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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1372.
Published online 2009 May 23. doi:  10.1107/S1600536809018595
PMCID: PMC2969785

11-(3-Chloro-2-hydroxy­prop­oxy)-2,3,9-trimethoxy­chromeno[3,4-b]chromen-12(6H)-one

Abstract

In the title compound, C22H21ClO8, the rotenoid core is nearly planar (r.m.s. deviation 0.114 Å), with the largest deviations from the least-squares plane being 0.286 (3) and 0.274 (2) Å. An inter­molecular O—H(...)O hydrogen bond links two mol­ecules into a centrosymmetric dimer having an R 2 2(18) ring motif.

Related literature

For a related structure, see: Roengsumran et al. (2003 [triangle]).

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Object name is e-65-o1372-scheme1.jpg

Experimental

Crystal data

  • C22H21ClO8
  • M r = 448.84
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1372-efi1.jpg
  • a = 7.1534 (4) Å
  • b = 11.7904 (6) Å
  • c = 12.7661 (7) Å
  • α = 76.901 (3)°
  • β = 86.991 (3)°
  • γ = 74.455 (3)°
  • V = 1010.30 (9) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.24 mm−1
  • T = 293 K
  • 0.30 × 0.24 × 0.20 mm

Data collection

  • Bruker SMART APEXII diffractometer
  • Absorption correction: none
  • 14308 measured reflections
  • 4517 independent reflections
  • 2879 reflections with I > 2σ(I)
  • R int = 0.027

Refinement

  • R[F 2 > 2σ(F 2)] = 0.080
  • wR(F 2) = 0.268
  • S = 1.05
  • 4517 reflections
  • 272 parameters
  • 7 restraints
  • H-atom parameters constrained
  • Δρmax = 0.82 e Å−3
  • Δρmin = −0.91 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809018595/ng2583sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809018595/ng2583Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors gratefully acknowledge funding from the Thailand Research Fund (TRF) (to NM), and from the Department of Chemistry and the Research Centre for Bioorganic Chemistry of Chulalongkorn University.

supplementary crystallographic information

Comment

6-Deoxyclitoriacetal, extracted from the roots of Stemona Collinsae Craib, showed strong cytotoxic activity against various human carcinoma (Roengsumran et al., 2003). In order to enhance its cytotoxic activities, the title compound was synthesized and its crystal structure was reported herein.

The bond lengths and angles in the molecules (Fig. 1) are within normal ranges and are comparable to a closely related structure (Roengsumran et al., 2003). The rotenoid core is nearly flattened with the largest deviations from the least-squares plane of 0.286 (3) at C14 and -0.274 (2) at O2.

In the crystal structure, interatomic OH···O hydrogen bonds link the molecules into centrosymmetric dimers, forming R22(18) ring motifs, in which they may help in stabilize the crystal structure (Table 1).

Experimental

To the reaction mixture of 3-(4,5-dimethoxy-2-oxiranylmethoxy-phenyl)-3-hydroxy-7-methoxy-2-methyl-5-oxiranylmethoxy-chroman-4-one (20 mg, 0.046 mmol) in 3 ml of aqueous ethyl acetate was added 1M HCl (3 ml). The mixture solution was stirred for 30 min at room temperature. The reaction mixture was evaporated to remove solvent under reduced pressure. The residue was washed with water. Organic layer was extracted with dichloromethane and dried over MgSO4. Solvent was removed under reduced pressure and the crude product was purified by silica gel column chromatography with dichloromethane:ethyl acetate:dichloromethane (2:1:2, v/v) as elutent to give the title compound as yellow crystal (70% yield).

Refinement

All non-H atoms were anisotropically refined. The O8 atom is disordered over two positions with site occupancies of 0.710 (5) and 0.290 (5). Restraints were used (SADI, DFIX and ISOR). The H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å (aromatic), 0.97 Å (CH2), 0.98 Å (CH3) and O—H = 0.82 Å, and Uiso(H) = 1.2Ueq (Caromatic), 1.5Ueq (CCH2), 1.5Ueq (CCH3) and 1.2Ueq (CO), respectively.

