organic compounds
3-Methyl-4-oxo-2-phenyl-4H-chromene-8-carboxylic acid
aSchool of Pharmaceutical and Chemical Engineering, Taizhou University, Linhai 317000, People's Republic of China
*Correspondence e-mail: hongxiuzhi@yahoo.com.cn
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 is governed by C—H⋯O and O—H⋯O hydrogen-bonding interactions.
Related literature
For related literature, see: Uneyama et al. (1985); Ghoneim et al. (2007); Da Re (1960, 1968); Sianesi (1972).
Experimental
Crystal data
|
Refinement
|
Data collection: SMART (Bruker, 2002); cell SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536808009732/at2554sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808009732/at2554Isup2.hkl
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.
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
in riding motion approximation with Uiso(H) = 1.2 or 1.5Ueq of the carrier atom.Data collection: SMART (Bruker, 2002); cell
SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. A view of the title compound, showing 30% probability ellipsoids for the non-hydrogen atoms and the atom-labelling scheme. |
C17H12O4 | Z = 2 |
Mr = 280.27 | F(000) = 292 |
Triclinic, P1 | Dx = 1.381 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2760 (8) Å | Cell parameters from 1477 reflections |
b = 9.6551 (10) Å | θ = 2.5–27.7° |
c = 11.3095 (12) Å | µ = 0.10 mm−1 |
α = 65.965 (2)° | T = 298 K |
β = 79.748 (2)° | Block, colourless |
γ = 68.286 (2)° | 0.35 × 0.27 × 0.18 mm |
V = 673.78 (12) Å3 |
Bruker APEX area-detector diffractometer | 2354 independent reflections |
Radiation source: fine-focus sealed tube | 2086 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −8→8 |
Tmin = 0.969, Tmax = 0.989 | k = −11→11 |
3569 measured reflections | l = −13→12 |
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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0631P)2 + 0.2396P] where P = (Fo2 + 2Fc2)/3 |
2354 reflections | (Δ/σ)max = 0.004 |
192 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C17H12O4 | γ = 68.286 (2)° |
Mr = 280.27 | V = 673.78 (12) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.2760 (8) Å | Mo Kα radiation |
b = 9.6551 (10) Å | µ = 0.10 mm−1 |
c = 11.3095 (12) Å | T = 298 K |
α = 65.965 (2)° | 0.35 × 0.27 × 0.18 mm |
β = 79.748 (2)° |
Bruker APEX area-detector diffractometer | 2354 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 2086 reflections with I > 2σ(I) |
Tmin = 0.969, Tmax = 0.989 | Rint = 0.015 |
