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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1415.
Published online 2008 July 5. doi:  10.1107/S1600536808019454
PMCID: PMC2962049

6-Bromo-3-hydr­oxy-4-oxo-2-phenyl-4H-chromene-8-carboxylic acid dimethyl­formamide disolvate

Abstract

In the title compound, C16H9BrO5·2C3H7NO, the chromene ring system is essentially planar. The two dimethyl­formamide solvent mol­ecules are linked by inter­molecular O—H(...)O hydrogen bonds to the 6-bromo-3-hydr­oxy-4-oxo-2-phenyl-4H-chromene-8-carboxylic acid molecules.

Related literature

For related literature, see: Gills et al. (1980 [triangle]); Liu et al. (2007 [triangle]); Jin & Xiao (2005 [triangle]); Kagechika et al. (1989 [triangle]); Valenti et al. (1998 [triangle]); Walenta et al. (1991 [triangle]); Zwaagstra et al. (1996 [triangle], 1998a [triangle],b [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1415-scheme1.jpg

Experimental

Crystal data

  • C16H9BrO5·2C3H7NO
  • M r = 507.33
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1415-efi1.jpg
  • a = 10.489 (2) Å
  • b = 11.470 (2) Å
  • c = 18.803 (4) Å
  • β = 92.127 (3)°
  • V = 2260.6 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.86 mm−1
  • T = 294 (2) K
  • 0.49 × 0.38 × 0.17 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.462, T max = 0.742
  • 14295 measured reflections
  • 4203 independent reflections
  • 2889 reflections with I > 2σ(I)
  • R int = 0.028

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.098
  • S = 0.99
  • 4203 reflections
  • 294 parameters
  • H-atom parameters constrained
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.34 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1998 [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: ORTEPIII (Burnett & Johnson,1996 [triangle]); ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808019454/dn2358sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808019454/dn2358Isup2.hkl

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

Acknowledgments

This work is supported by the National Natural Science Foundation of China (20662007) and the Key Laboratory Open Foundation of Food Science of the Ministry of Education, Nanchang University (NCU200407).

supplementary crystallographic information

Comment

Flavonoids are widely present in nature, which have potential biological activity such as antiviral (Zwaagstra et al., 1996; Zwaagstra et al., 1998a), anticancer (Valenti et al., 1998), treating leukemia (Kagechika et al., 1989), antihypertensive, antimicrobial (Gills et al., 1980; Walenta et al., 1991) et al. Due to the varieties of its biological activity, the structure-activity relationships study of flavonoids carboxylic acids has been the hot spot all along. In a continuation of our recent studies of flavonoids carboxylic acids (Liu et al., 2007), we report here the title compound, C16H9BrO5—C6H14N2O2, (I).

In compound (I), the chromene molecule is roughly planar, with a mean deviation of 0.0521 Å. The dihedral angle between the chromene ring and the phenyl ring is 7.5 (2)°. Two O—H···O hydrogen bonds (Table 1, Fig. 1) involving the H atoms of hydroxyl group and carboxylic acid group connect the dimethylformamide molecules and 6-bromo-3-hydroxy-4-oxo-2-phenyl-4H-chromene-8-carboxylic acid.

Experimental

The title compound was synthesized by the ring closure of 5'-bromo-3'-carboxy-2'-hydroxychalcone under the existence of a certain oxidant, according to the route published by Zwaagstra et al. (Zwaagstra et al., 1998b). Single crystals of (I) suitable for X-ray diffraction analysis were obtained from a solution in N,N-dimethylformamide.

Refinement

All H atoms attached to C atoms and O atom were fixed geometrically and treated as riding with C—H = 0.96 Å (methyl) or 0.93 Å (aromatic) and O—H = 0.82 Å with Uiso(H) = 1.2Ueq(Caromatic) or Uiso(H) = 1.5Ueq(Cmethyl and O).

Figures

Fig. 1.
: The molecular structure of (I), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are represented as small spheres of arbitrary radii. The hydrogen bonds are shown as dashed lines.

Crystal data

C16H9BrO5·2C3H7NOF000 = 1040
Mr = 507.33Dx = 1.491 Mg m3
Monoclinic, P2(1)/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3645 reflections
a = 10.489 (2) Åθ = 2.6–23.5º
b = 11.470 (2) ŵ = 1.86 mm1
c = 18.803 (4) ÅT = 294 (2) K
β = 92.127 (3)ºBlock, yellow
V = 2260.6 (8) Å30.49 × 0.38 × 0.17 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer4203 independent reflections
Radiation source: fine-focus sealed tube2889 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.028
T = 294(2) Kθmax = 25.5º
[var phi] and ω scansθmin = 2.6º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −12→11
Tmin = 0.462, Tmax = 0.742k = −13→13
14295 measured reflectionsl = −22→22