Figures

Fig. 1.
The molecular structure of the title compound, with disordered omitted. Displacement ellipsoids are drawn at 50% probability level.
Fig. 2.
Packing diagram of A hydrogen bonded dimer of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C22H21ClO8V = 1010.30 (9) Å3
Mr = 448.84Z = 2
Triclinic, P1F(000) = 468
Hall symbol: -P 1Dx = 1.475 Mg m3
a = 7.1534 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.7904 (6) Åθ = 1.6–27.4°
c = 12.7661 (7) ŵ = 0.24 mm1
α = 76.901 (3)°T = 293 K
β = 86.991 (3)°Prism, colourless
γ = 74.455 (3)°0.30 × 0.24 × 0.20 mm

Data collection

Bruker SMART APEXII diffractometerRint = 0.027
Radiation source: Moθmax = 27.4°, θmin = 1.6°
ω scansh = −8→9
14308 measured reflectionsk = −15→14
4517 independent reflectionsl = −16→16
2879 reflections with I > 2σ(I)

Refinement

Refinement on F27 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.080w = 1/[σ2(Fo2) + (0.1402P)2 + 1.0019P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.268(Δ/σ)max = 0.058
S = 1.05Δρmax = 0.82 e Å3
4517 reflectionsΔρmin = −0.91 e Å3
272 parameters

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<1)
Cl1−0.0091 (2)0.94031 (14)0.19387 (18)0.1035 (7)
O1−0.8374 (4)1.5195 (2)0.1837 (2)0.0440 (6)
O2−0.9242 (4)1.7345 (2)−0.0626 (2)0.0530 (7)
O3−0.6183 (5)1.2837 (2)−0.0085 (2)0.0565 (8)
O4−0.5594 (5)1.5045 (3)−0.3767 (2)0.0589 (8)
O5−0.7253 (5)1.7328 (3)−0.4252 (2)0.0598 (8)
O6−0.7703 (5)1.2142 (3)0.5002 (2)0.0646 (9)
O7−0.5510 (5)1.1103 (2)0.1704 (2)0.0566 (8)
C21−0.3641 (7)0.9229 (3)0.1446 (4)0.063
H21−0.45430.93730.08490.075*0.710 (5)
H21'−0.30230.8390.18560.075*0.290 (5)
O8−0.2980 (6)0.7966 (4)0.1808 (4)0.064*0.710 (5)
H8−0.31670.76360.13370.096*0.710 (5)
O8'−0.5162 (14)0.9032 (9)0.0844 (8)0.062*0.290 (5)
H8'−0.49750.92350.01980.093*0.290 (5)
C1−0.8078 (6)1.3721 (4)0.3395 (3)0.0460 (9)
H1−0.86471.43250.3760.055*
C2−0.7492 (6)1.2532 (4)0.3927 (3)0.0475 (9)
C3−0.6659 (6)1.1635 (4)0.3367 (3)0.0493 (9)
H3−0.62881.08330.37370.059*
C4−0.6377 (6)1.1925 (3)0.2272 (3)0.0440 (9)
C5−0.6986 (5)1.3151 (3)0.1675 (3)0.0368 (8)
C6−0.6830 (5)1.3541 (3)0.0510 (3)0.0384 (8)
C7−0.7431 (5)1.4857 (3)0.0087 (3)0.0334 (7)
C8−0.7322 (5)1.5470 (3)−0.1049 (3)0.0346 (7)
C9−0.6415 (5)1.4904 (3)−0.1873 (3)0.0383 (8)
H9−0.57961.4084−0.17040.046*
C10−0.6422 (6)1.5539 (3)−0.2928 (3)0.0418 (8)
C11−0.7324 (6)1.6778 (3)−0.3193 (3)0.0427 (8)
C12−0.8198 (5)1.7351 (3)−0.2397 (3)0.0437 (9)
H12−0.87861.8176−0.25650.052*
C13−0.8204 (5)1.6705 (3)−0.1351 (3)0.0392 (8)
C14−0.8613 (7)1.6920 (3)0.0448 (3)0.0506 (10)
H14A−0.9631.72570.0910.061*
H14B−0.74851.71950.05430.061*
C15−0.8106 (5)1.5572 (3)0.0779 (3)0.0386 (8)
C16−0.7789 (5)1.3987 (3)0.2294 (3)0.0389 (8)