3569 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.20 e Å−3 |
2354 reflections | Δρmin = −0.25 e Å−3 |
192 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 | 0.2307 (3) | 0.48247 (18) | 0.52007 (15) | 0.0620 (5) | |
H1 | 0.2521 | 0.5681 | 0.4842 | 0.093* | |
O2 | 0.3009 (3) | 0.4730 (2) | 0.32507 (15) | 0.0690 (6) | |
O3 | 0.2390 (2) | 0.22602 (15) | 0.30232 (13) | 0.0398 (4) | |
O4 | 0.2514 (3) | −0.23584 (17) | 0.47596 (17) | 0.0595 (5) | |
C1 | 0.2644 (3) | 0.4115 (2) | 0.43715 (19) | 0.0380 (5) | |
C2 | 0.2526 (3) | 0.2451 (2) | 0.50288 (18) | 0.0351 (5) | |
C3 | 0.2552 (3) | 0.1725 (2) | 0.63616 (19) | 0.0409 (5) | |
H3 | 0.2558 | 0.2307 | 0.6844 | 0.049* | |
C4 | 0.2568 (3) | 0.0150 (2) | 0.7004 (2) | 0.0451 (5) | |
H4 | 0.2597 | −0.0311 | 0.7903 | 0.054* | |
C5 | 0.2543 (3) | −0.0720 (2) | 0.6318 (2) | 0.0432 (5) | |
H5 | 0.2562 | −0.1776 | 0.6750 | 0.052* | |
C6 | 0.2490 (3) | −0.0033 (2) | 0.49658 (19) | 0.0368 (5) | |
C7 | 0.2471 (3) | 0.1545 (2) | 0.43312 (18) | 0.0337 (4) | |
C8 | 0.2394 (3) | 0.1420 (2) | 0.2298 (2) | 0.0396 (5) | |
C9 | 0.2489 (3) | −0.0139 (2) | 0.2816 (2) | 0.0443 (5) | |
C10 | 0.2678 (4) | −0.1097 (3) | 0.2009 (3) | 0.0621 (7) | |
H10A | 0.1433 | −0.1234 | 0.2021 | 0.093* | |
H10B | 0.3672 | −0.2131 | 0.2357 | 0.093* | |
H10C | 0.3050 | −0.0539 | 0.1134 | 0.093* | |
C11 | 0.2487 (3) | −0.0952 (2) | 0.4206 (2) | 0.0422 (5) | |
C12 | 0.2342 (3) | 0.2459 (2) | 0.0909 (2) | 0.0466 (5) | |
C13 | 0.3714 (4) | 0.3244 (3) | 0.0379 (2) | 0.0570 (6) | |
H13 | 0.4675 | 0.3111 | 0.0896 | 0.068* | |
C14 | 0.3666 (5) | 0.4226 (3) | −0.0916 (3) | 0.0748 (8) | |
H14 | 0.4607 | 0.4738 | −0.1270 | 0.090* | |
C15 | 0.2250 (6) | 0.4448 (4) | −0.1677 (3) | 0.0846 (10) | |
H15 | 0.2233 | 0.5103 | −0.2550 | 0.102* | |
C16 | 0.0850 (6) | 0.3712 (4) | −0.1163 (3) | 0.0834 (10) | |
H16 | −0.0139 | 0.3893 | −0.1681 | 0.100* | |
C17 | 0.0903 (4) | 0.2697 (3) | 0.0127 (2) | 0.0647 (7) | |
H17 | −0.0030 | 0.2176 | 0.0469 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.1144 (15) | 0.0418 (9) | 0.0473 (9) | −0.0423 (10) | 0.0084 (9) | −0.0233 (7) |
O2 | 0.1327 (17) | 0.0529 (10) | 0.0399 (9) | −0.0575 (11) | 0.0093 (9) | −0.0161 (8) |
O3 | 0.0565 (9) | 0.0317 (7) | 0.0375 (8) | −0.0167 (6) | −0.0028 (6) | −0.0168 (6) |
O4 | 0.0792 (12) | 0.0333 (8) | 0.0753 (12) | −0.0259 (8) | −0.0028 (9) | −0.0224 (8) |
C1 | 0.0499 (12) | 0.0313 (10) | 0.0385 (12) | −0.0178 (9) | −0.0023 (9) | −0.0141 (9) |