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.098  w = 1/[σ2(Fo2) + (0.0482P)2 + 0.6824P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.017
4203 reflectionsΔρmax = 0.32 e Å3
294 parametersΔρmin = −0.34 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)

xyzUiso*/Ueq
Br10.06013 (3)0.88028 (2)0.582768 (19)0.07113 (15)
O1−0.0368 (2)0.44074 (18)0.65009 (12)0.0911 (8)
O20.06856 (17)0.31912 (16)0.58290 (9)0.0577 (5)
H2A0.02790.27040.60460.087*
O30.24560 (16)0.40314 (13)0.50359 (9)0.0460 (4)
O40.41242 (18)0.68075 (16)0.41187 (10)0.0652 (6)
O50.49923 (18)0.46087 (15)0.38343 (11)0.0610 (5)
H50.53030.52370.37270.091*
C10.1082 (2)0.5216 (2)0.57023 (13)0.0439 (6)
C20.0684 (2)0.6327 (2)0.58763 (14)0.0517 (7)
H20.00410.64160.61990.062*
C30.1222 (2)0.7312 (2)0.55796 (14)0.0495 (7)
C40.2183 (2)0.7207 (2)0.51073 (14)0.0485 (6)
H40.25440.78690.49120.058*
C50.2615 (2)0.6101 (2)0.49221 (13)0.0422 (6)
C60.2067 (2)0.5112 (2)0.52147 (12)0.0411 (6)
C70.3634 (2)0.5972 (2)0.44191 (14)0.0456 (6)
C80.4030 (2)0.4787 (2)0.42805 (13)0.0443 (6)
C90.3421 (2)0.3864 (2)0.45729 (13)0.0429 (6)
C100.0406 (3)0.4222 (2)0.60528 (14)0.0518 (7)
C110.3633 (2)0.2608 (2)0.44578 (13)0.0442 (6)
C120.4628 (3)0.2186 (3)0.40674 (19)0.0821 (11)
H120.51880.27080.38650.099*
C130.4800 (4)0.1012 (3)0.3976 (2)0.0944 (13)
H130.54820.07520.37160.113*
C140.3998 (3)0.0217 (2)0.42550 (17)0.0686 (9)
H140.4114−0.05780.41840.082*
C150.3021 (3)0.0619 (2)0.46419 (18)0.0736 (9)
H150.24640.00890.48390.088*
C160.2840 (3)0.1793 (2)0.47476 (16)0.0629 (8)
H160.21690.20410.50200.075*
N1−0.2166 (3)0.1136 (2)0.71663 (13)0.0631 (7)
O6−0.0563 (2)0.15290 (18)0.64329 (11)0.0722 (6)
C17−0.1516 (3)0.1828 (3)0.67549 (16)0.0626 (8)
H17−0.17920.25950.67030.075*
C18−0.3276 (4)0.1567 (3)0.7524 (2)0.0983 (13)
H18A−0.30720.16490.80240.147*
H18B−0.39680.10260.74560.147*
H18C−0.35210.23110.73290.147*
C19−0.1781 (3)−0.0070 (3)0.72818 (18)0.0840 (10)
H19A−0.2251−0.05650.69550.126*
H19B−0.1953−0.02940.77610.126*
H19C−0.0885−0.01470.72060.126*
N20.7254 (2)0.78411 (18)0.28823 (12)0.0554 (6)
O70.6435 (2)0.60874 (17)0.31631 (12)0.0773 (7)
C200.6539 (3)0.7141 (3)0.32545 (16)0.0642 (8)
H200.60760.74730.36150.077*
C210.7365 (4)0.9061 (3)0.3036 (3)0.1108 (15)
H21A0.69090.92390.34560.166*
H21B0.70120.95030.26420.166*
H21C0.82480.92600.31130.166*
C220.8037 (3)0.7385 (3)0.23293 (16)0.0746 (9)
