PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 May 1; 64(Pt 5): o857.
Published online 2008 April 16. doi:  10.1107/S1600536808009732
PMCID: PMC2961157

3-Methyl-4-oxo-2-phenyl-4H-chromene-8-carboxylic acid

Abstract

In the title compound, C17H12O4, the chromene unit is approximately planar, the maximum deviation from the mean plane being 0.0166 Å. The attached phenyl ring makes a dihedral angle of 53.2 (1)° with the fused ring system. The packing of the mol­ecules in the crystal structure is governed by C—H(...)O and O—H(...)O hydrogen-bonding inter­actions.

Related literature

For related literature, see: Uneyama et al. (1985 [triangle]); Ghoneim et al. (2007 [triangle]); Da Re (1960 [triangle], 1968 [triangle]); Sianesi (1972 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o857-scheme1.jpg

Experimental

Crystal data

  • C17H12O4
  • M r = 280.27
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o857-efi1.jpg
  • a = 7.2760 (8) Å
  • b = 9.6551 (10) Å
  • c = 11.3095 (12) Å
  • α = 65.965 (2)°
  • β = 79.748 (2)°
  • γ = 68.286 (2)°
  • V = 673.78 (12) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 298 (2) K
  • 0.35 × 0.27 × 0.18 mm

Data collection

  • Bruker APEX area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2002 [triangle]) T min = 0.969, T max = 0.989
  • 3569 measured reflections
  • 2354 independent reflections
  • 2086 reflections with I > 2σ(I)
  • R int = 0.015

Refinement

  • R[F 2 > 2σ(F 2)] = 0.058
  • wR(F 2) = 0.144
  • S = 1.10
  • 2354 reflections
  • 192 parameters
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [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: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808009732/at2554sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808009732/at2554Isup2.hkl

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

Acknowledgments

The authors thank the Materia Medica Institute of Taizhou University for supporting this work.

supplementary crystallographic information

Comment

In the title compound, 3-Methyl-4-oxo-2-phenyl-4H-chromene-8-carboxylic acid, is the key intermediate of flavoxate hydrochloride (Uneyama et al., 1985). The flavoxate hydrochloride is a smooth muscle antispasmodic, especially on the urogenital tract (Ghoneim et al., 2007). We report here the crystal structure of the title compound.

The 1-benzopyran unit is approximately planar, with a maximum deviation from the mean plane being 0.0166 A. The attached phenyl ring makes a dihedral angle of 53.2 (1)° with the fused ring system.The packing of the molecules in the crystal structure is mainly governed by C—H—Oπ hydrogen bonding interactions.

Experimental

To a solution of 8-formyl-3-methyl-2-phenyl-4H-chromen-4-one (4 g, 15 mmol) in 2-butanone heated to 363–368 K, 31% of H2O2 (50 ml) was added four times at every 10 h intervals. After being stirred for 10 h, H2O2 was quenched with NaHSO3. The reaction mixture was acidified with 10% HCl and extracted with AcOEt. The extracts were concentrated in vacuo. The residue was dissolved in sat. NaHCO3 and extracted with AcOEt. The aqueous layer was acidified with 10% HCl and extracted with AcOEt. The extracts were dried with Na2SO4 and concentrated in vacuo. The residue was recrystallized from ethanol to give the title compound in a yield of 81%. m.p. 500.6–501.2 K. Crystals suitable for single-crystal X-ray diffraction were obtained by recrystallization from a mixed solvent of ethanol and dichloromethane (2:1 v/v) at room temperature.

Refinement

All H atoms were placed geometrically at the distances of 0.93–0.96 Å for C—H and 0.826 Å for O—H and included in the refinement in riding motion approximation with Uiso(H) = 1.2 or 1.5Ueq of the carrier atom.

Figures

Fig. 1.
A view of the title compound, showing 30% probability ellipsoids for the non-hydrogen atoms and the atom-labelling scheme.