C17−0.4440 (7)1.3837 (4)−0.3532 (3)0.0577 (11)
H17A−0.39511.3606−0.41890.087*
H17B−0.52121.3315−0.31720.087*
H17C−0.33731.3769−0.30750.087*
C18−0.8071 (8)1.8595 (4)−0.4555 (4)0.0658 (13)
H18A−0.79161.8867−0.53150.099*
H18B−0.74231.8994−0.41720.099*
H18C−0.94271.878−0.43840.099*
C19−0.8712 (9)1.3025 (5)0.5581 (4)0.0774 (15)
H19A−0.87781.26460.63260.116*
H19B−1.00021.33840.52930.116*
H19C−0.80341.36390.55120.116*
C20−0.4775 (7)0.9901 (3)0.2280 (4)0.0574 (11)
H20A−0.58230.95530.25790.069*
H20B−0.39260.98670.28610.069*
C22−0.1968 (9)0.9713 (4)0.0981 (5)0.0854 (19)
H22A−0.24271.05790.07140.102*
H22B−0.14530.93570.03770.102*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0831 (11)0.0732 (10)0.1646 (18)−0.0261 (8)0.0238 (10)−0.0457 (11)
O10.0532 (15)0.0392 (14)0.0383 (14)−0.0067 (11)0.0102 (11)−0.0147 (11)
O20.0622 (18)0.0374 (14)0.0484 (16)0.0066 (12)0.0055 (13)−0.0121 (12)
O30.087 (2)0.0332 (14)0.0452 (16)−0.0064 (13)0.0152 (14)−0.0156 (12)
O40.093 (2)0.0470 (16)0.0332 (14)−0.0100 (15)0.0080 (13)−0.0128 (12)
O50.084 (2)0.0487 (16)0.0385 (15)−0.0118 (15)−0.0030 (14)−0.0003 (12)
O60.078 (2)0.072 (2)0.0392 (16)−0.0197 (16)0.0067 (14)−0.0040 (15)
O70.078 (2)0.0320 (14)0.0488 (16)−0.0001 (13)0.0084 (14)−0.0057 (12)
C210.0850.0330.0630−0.011−0.011
C10.050 (2)0.053 (2)0.040 (2)−0.0170 (17)0.0080 (16)−0.0177 (17)
C20.048 (2)0.057 (2)0.040 (2)−0.0202 (18)0.0058 (16)−0.0085 (18)
C30.048 (2)0.045 (2)0.051 (2)−0.0122 (17)0.0055 (17)−0.0033 (18)
C40.046 (2)0.0394 (19)0.044 (2)−0.0087 (15)0.0068 (15)−0.0075 (16)
C50.0376 (18)0.0336 (17)0.0400 (19)−0.0086 (13)0.0051 (14)−0.0117 (14)
C60.0443 (19)0.0310 (17)0.0410 (19)−0.0091 (14)0.0063 (15)−0.0124 (15)
C70.0331 (17)0.0309 (16)0.0372 (17)−0.0072 (12)0.0040 (13)−0.0121 (14)
C80.0335 (17)0.0331 (17)0.0386 (18)−0.0091 (13)0.0018 (13)−0.0107 (14)
C90.047 (2)0.0303 (16)0.0366 (18)−0.0076 (14)0.0031 (14)−0.0095 (14)
C100.049 (2)0.0412 (19)0.0370 (19)−0.0118 (15)0.0010 (15)−0.0116 (15)
C110.049 (2)0.0403 (19)0.0364 (19)−0.0126 (16)−0.0054 (15)−0.0024 (15)
C120.046 (2)0.0349 (18)0.046 (2)−0.0046 (15)−0.0035 (16)−0.0057 (16)
C130.0401 (19)0.0341 (18)0.0427 (19)−0.0053 (14)0.0017 (14)−0.0126 (15)
C140.062 (3)0.0362 (19)0.049 (2)−0.0019 (17)0.0034 (18)−0.0157 (17)
C150.0379 (18)0.0354 (18)0.0417 (19)−0.0064 (14)0.0038 (14)−0.0114 (15)
C160.0381 (18)0.0401 (19)0.0404 (19)−0.0105 (14)0.0043 (14)−0.0135 (15)
C170.079 (3)0.051 (2)0.044 (2)−0.013 (2)0.015 (2)−0.0207 (19)
C180.086 (3)0.050 (2)0.052 (3)−0.013 (2)−0.007 (2)0.006 (2)
C190.102 (4)0.093 (4)0.038 (2)−0.025 (3)0.011 (2)−0.018 (2)
C200.065 (3)0.039 (2)0.061 (3)−0.0100 (18)0.003 (2)−0.0015 (19)
C220.117 (5)0.037 (2)0.079 (4)0.004 (2)0.039 (3)−0.007 (2)