H22A0.88530.71600.25320.112*
H22B0.81510.79740.19750.112*
H22C0.76260.67180.21140.112*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0723 (2)0.04462 (18)0.0983 (3)0.00670 (14)0.02689 (18)−0.00929 (15)
O10.1120 (19)0.0564 (13)0.1106 (18)−0.0065 (12)0.0794 (16)−0.0021 (12)
O20.0641 (13)0.0440 (11)0.0672 (12)−0.0095 (9)0.0321 (10)0.0013 (9)
O30.0491 (10)0.0358 (9)0.0546 (10)−0.0028 (7)0.0219 (8)0.0004 (7)
O40.0696 (14)0.0428 (11)0.0860 (14)−0.0029 (9)0.0389 (11)0.0106 (10)
O50.0621 (13)0.0421 (10)0.0814 (13)−0.0017 (9)0.0392 (10)0.0058 (9)
C10.0440 (15)0.0429 (14)0.0454 (14)−0.0045 (11)0.0098 (12)0.0000 (11)
C20.0483 (16)0.0522 (16)0.0557 (16)−0.0010 (12)0.0179 (13)−0.0043 (12)
C30.0501 (16)0.0402 (14)0.0587 (17)0.0007 (12)0.0073 (13)−0.0050 (12)
C40.0486 (16)0.0375 (13)0.0600 (17)−0.0043 (11)0.0085 (13)0.0032 (12)
C50.0411 (14)0.0389 (13)0.0472 (14)−0.0012 (11)0.0078 (11)0.0025 (11)
C60.0411 (14)0.0372 (13)0.0455 (14)−0.0011 (11)0.0080 (11)−0.0015 (11)
C70.0425 (15)0.0412 (14)0.0540 (15)−0.0033 (11)0.0125 (12)0.0060 (11)
C80.0413 (15)0.0429 (14)0.0494 (14)−0.0025 (11)0.0131 (12)0.0040 (11)
C90.0401 (14)0.0432 (13)0.0460 (14)−0.0022 (11)0.0116 (11)0.0022 (11)
C100.0528 (17)0.0501 (15)0.0537 (16)−0.0041 (13)0.0197 (14)−0.0009 (12)
C110.0448 (15)0.0383 (13)0.0500 (15)−0.0009 (11)0.0102 (12)−0.0001 (11)
C120.083 (2)0.0446 (16)0.123 (3)−0.0012 (15)0.061 (2)0.0002 (17)
C130.099 (3)0.0519 (19)0.137 (3)0.0085 (18)0.070 (3)−0.0067 (19)
C140.079 (2)0.0396 (16)0.089 (2)0.0024 (15)0.0210 (18)−0.0071 (15)
C150.085 (2)0.0397 (15)0.099 (2)−0.0087 (16)0.0338 (19)0.0043 (16)
C160.069 (2)0.0440 (15)0.078 (2)−0.0023 (14)0.0344 (16)−0.0023 (14)
N10.0694 (17)0.0582 (15)0.0630 (15)−0.0122 (12)0.0213 (13)0.0075 (11)
O60.0710 (15)0.0588 (12)0.0889 (15)−0.0066 (10)0.0320 (12)0.0131 (11)
C170.064 (2)0.0532 (17)0.072 (2)−0.0080 (15)0.0209 (16)0.0106 (15)
C180.096 (3)0.088 (3)0.114 (3)−0.014 (2)0.057 (2)0.004 (2)
C190.104 (3)0.064 (2)0.084 (2)−0.0043 (19)0.016 (2)0.0247 (18)
N20.0544 (14)0.0404 (12)0.0727 (15)−0.0045 (10)0.0200 (12)0.0015 (11)
O70.0906 (17)0.0485 (13)0.0959 (16)−0.0178 (10)0.0453 (13)−0.0037 (10)
C200.065 (2)0.0550 (18)0.075 (2)−0.0054 (15)0.0276 (16)−0.0033 (15)
C210.114 (3)0.0420 (18)0.180 (4)−0.0070 (19)0.056 (3)−0.007 (2)
C220.087 (2)0.072 (2)0.067 (2)−0.0156 (17)0.0320 (18)−0.0041 (16)