Crystal data

C17H12O4Z = 2
Mr = 280.27F000 = 292
Triclinic, P1Dx = 1.381 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 7.2760 (8) ÅCell parameters from 1477 reflections
b = 9.6551 (10) Åθ = 2.5–27.7º
c = 11.3095 (12) ŵ = 0.10 mm1
α = 65.965 (2)ºT = 298 (2) K
β = 79.748 (2)ºBlock, colourless
γ = 68.286 (2)º0.35 × 0.27 × 0.18 mm
V = 673.78 (12) Å3

Data collection

Bruker APEX area-detector diffractometer2354 independent reflections
Radiation source: fine-focus sealed tube2086 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.015
T = 298(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 2.0º
Absorption correction: multi-scan(SADABS; Bruker, 2002)h = −8→8
Tmin = 0.969, Tmax = 0.989k = −11→11
3569 measured reflectionsl = −13→12

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.144  w = 1/[σ2(Fo2) + (0.0631P)2 + 0.2396P] where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.004
2354 reflectionsΔρmax = 0.20 e Å3
192 parametersΔρmin = −0.25 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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.
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
O10.2307 (3)0.48247 (18)0.52007 (15)0.0620 (5)
H10.25210.56810.48420.093*
O20.3009 (3)0.4730 (2)0.32507 (15)0.0690 (6)
O30.2390 (2)0.22602 (15)0.30232 (13)0.0398 (4)
O40.2514 (3)−0.23584 (17)0.47596 (17)0.0595 (5)
C10.2644 (3)0.4115 (2)0.43715 (19)0.0380 (5)
C20.2526 (3)0.2451 (2)0.50288 (18)0.0351 (5)
C30.2552 (3)0.1725 (2)0.63616 (19)0.0409 (5)
H30.25580.23070.68440.049*
C40.2568 (3)0.0150 (2)0.7004 (2)0.0451 (5)
H40.2597−0.03110.79030.054*
C50.2543 (3)−0.0720 (2)0.6318 (2)0.0432 (5)
H50.2562−0.17760.67500.052*
C60.2490 (3)−0.0033 (2)0.49658 (19)0.0368 (5)
C70.2471 (3)0.1545 (2)0.43312 (18)0.0337 (4)
C80.2394 (3)0.1420 (2)0.2298 (2)0.0396 (5)
C90.2489 (3)−0.0139 (2)0.2816 (2)0.0443 (5)
C100.2678 (4)−0.1097 (3)0.2009 (3)0.0621 (7)
H10A0.1433−0.12340.20210.093*
H10B0.3672−0.21310.23570.093*
H10C0.3050−0.05390.11340.093*