Geometric parameters (Å, °)

Cl1—C221.772 (7)C5—C161.389 (5)
O1—C151.343 (4)C5—C61.462 (5)
O1—C161.369 (4)C6—C71.473 (5)
O2—C131.386 (4)C7—C151.342 (5)
O2—C141.402 (5)C7—C81.474 (5)
O3—C61.233 (4)C8—C131.394 (5)
O4—C101.367 (5)C8—C91.410 (5)
O4—C171.415 (5)C9—C101.383 (5)
O5—C111.366 (4)C9—H90.93
O5—C181.420 (5)C10—C111.400 (5)
O6—C21.359 (5)C11—C121.379 (6)
O6—C191.428 (6)C12—C131.379 (5)
O7—C41.342 (5)C12—H120.93
O7—C201.412 (5)C14—C151.496 (5)
C21—O81.410 (5)C14—H14A0.97
C21—O8'1.460 (7)C14—H14B0.97
C21—C221.500 (8)C17—H17A0.96
C21—C201.538 (6)C17—H17B0.96
C21—H210.98C17—H17C0.96
C21—H21'1.0012C18—H18A0.96
O8—H21'0.5101C18—H18B0.96
O8—H80.82C18—H18C0.96
O8'—H8'0.82C19—H19A0.96
C1—C21.373 (6)C19—H19B0.96
C1—C161.386 (5)C19—H19C0.96
C1—H10.93C20—H20A0.97
C2—C31.394 (6)C20—H20B0.97
C3—C41.379 (6)C22—H22A0.97
C3—H30.93C22—H22B0.97
C4—C51.435 (5)
C15—O1—C16119.0 (3)O4—C10—C11115.4 (3)
C13—O2—C14115.8 (3)C9—C10—C11119.8 (3)
C10—O4—C17118.1 (3)O5—C11—C12124.9 (3)
C11—O5—C18117.9 (3)O5—C11—C10115.7 (3)
C2—O6—C19117.0 (4)C12—C11—C10119.4 (3)
C4—O7—C20117.3 (3)C13—C12—C11120.2 (3)
O8—C21—O8'88.0 (5)C13—C12—H12119.9
O8—C21—C22109.0 (4)C11—C12—H12119.9
O8'—C21—C22126.5 (6)C12—C13—O2115.7 (3)
O8—C21—C20115.0 (4)C12—C13—C8122.5 (3)
O8'—C21—C20103.5 (5)O2—C13—C8121.7 (3)
C22—C21—C20112.9 (4)O2—C14—C15112.2 (3)
O8—C21—H21106.4O2—C14—H14A109.2
O8'—C21—H2122.8C15—C14—H14A109.2
C22—C21—H21106.4O2—C14—H14B109.2
C20—C21—H21106.4C15—C14—H14B109.2
O8—C21—H21'14.8H14A—C14—H14B107.9
O8'—C21—H21'101.7O1—C15—C7125.7 (3)
C22—C21—H21'104.5O1—C15—C14111.6 (3)
C20—C21—H21'105.8C7—C15—C14122.7 (3)
H21—C21—H21'121O1—C16—C5121.0 (3)
C21—O8—H21'30O1—C16—C1113.4 (3)
C21—O8—H8109.5C5—C16—C1125.6 (3)
H21'—O8—H8138.7O4—C17—H17A109.5
C21—O8'—H8'109.5O4—C17—H17B109.5
C2—C1—C16117.5 (4)H17A—C17—H17B109.5
C2—C1—H1121.2O4—C17—H17C109.5
C16—C1—H1121.2H17A—C17—H17C109.5
O6—C2—C1123.8 (4)H17B—C17—H17C109.5
O6—C2—C3115.7 (4)O5—C18—H18A109.5
C1—C2—C3120.6 (4)O5—C18—H18B109.5
C4—C3—C2120.8 (4)H18A—C18—H18B109.5
C4—C3—H3119.6O5—C18—H18C109.5
C2—C3—H3119.6H18A—C18—H18C109.5
O7—C4—C3123.1 (3)H18B—C18—H18C109.5
O7—C4—C5116.0 (3)O6—C19—H19A109.5
C3—C4—C5120.9 (3)O6—C19—H19B109.5
C16—C5—C4114.6 (3)H19A—C19—H19B109.5
C16—C5—C6120.4 (3)O6—C19—H19C109.5
C4—C5—C6125.0 (3)H19A—C19—H19C109.5
O3—C6—C5123.4 (3)H19B—C19—H19C109.5
O3—C6—C7121.5 (3)O7—C20—C21104.9 (3)
C5—C6—C7115.1 (3)O7—C20—H20A110.8
C15—C7—C8116.3 (3)C21—C20—H20A110.8
C15—C7—C6118.4 (3)O7—C20—H20B110.8
C8—C7—C6125.2 (3)C21—C20—H20B110.8
C13—C8—C9116.4 (3)H20A—C20—H20B108.8
C13—C8—C7118.4 (3)C21—C22—Cl1112.2 (4)
C9—C8—C7125.2 (3)C21—C22—H22A109.2
C10—C9—C8121.7 (3)Cl1—C22—H22A109.2
C10—C9—H9119.1C21—C22—H22B109.2
C8—C9—H9119.1Cl1—C22—H22B109.2
O4—C10—C9124.7 (3)H22A—C22—H22B107.9

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O8'—H8'···O8'i0.822.22.81 (2)132
O8'—H8'···O7i0.822.543.297 (10)154
O8—H8···O3i0.821.922.735 (6)169

Symmetry codes: (i) −x−1, −y+2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2583).

References

  • Bruker (2005). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Roengsumran, S., Khorphueng, P., Chaichit, N., Jaiboon-Muangsin, N. & Petsom, A. (2003). Z. Kristallogr. New Cryst. Struct.218, 105–106.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2009). publCIF In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography