organic compounds
2,3:6,7-Bis(methylenedioxy)phenanthrene
aState Key Laboratory of Food Science and Technology, Nanchang University, Nanchang 330047, People's Republic of China, bSchool of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, People's Republic of China, and cCollege of Environmental and Chemical Engineering, Nanchang University of Aeronautics, Nanchang 330063, People's Republic of China
*Correspondence e-mail: yuanxingwang@tom.com
In the title molecule, C16H10O4, all the non-H atoms are coplanar. The is stabilized by weak intermolecular C—H⋯O contacts and π–π stacking interactions (the interplanar distance is 3.43 Å).
Related literature
For related literature, see: Cragg et al. (1982); Nordlander & Njoroge (1987); Pausacker (1953); Wang et al. (2007).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1998); cell 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.
Supporting information
https://doi.org/10.1107/S1600536807065592/hj2009sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807065592/hj2009Isup2.hkl
The title compound was synthesized by the route depicted in Fig. 2 [Pausacker, 1953; Cragg et al., 1982; Nordlander & Njoroge, 1987] and recrystallized from chloroform–anhydrous ethanol (1:3, v/v) to give 2.2 g (50.3%) of block yellow crystals.
All H atoms were positioned geometrically and treated as riding (C—H = 0.97 Å for methylene and C—H = 0.93 Å for phenyl). Uiso(H) = 1.5 for methyl and 1.2 Ueq(C) for others of the carrier atom.
Recently, our group (Wang et al., 2007) decribed the π–π stacking interactions between the parallel molecules; the interplanar distance is 3.43 Å (symmetry code: -1 + x, y, z).
of 2,3-Dimethoxy-6,7- methylenedioxyphenanthrene [1] (C17H14O4). Here we report the of 2,3:6,7-bis(methylenedioxy)phenanthrene, another important intermediate in the synthesis of phenanthroindolizidine and phenanthroquinolizidine analogs. In the title molecule, all the non-hydrogen atoms are nearly coplanar, with the mean deviation of 0.0763 Å, The is stabilized by weak intermolecular C11—H11···O1 contacts with C···O distance 3.442 (3) Å andFor related literature, see: Cragg et al. (1982); Nordlander & Njoroge (1987); Pausacker (1953); Wang et al. (2007).
Data collection: SMART (Bruker, 1998); cell
SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 (Bruker, 1998).Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids. | |
Fig. 2. Synthesis of the title compound. |
C16H10O4 | Z = 2 |
Mr = 266.24 | F(000) = 276 |
Triclinic, P1 | Dx = 1.531 Mg m−3 |
Hall symbol: -p 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.862 (2) Å | Cell parameters from 1555 reflections |
b = 7.775 (2) Å | θ = 2.7–28.2° |
c = 11.495 (3) Å | µ = 0.11 mm−1 |
α = 75.084 (3)° | T = 293 K |
β = 77.118 (3)° | Block, yellow |
γ = 86.460 (4)° | 0.34 × 0.30 × 0.25 mm |
V = 577.7 (3) Å3 |
Bruker SMART CCD diffractometer | 2126 independent reflections |
Radiation source: fine-focus sealed tube | 1543 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
φ and ω scans | θmax = 25.5°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→7 |
Tmin = 0.963, Tmax = 0.973 | k = −9→9 |