C110.2487 (3)−0.0952 (2)0.4206 (2)0.0422 (5)
C120.2342 (3)0.2459 (2)0.0909 (2)0.0466 (5)
C130.3714 (4)0.3244 (3)0.0379 (2)0.0570 (6)
H130.46750.31110.08960.068*
C140.3666 (5)0.4226 (3)−0.0916 (3)0.0748 (8)
H140.46070.4738−0.12700.090*
C150.2250 (6)0.4448 (4)−0.1677 (3)0.0846 (10)
H150.22330.5103−0.25500.102*
C160.0850 (6)0.3712 (4)−0.1163 (3)0.0834 (10)
H16−0.01390.3893−0.16810.100*
C170.0903 (4)0.2697 (3)0.0127 (2)0.0647 (7)
H17−0.00300.21760.04690.078*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.1144 (15)0.0418 (9)0.0473 (9)−0.0423 (10)0.0084 (9)−0.0233 (7)
O20.1327 (17)0.0529 (10)0.0399 (9)−0.0575 (11)0.0093 (9)−0.0161 (8)
O30.0565 (9)0.0317 (7)0.0375 (8)−0.0167 (6)−0.0028 (6)−0.0168 (6)
O40.0792 (12)0.0333 (8)0.0753 (12)−0.0259 (8)−0.0028 (9)−0.0224 (8)
C10.0499 (12)0.0313 (10)0.0385 (12)−0.0178 (9)−0.0023 (9)−0.0141 (9)
C20.0380 (11)0.0307 (10)0.0391 (11)−0.0123 (8)0.0004 (8)−0.0153 (8)
C30.0480 (12)0.0370 (11)0.0402 (12)−0.0140 (9)−0.0002 (9)−0.0174 (9)
C40.0543 (13)0.0380 (11)0.0372 (11)−0.0164 (10)0.0012 (9)−0.0087 (9)
C50.0482 (12)0.0269 (10)0.0497 (13)−0.0150 (9)0.0008 (9)−0.0086 (9)
C60.0342 (10)0.0296 (10)0.0494 (12)−0.0119 (8)0.0000 (8)−0.0169 (9)
C70.0355 (10)0.0298 (9)0.0364 (11)−0.0115 (8)0.0009 (8)−0.0133 (8)
C80.0399 (11)0.0419 (11)0.0452 (12)−0.0128 (9)−0.0004 (9)−0.0250 (9)
C90.0420 (12)0.0424 (11)0.0598 (14)−0.0149 (9)0.0019 (10)−0.0307 (10)
C100.0734 (17)0.0547 (14)0.0766 (18)−0.0214 (13)0.0020 (13)−0.0439 (13)
C110.0400 (11)0.0326 (10)0.0600 (14)−0.0138 (9)0.0007 (9)−0.0224 (10)
C120.0565 (13)0.0405 (11)0.0449 (12)−0.0065 (10)−0.0022 (10)−0.0262 (10)
C130.0740 (17)0.0481 (13)0.0502 (14)−0.0209 (12)0.0011 (12)−0.0203 (11)
C140.113 (2)0.0549 (15)0.0545 (16)−0.0303 (16)0.0168 (16)−0.0239 (13)
C150.142 (3)0.0570 (17)0.0416 (15)−0.0107 (19)−0.0024 (18)−0.0259 (13)
C160.110 (3)0.078 (2)0.0595 (18)0.0011 (18)−0.0324 (17)−0.0400 (16)
C170.0720 (17)0.0719 (17)0.0586 (16)−0.0143 (14)−0.0126 (13)−0.0368 (13)

