—O2 | 1.7 (3) |
C16—O3—C10—C9 | −174.9 (2) | C2—O2—C15—O1 | −1.2 (3) |
C8—C9—C10—C11 | 1.3 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C17—H17B···O3i | 0.96 | 2.51 | 3.465 (3) | 174 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C17H14O4 |
Mr | 282.28 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.370 (2), 18.375 (5), 9.840 (3) |
β (°) | 96.363 (4) |
V (Å3) | 1324.3 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.20 × 0.15 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.980, 0.994 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8248, 2452, 1011 |
Rint | 0.078 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.096, 1.04 |
No. of reflections | 2452 |
No. of parameters | 193 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.21 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C17—H17B···O3i | 0.96 | 2.51 | 3.465 (3) | 174 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
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Phenanthroindolizidine alkaloids are extensively present in various plants of the Asclepiadaceae family (Gellert, 1982; Staerk et al., 2000). These natural products exhibit interesting biological properties, such as emetic and vesicant properties, unusual cardiovascular and immunological efects, nerve growth stimulation and probable anti-inflammatory, especially anti-tumor activity. Since the first isolation of (-)-tylophorine in 1935 (Ratnagiriswaran & Venkatachalam, 1935), phenanthroindolizidine alkaloids have engendered a great deal of synthetic work. To further evaluate the antitumor potential of these analogs (Gao et al., 2004; Wu et al., 2002), we plan to synthesize some tylophorine analogs that have a mode of action different from known antitumor drugs. 2,3-Dimethoxy-6,7-methylenedioxyphenanthrene is an important intermediate in the synthesis of phenanthroindolizidine alkaloid analogs. Here we report the synthesis and structure of the title compound. In the title molecule all non-hydrogen atoms are essentially coplanar, with the mean deviation of 0.0432 Å. The crystal structure is stabilized by weak intermolecular C—H···O hydrogen bonds.