4267 measured reflections | l = −13→13 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0713P)2 + 0.0394P] where P = (Fo2 + 2Fc2)/3 |
2126 reflections | (Δ/σ)max < 0.001 |
181 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C16H10O4 | γ = 86.460 (4)° |
Mr = 266.24 | V = 577.7 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.862 (2) Å | Mo Kα radiation |
b = 7.775 (2) Å | µ = 0.11 mm−1 |
c = 11.495 (3) Å | T = 293 K |
α = 75.084 (3)° | 0.34 × 0.30 × 0.25 mm |
β = 77.118 (3)° |
Bruker SMART CCD diffractometer | 2126 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1543 reflections with I > 2σ(I) |
Tmin = 0.963, Tmax = 0.973 | Rint = 0.024 |
4267 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.17 e Å−3 |
2126 reflections | Δρmin = −0.27 e Å−3 |
181 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 | 0.98631 (17) | 0.29142 (18) | 0.28720 (11) | 0.0600 (4) | |
O2 | 0.76359 (19) | 0.46464 (18) | 0.18194 (11) | 0.0593 (4) | |
O3 | 0.60609 (18) | −0.23746 (17) | 0.93565 (11) | 0.0600 (4) | |
O4 | 0.27411 (19) | −0.20727 (18) | 1.02816 (11) | 0.0635 (4) | |
C1 | 0.7991 (2) | 0.2792 (2) | 0.36405 (16) | 0.0419 (4) | |
C2 | 0.6664 (2) | 0.3858 (2) | 0.30069 (15) | 0.0431 (4) | |
C3 | 0.4708 (2) | 0.3990 (2) | 0.35505 (15) | 0.0440 (4) | |
H3 | 0.3823 | 0.4701 | 0.3126 | 0.053* | |
C4 | 0.4065 (2) | 0.3002 (2) | 0.47905 (15) | 0.0386 (4) | |
C5 | 0.2024 (2) | 0.3094 (2) | 0.53970 (16) | 0.0455 (4) | |
H5 | 0.1136 | 0.3796 | 0.4970 | 0.055* | |
C6 | 0.1352 (2) | 0.2188 (2) | 0.65725 (16) | 0.0461 (4) | |
H6 | 0.0013 | 0.2291 | 0.6942 | 0.055* | |
C7 | 0.2640 (2) | 0.1071 (2) | 0.72689 (15) | 0.0399 (4) | |
C8 | 0.1875 (3) | 0.0104 (2) | 0.84929 (16) | 0.0481 (5) | |
H8 | 0.0540 | 0.0210 | 0.8869 | 0.058* | |
C9 | 0.3135 (3) | −0.0980 (2) | 0.91036 (16) | 0.0459 (4) | |
C10 | 0.5148 (2) | −0.1147 (2) | 0.85469 (16) | 0.0424 (4) | |
C11 | 0.5953 (2) | −0.0243 (2) | 0.73845 (14) | 0.0398 (4) | |
H11 | 0.7298 | −0.0374 | 0.7040 | 0.048* | |
C12 | 0.4690 (2) | 0.0916 (2) | 0.66999 (14) | 0.0359 (4) | |
C13 | 0.5411 (2) | 0.1911 (2) | 0.54379 (14) | 0.0356 (4) | |
C14 | 0.7449 (2) | 0.1829 (2) | 0.48162 (15) | 0.0403 (4) | |
H14 | 0.8375 | 0.1130 | 0.5211 | 0.048* | |
C15 | 0.9666 (3) | 0.4100 (3) | 0.17378 (17) | 0.0599 (5) | |
H15A | 1.0083 | 0.3512 | 0.1073 | 0.072* | |
H15B | 1.0511 | 0.5130 | 0.1564 | 0.072* | |
C16 | 0.4614 (3) | −0.2862 (2) | 1.04828 (16) | 0.0522 (5) | |
H16A | 0.5025 | −0.2446 | 1.1118 | 0.063* | |
H16B | 0.4489 | −0.4147 | 1.0753 | 0.063* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0334 (7) | 0.0854 (9) | 0.0466 (8) | 0.0035 (6) | 0.0006 (5) | 0.0004 (7) |
O2 | 0.0483 (8) | 0.0723 (9) | 0.0444 (8) | 0.0037 (6) | −0.0038 (6) | 0.0023 (6) |
O3 | 0.0475 (8) | 0.0713 (9) | 0.0447 (8) | 0.0138 (6) | −0.0030 (6) | 0.0055 (6) |
O4 | 0.0509 (8) | 0.0801 (9) | 0.0424 (8) | 0.0079 (7) | 0.0017 (6) | 0.0029 (7) |
C1 | 0.0294 (8) | 0.0502 (10) | 0.0448 (10) | −0.0010 (7) | −0.0045 (7) | −0.0120 (8) |
C2 | 0.0419 (10) | 0.0460 (10) | 0.0395 (10) | −0.0014 (7) | −0.0081 (8) | −0.0073 (8) |
C3 | 0.0399 (10) | 0.0484 (10) | 0.0439 (10) | 0.0062 (7) | −0.0146 (8) | −0.0085 (8) |