Geometric parameters (Å, °)

O1—C11.314 (2)C8—C121.478 (3)
O1—H10.8200C9—C111.443 (3)
O2—C11.189 (2)C9—C101.502 (3)
O3—C71.355 (2)C10—H10A0.9600
O3—C81.367 (2)C10—H10B0.9600
O4—C111.236 (2)C10—H10C0.9600
C1—C21.499 (3)C12—C131.381 (3)
C2—C31.380 (3)C12—C171.385 (3)
C2—C71.410 (3)C13—C141.381 (4)
C3—C41.390 (3)C13—H130.9300
C3—H30.9300C14—C151.360 (5)
C4—C51.362 (3)C14—H140.9300
C4—H40.9300C15—C161.366 (5)
C5—C61.398 (3)C15—H150.9300
C5—H50.9300C16—C171.385 (4)
C6—C71.391 (3)C16—H160.9300
C6—C111.466 (3)C17—H170.9300
C8—C91.354 (3)
C1—O1—H1109.5C11—C9—C10117.80 (19)
C7—O3—C8120.38 (15)C9—C10—H10A109.5
O2—C1—O1123.45 (17)C9—C10—H10B109.5
O2—C1—C2125.38 (18)H10A—C10—H10B109.5
O1—C1—C2111.17 (17)C9—C10—H10C109.5
C3—C2—C7117.48 (17)H10A—C10—H10C109.5
C3—C2—C1120.09 (17)H10B—C10—H10C109.5
C7—C2—C1122.37 (17)O4—C11—C9123.31 (19)
C2—C3—C4121.87 (19)O4—C11—C6120.0 (2)
C2—C3—H3119.1C9—C11—C6116.63 (17)
C4—C3—H3119.1C13—C12—C17118.9 (2)
C5—C4—C3120.06 (19)C13—C12—C8119.9 (2)
C5—C4—H4120.0C17—C12—C8121.1 (2)
C3—C4—H4120.0C12—C13—C14120.3 (3)
C4—C5—C6120.32 (17)C12—C13—H13119.9
C4—C5—H5119.8C14—C13—H13119.9
C6—C5—H5119.8C15—C14—C13120.3 (3)
C7—C6—C5119.23 (17)C15—C14—H14119.8
C7—C6—C11119.48 (18)C13—C14—H14119.8
C5—C6—C11121.28 (17)C14—C15—C16120.2 (3)
O3—C7—C6120.94 (17)C14—C15—H15119.9
O3—C7—C2118.04 (16)C16—C15—H15119.9
C6—C7—C2121.02 (18)C15—C16—C17120.1 (3)
C9—C8—O3123.39 (19)C15—C16—H16119.9
C9—C8—C12127.06 (18)C17—C16—H16119.9
O3—C8—C12109.53 (16)C12—C17—C16120.1 (3)
C8—C9—C11119.07 (18)C12—C17—H17120.0
C8—C9—C10123.1 (2)C16—C17—H17120.0
O2—C1—C2—C3164.8 (2)C12—C8—C9—C11−178.8 (2)
O1—C1—C2—C3−14.5 (3)O3—C8—C9—C10−174.3 (2)
O2—C1—C2—C7−12.4 (3)C12—C8—C9—C103.7 (4)
O1—C1—C2—C7168.23 (18)C8—C9—C11—O4177.9 (2)
C7—C2—C3—C41.4 (3)C10—C9—C11—O4−4.4 (3)
C1—C2—C3—C4−176.0 (2)C8—C9—C11—C6−3.3 (3)
C2—C3—C4—C5−0.5 (3)C10—C9—C11—C6174.40 (19)
C3—C4—C5—C6−0.3 (3)C7—C6—C11—O4179.63 (19)
C4—C5—C6—C70.2 (3)C5—C6—C11—O40.6 (3)
C4—C5—C6—C11179.2 (2)C7—C6—C11—C90.8 (3)
C8—O3—C7—C6−2.2 (3)C5—C6—C11—C9−178.21 (18)
C8—O3—C7—C2178.03 (17)C9—C8—C12—C13−125.6 (2)
C5—C6—C7—O3−179.03 (17)O3—C8—C12—C1352.7 (3)
C11—C6—C7—O31.9 (3)C9—C8—C12—C1756.1 (3)
C5—C6—C7—C20.7 (3)O3—C8—C12—C17−125.6 (2)
C11—C6—C7—C2−178.32 (17)C17—C12—C13—C14−1.2 (3)
C3—C2—C7—O3178.24 (17)C8—C12—C13—C14−179.5 (2)
C1—C2—C7—O3−4.5 (3)C12—C13—C14—C151.0 (4)
C3—C2—C7—C6−1.5 (3)C13—C14—C15—C160.6 (4)
C1—C2—C7—C6175.80 (18)C14—C15—C16—C17−1.9 (4)
C7—O3—C8—C9−0.4 (3)C13—C12—C17—C16−0.1 (3)
C7—O3—C8—C12−178.76 (16)C8—C12—C17—C16178.2 (2)
O3—C8—C9—C113.2 (3)C15—C16—C17—C121.7 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O4i0.821.862.615 (3)154
C3—H3···O10.932.352.683 (3)101
C14—H14···O2ii0.932.573.347 (4)141
C16—H16···O2iii0.932.573.473 (5)163

Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z; (iii) −x, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2554).

References

  • Bruker (2002). SADABS, SAINT and SMART Bruker AXS Inc., Madison, Winsonsin, USA.
  • Da Re, P. (1960). US Patent 2921070.
  • Da Re, P. (1968). US Patent 3350411.
  • Ghoneim, M. M., El-Attar, M. A. & Razeq, S. A. (2007). Cent. Eur. J. Chem.5, 496–507.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sianesi, E. (1972). Ger. Patent 2059296.
  • Uneyama, K., Masatsugu, Y. & Torll, S. (1985). Bull. Chem. Soc. Jpn, 58, 2361–2365.

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