2,3-Dimeth­oxy-6,7-methyl­enedioxy­phenanthrene

Wang, Y.-X.; Liu, C.-B.; Fang, Z.-J.; Wen, H.-L.; Xie, M.-Y.

doi:10.1107/S1600536807041116

2,3-Dimethoxy-6,7-methylenedioxyphenanthrene

Y.-X. Wang, C.-B. Liu, Z.-J. Fang, H.-L. Wen and M.-Y. Xie

In the title molecule, C₁₇H₁₄O₄, all non-H atoms are essentially coplanar. The crystal structure is stabilized by weak intermolecular C—H

O hydrogen bonds.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041116/lh2479sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041116/lh2479Isup2.hkl Contains datablock I

CCDC reference: 660364

checkCIF report

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

Comment top

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.

Related literature top

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).

Experimental top

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.

Structure description top

Computing details top

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.

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. The packing of the title compound along the a axis, H-bonds are shown as dashed lines.
	Fig. 3. Reaction Scheme

2,3-Dimethoxy-6,7-methylenedioxyphenanthrene top

Crystal data top

C₁₇H₁₄O₄	F(000) = 592
M_r = 282.28	D_x = 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

Data collection top

Bruker SMART CCD area-detector diffractometer	2452 independent reflections
Radiation source: fine-focus sealed tube	1011 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.078
φ and ω scans	θ_max = 25.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.980, T_max = 0.994	k = −22→22
8248 measured reflections	l = −11→11

Refinement top

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(F_o²) + (0.0197P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2452 reflections	Δρ_max = 0.15 e Å⁻³
193 parameters	Δρ_min = −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)

Crystal data top

C₁₇H₁₄O₄	V = 1324.3 (6) Å³
M_r = 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)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2452 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1011 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.994	R_int = 0.078
8248 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.04	Δρ_max = 0.15 e Å⁻³
2452 reflections	Δρ_min = −0.21 e Å⁻³
193 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	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.980, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	8248, 2452, 1011
R_int	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
Δρ_max, Δρ_min (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.