C4 | 0.0327 (9) | 0.0420 (9) | 0.0442 (10) | 0.0031 (7) | −0.0102 (7) | −0.0154 (7) |
C5 | 0.0340 (9) | 0.0530 (10) | 0.0517 (11) | 0.0112 (7) | −0.0147 (8) | −0.0149 (8) |
C6 | 0.0283 (8) | 0.0606 (11) | 0.0507 (11) | 0.0081 (8) | −0.0058 (7) | −0.0204 (9) |
C7 | 0.0326 (9) | 0.0474 (9) | 0.0413 (10) | 0.0030 (7) | −0.0061 (7) | −0.0165 (7) |
C8 | 0.0333 (9) | 0.0626 (11) | 0.0445 (10) | 0.0037 (8) | 0.0007 (7) | −0.0153 (9) |
C9 | 0.0431 (10) | 0.0518 (10) | 0.0402 (10) | 0.0001 (8) | −0.0028 (7) | −0.0121 (8) |
C10 | 0.0397 (9) | 0.0443 (9) | 0.0420 (10) | 0.0051 (7) | −0.0098 (7) | −0.0088 (7) |
C11 | 0.0305 (8) | 0.0465 (9) | 0.0397 (9) | 0.0033 (7) | −0.0026 (7) | −0.0110 (7) |
C12 | 0.0310 (8) | 0.0390 (8) | 0.0403 (9) | 0.0019 (7) | −0.0074 (7) | −0.0152 (7) |
C13 | 0.0308 (8) | 0.0389 (9) | 0.0398 (9) | 0.0013 (7) | −0.0093 (7) | −0.0135 (7) |
C14 | 0.0286 (8) | 0.0483 (10) | 0.0433 (10) | 0.0031 (7) | −0.0092 (7) | −0.0094 (8) |
C15 | 0.0429 (11) | 0.0717 (13) | 0.0524 (12) | −0.0024 (9) | −0.0011 (9) | −0.0005 (10) |
C16 | 0.0535 (11) | 0.0535 (11) | 0.0422 (10) | 0.0043 (8) | −0.0037 (8) | −0.0059 (8) |
O1—C1 | 1.3804 (19) | C6—C7 | 1.428 (2) |
O1—C15 | 1.419 (2) | C6—H6 | 0.9300 |
O2—C2 | 1.3776 (19) | C7—C8 | 1.413 (2) |
O2—C15 | 1.421 (2) | C7—C12 | 1.425 (2) |
O3—C10 | 1.378 (2) | C8—C9 | 1.352 (2) |
O3—C16 | 1.423 (2) | C8—H8 | 0.9300 |
O4—C9 | 1.379 (2) | C9—C10 | 1.400 (2) |
O4—C16 | 1.430 (2) | C10—C11 | 1.349 (2) |
C1—C14 | 1.347 (2) | C11—C12 | 1.423 (2) |
C1—C2 | 1.392 (2) | C11—H11 | 0.9300 |
C2—C3 | 1.358 (2) | C12—C13 | 1.448 (2) |
C3—C4 | 1.419 (2) | C13—C14 | 1.427 (2) |
C3—H3 | 0.9300 | C14—H14 | 0.9300 |
C4—C13 | 1.418 (2) | C15—H15A | 0.9700 |
C4—C5 | 1.425 (2) | C15—H15B | 0.9700 |
C5—C6 | 1.344 (2) | C16—H16A | 0.9700 |
C5—H5 | 0.9300 | C16—H16B | 0.9700 |
C1—O1—C15 | 106.30 (13) | C8—C9—C10 | 121.33 (17) |
C2—O2—C15 | 105.66 (13) | O4—C9—C10 | 109.68 (15) |
C10—O3—C16 | 106.44 (13) | C11—C10—O3 | 128.20 (15) |
C9—O4—C16 | 105.87 (13) | C11—C10—C9 | 122.71 (16) |
C14—C1—O1 | 127.84 (15) | O3—C10—C9 | 109.07 (15) |
C14—C1—C2 | 123.24 (15) | C10—C11—C12 | 118.25 (15) |
O1—C1—C2 | 108.91 (15) | C10—C11—H11 | 120.9 |
C3—C2—O2 | 128.62 (16) | C12—C11—H11 | 120.9 |
C3—C2—C1 | 121.32 (16) | C11—C12—C7 | 118.78 (15) |
O2—C2—C1 | 110.05 (14) | C11—C12—C13 | 122.16 (14) |
C2—C3—C4 | 117.53 (16) | C7—C12—C13 | 119.06 (15) |
C2—C3—H3 | 121.2 | C4—C13—C14 | 118.50 (15) |
C4—C3—H3 | 121.2 | C4—C13—C12 | 119.54 (14) |
C13—C4—C3 | 121.32 (15) | C14—C13—C12 | 121.96 (14) |
C13—C4—C5 | 119.18 (15) | C1—C14—C13 | 118.09 (15) |
C3—C4—C5 | 119.50 (15) | C1—C14—H14 | 121.0 |
C6—C5—C4 | 121.52 (16) | C13—C14—H14 | 121.0 |
C6—C5—H5 | 119.2 | O1—C15—O2 | 109.01 (14) |
C4—C5—H5 | 119.2 | O1—C15—H15A | 109.9 |
C5—C6—C7 | 121.71 (15) | O2—C15—H15A | 109.9 |
C5—C6—H6 | 119.1 | O1—C15—H15B | 109.9 |
C7—C6—H6 | 119.1 | O2—C15—H15B | 109.9 |
C8—C7—C12 | 120.73 (15) | H15A—C15—H15B | 108.3 |
C8—C7—C6 | 120.27 (15) | O3—C16—O4 | 108.43 (14) |
C12—C7—C6 | 118.99 (15) | O3—C16—H16A | 110.0 |
C9—C8—C7 | 118.20 (16) | O4—C16—H16A | 110.0 |
C9—C8—H8 | 120.9 | O3—C16—H16B | 110.0 |
C7—C8—H8 | 120.9 | O4—C16—H16B | 110.0 |
C8—C9—O4 | 128.98 (16) | H16A—C16—H16B | 108.4 |