Geometric parameters (Å, °)

Br1—C31.894 (2)C14—C151.359 (4)
O1—C101.210 (3)C14—H140.9300
O2—C101.293 (3)C15—C161.376 (4)
O2—H2A0.8200C15—H150.9300
O3—C61.351 (3)C16—H160.9300
O3—C91.372 (3)N1—C171.316 (3)
O4—C71.235 (3)N1—C181.453 (4)
O5—C81.352 (3)N1—C191.455 (4)
O5—H50.8200O6—C171.236 (3)
C1—C21.384 (3)C17—H170.9300
C1—C61.412 (3)C18—H18A0.9600
C1—C101.507 (3)C18—H18B0.9600
C2—C31.389 (4)C18—H18C0.9600
C2—H20.9300C19—H19A0.9600
C3—C41.373 (3)C19—H19B0.9600
C4—C51.396 (3)C19—H19C0.9600
C4—H40.9300N2—C201.318 (3)
C5—C61.394 (3)N2—C211.433 (4)
C5—C71.460 (3)N2—C221.447 (3)
C7—C81.447 (3)O7—C201.225 (3)
C8—C91.363 (3)C20—H200.9300
C9—C111.475 (3)C21—H21A0.9600
C11—C161.377 (3)C21—H21B0.9600
C11—C121.386 (4)C21—H21C0.9600
C12—C131.371 (4)C22—H22A0.9600
C12—H120.9300C22—H22B0.9600
C13—C141.359 (4)C22—H22C0.9600
C13—H130.9300
C10—O2—H2A109.5C13—C14—H14121.0
C6—O3—C9121.48 (18)C14—C15—C16121.4 (3)
C8—O5—H5109.5C14—C15—H15119.3
C2—C1—C6117.8 (2)C16—C15—H15119.3
C2—C1—C10116.2 (2)C15—C16—C11121.2 (3)
C6—C1—C10126.0 (2)C15—C16—H16119.4
C1—C2—C3121.6 (2)C11—C16—H16119.4
C1—C2—H2119.2C17—N1—C18120.6 (3)
C3—C2—H2119.2C17—N1—C19120.9 (3)
C4—C3—C2120.5 (2)C18—N1—C19118.5 (3)
C4—C3—Br1120.38 (19)O6—C17—N1124.5 (3)
C2—C3—Br1119.14 (19)O6—C17—H17117.7
C3—C4—C5119.6 (2)N1—C17—H17117.7
C3—C4—H4120.2N1—C18—H18A109.5
C5—C4—H4120.2N1—C18—H18B109.5
C6—C5—C4119.9 (2)H18A—C18—H18B109.5
C6—C5—C7119.7 (2)N1—C18—H18C109.5
C4—C5—C7120.4 (2)H18A—C18—H18C109.5
O3—C6—C5121.0 (2)H18B—C18—H18C109.5
O3—C6—C1118.3 (2)N1—C19—H19A109.5
C5—C6—C1120.6 (2)N1—C19—H19B109.5
O4—C7—C8121.3 (2)H19A—C19—H19B109.5
O4—C7—C5123.0 (2)N1—C19—H19C109.5
C8—C7—C5115.7 (2)H19A—C19—H19C109.5
O5—C8—C9120.3 (2)H19B—C19—H19C109.5
O5—C8—C7118.7 (2)C20—N2—C21122.1 (3)
C9—C8—C7120.9 (2)C20—N2—C22120.7 (2)
C8—C9—O3121.0 (2)C21—N2—C22117.0 (2)
C8—C9—C11128.6 (2)O7—C20—N2125.2 (3)
O3—C9—C11110.38 (19)O7—C20—H20117.4
O1—C10—O2123.6 (2)N2—C20—H20117.4
O1—C10—C1120.7 (2)N2—C21—H21A109.5
O2—C10—C1115.7 (2)N2—C21—H21B109.5
C16—C11—C12116.8 (2)H21A—C21—H21B109.5
C16—C11—C9120.6 (2)N2—C21—H21C109.5
C12—C11—C9122.7 (2)H21A—C21—H21C109.5
C13—C12—C11121.0 (3)H21B—C21—H21C109.5
C13—C12—H12119.5N2—C22—H22A109.5
C11—C12—H12119.5N2—C22—H22B109.5
C14—C13—C12121.6 (3)H22A—C22—H22B109.5
C14—C13—H13119.2N2—C22—H22C109.5
C12—C13—H13119.2H22A—C22—H22C109.5
C15—C14—C13118.0 (3)H22B—C22—H22C109.5
C15—C14—H14121.0

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2A···O60.821.782.598 (2)173
O5—H5···O70.821.892.627 (2)149
O5—H5···O40.822.322.741 (3)113

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DN2358).

References

  • Bruker (1998). SAINT and SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Gills, P. M., Haemers, A. & Bollaert, W. (1980). Eur. J. Med. Chem. Chim. Ther.15, 185–190.
  • Jin, L.-F. & Xiao, F.-P. (2005). Acta Cryst. E61, o1198–o1199.
  • Kagechika, H., Kawachi, E., Hashimoto, Y. & Shudo, K. (1989). J. Med. Chem 32, 834–840. [PubMed]
  • Liu, C.-B., Chen, Y.-H., Zhou, X.-Y., Ding, L. & Wen, H.-L. (2007). Acta Cryst. E63, o90–o91.
  • Sheldrick, G. M. (1996). SADABS, University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Valenti, P., Bisi, A., Rampa, A., Gobbi, S., Belluti, F., Da Re, P., Cima, L. & Carrara, M. (1998). Anti Cancer Drug Des 13, 881–892. [PubMed]
  • Walenta, R., Muller-Peddinghaus, R., Ban, I., Wurl, M. & Preuschoff, U. (1991). US Patent 5 013 852.
  • Zwaagstra, M. E., Korthouwer, R. E. M., Timmerman, H. & Zhang, M.-Q. (1998a). Eur J. Med. Chem 33, 95–102.
  • Zwaagstra, M. E., Timmerman, H., Abdoelgafoe, R. S. & Zhang, M.-Q. (1996). Eur J. Med. Chem.31, 861–874.
  • Zwaagstra, M. E., Zhang, M., Timmermann, H., Tamura, M. & Wada, Y. (1998b). European Patent 8 345 10.

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