C15—O1—C1—C14 | −179.56 (17) | C8—C9—C10—O3 | −177.95 (16) |
C15—O1—C1—C2 | 0.33 (19) | O4—C9—C10—O3 | 1.0 (2) |
C15—O2—C2—C3 | 178.81 (18) | O3—C10—C11—C12 | 177.57 (15) |
C15—O2—C2—C1 | −2.50 (19) | C9—C10—C11—C12 | −0.4 (3) |
C14—C1—C2—C3 | 0.1 (3) | C10—C11—C12—C7 | 0.0 (2) |
O1—C1—C2—C3 | −179.80 (14) | C10—C11—C12—C13 | −178.68 (14) |
C14—C1—C2—O2 | −178.70 (15) | C8—C7—C12—C11 | 0.5 (2) |
O1—C1—C2—O2 | 1.40 (19) | C6—C7—C12—C11 | −178.00 (14) |
O2—C2—C3—C4 | 178.62 (15) | C8—C7—C12—C13 | 179.20 (14) |
C1—C2—C3—C4 | 0.1 (2) | C6—C7—C12—C13 | 0.7 (2) |
C2—C3—C4—C13 | −0.2 (2) | C3—C4—C13—C14 | 0.3 (2) |
C2—C3—C4—C5 | −179.74 (14) | C5—C4—C13—C14 | 179.76 (13) |
C13—C4—C5—C6 | 0.8 (2) | C3—C4—C13—C12 | −179.58 (14) |
C3—C4—C5—C6 | −179.66 (16) | C5—C4—C13—C12 | −0.1 (2) |
C4—C5—C6—C7 | −0.8 (3) | C11—C12—C13—C4 | 178.00 (14) |
C5—C6—C7—C8 | −178.48 (16) | C7—C12—C13—C4 | −0.7 (2) |
C5—C6—C7—C12 | 0.0 (2) | C11—C12—C13—C14 | −1.8 (2) |
C12—C7—C8—C9 | −0.5 (3) | C7—C12—C13—C14 | 179.49 (13) |
C6—C7—C8—C9 | 177.93 (16) | O1—C1—C14—C13 | 179.80 (15) |
C7—C8—C9—O4 | −178.66 (16) | C2—C1—C14—C13 | −0.1 (3) |
C7—C8—C9—C10 | 0.1 (3) | C4—C13—C14—C1 | −0.1 (2) |
C16—O4—C9—C8 | −177.63 (18) | C12—C13—C14—C1 | 179.74 (14) |
C16—O4—C9—C10 | 3.49 (19) | C1—O1—C15—O2 | −1.9 (2) |
C16—O3—C10—C11 | 176.67 (17) | C2—O2—C15—O1 | 2.7 (2) |
C16—O3—C10—C9 | −5.13 (19) | C10—O3—C16—O4 | 7.28 (19) |
C8—C9—C10—C11 | 0.4 (3) | C9—O4—C16—O3 | −6.63 (19) |
O4—C9—C10—C11 | 179.36 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O1i | 0.93 | 2.69 | 3.442 (3) | 139 |
Symmetry code: (i) −x+2, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C16H10O4 |
Mr | 266.24 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.862 (2), 7.775 (2), 11.495 (3) |
α, β, γ (°) | 75.084 (3), 77.118 (3), 86.460 (4) |
V (Å3) | 577.7 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.34 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.963, 0.973 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4267, 2126, 1543 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.126, 1.04 |
No. of reflections | 2126 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.27 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O1i | 0.93 | 2.686 | 3.442 (3) | 138.8 |
Symmetry code: (i) −x+2, −y, −z+1. |
Acknowledgements
This work is supported by the Natural Science Foundation of Jiangxi Province (0420040).
References
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Recently, our group (Wang et al., 2007) decribed the crystal structure of 2,3-Dimethoxy-6,7- methylenedioxyphenanthrene [1] (C17H14O4). Here we report the crystal structure of 2,3:6,7-bis(methylenedioxy)phenanthrene, another important intermediate in the synthesis of phenanthroindolizidine and phenanthroquinolizidine alkaloids analogs. In the title molecule, all the non-hydrogen atoms are nearly coplanar, with the mean deviation of 0.0763 Å, The crystal structure is stabilized by weak intermolecular C11—H11···O1 contacts with C···O distance 3.442 (3) Å and π–π stacking interactions between the parallel molecules; the interplanar distance is 3.43 Å (symmetry code: -1 + x, y, z).