C2 | 0.0380 (11) | 0.0307 (10) | 0.0391 (11) | −0.0123 (8) | 0.0004 (8) | −0.0153 (8) |
C3 | 0.0480 (12) | 0.0370 (11) | 0.0402 (12) | −0.0140 (9) | −0.0002 (9) | −0.0174 (9) |
C4 | 0.0543 (13) | 0.0380 (11) | 0.0372 (11) | −0.0164 (10) | 0.0012 (9) | −0.0087 (9) |
C5 | 0.0482 (12) | 0.0269 (10) | 0.0497 (13) | −0.0150 (9) | 0.0008 (9) | −0.0086 (9) |
C6 | 0.0342 (10) | 0.0296 (10) | 0.0494 (12) | −0.0119 (8) | 0.0000 (8) | −0.0169 (9) |
C7 | 0.0355 (10) | 0.0298 (9) | 0.0364 (11) | −0.0115 (8) | 0.0009 (8) | −0.0133 (8) |
C8 | 0.0399 (11) | 0.0419 (11) | 0.0452 (12) | −0.0128 (9) | −0.0004 (9) | −0.0250 (9) |
C9 | 0.0420 (12) | 0.0424 (11) | 0.0598 (14) | −0.0149 (9) | 0.0019 (10) | −0.0307 (10) |
C10 | 0.0734 (17) | 0.0547 (14) | 0.0766 (18) | −0.0214 (13) | 0.0020 (13) | −0.0439 (13) |
C11 | 0.0400 (11) | 0.0326 (10) | 0.0600 (14) | −0.0138 (9) | 0.0007 (9) | −0.0224 (10) |
C12 | 0.0565 (13) | 0.0405 (11) | 0.0449 (12) | −0.0065 (10) | −0.0022 (10) | −0.0262 (10) |
C13 | 0.0740 (17) | 0.0481 (13) | 0.0502 (14) | −0.0209 (12) | 0.0011 (12) | −0.0203 (11) |
C14 | 0.113 (2) | 0.0549 (15) | 0.0545 (16) | −0.0303 (16) | 0.0168 (16) | −0.0239 (13) |
C15 | 0.142 (3) | 0.0570 (17) | 0.0416 (15) | −0.0107 (19) | −0.0024 (18) | −0.0259 (13) |
C16 | 0.110 (3) | 0.078 (2) | 0.0595 (18) | 0.0011 (18) | −0.0324 (17) | −0.0400 (16) |
C17 | 0.0720 (17) | 0.0719 (17) | 0.0586 (16) | −0.0143 (14) | −0.0126 (13) | −0.0368 (13) |
O1—C1 | 1.314 (2) | C8—C12 | 1.478 (3) |
O1—H1 | 0.8200 | C9—C11 | 1.443 (3) |
O2—C1 | 1.189 (2) | C9—C10 | 1.502 (3) |
O3—C7 | 1.355 (2) | C10—H10A | 0.9600 |
O3—C8 | 1.367 (2) | C10—H10B | 0.9600 |
O4—C11 | 1.236 (2) | C10—H10C | 0.9600 |
C1—C2 | 1.499 (3) | C12—C13 | 1.381 (3) |
C2—C3 | 1.380 (3) | C12—C17 | 1.385 (3) |
C2—C7 | 1.410 (3) | C13—C14 | 1.381 (4) |
C3—C4 | 1.390 (3) | C13—H13 | 0.9300 |
C3—H3 | 0.9300 | C14—C15 | 1.360 (5) |
C4—C5 | 1.362 (3) | C14—H14 | 0.9300 |
C4—H4 | 0.9300 | C15—C16 | 1.366 (5) |
C5—C6 | 1.398 (3) | C15—H15 | 0.9300 |
C5—H5 | 0.9300 | C16—C17 | 1.385 (4) |
C6—C7 | 1.391 (3) | C16—H16 | 0.9300 |
C6—C11 | 1.466 (3) | C17—H17 | 0.9300 |
C8—C9 | 1.354 (3) | ||
C1—O1—H1 | 109.5 | C11—C9—C10 | 117.80 (19) |
C7—O3—C8 | 120.38 (15) | C9—C10—H10A | 109.5 |
O2—C1—O1 | 123.45 (17) | C9—C10—H10B | 109.5 |
O2—C1—C2 | 125.38 (18) | H10A—C10—H10B | 109.5 |
O1—C1—C2 | 111.17 (17) | C9—C10—H10C | 109.5 |
C3—C2—C7 | 117.48 (17) | H10A—C10—H10C | 109.5 |
C3—C2—C1 | 120.09 (17) | H10B—C10—H10C | 109.5 |
C7—C2—C1 | 122.37 (17) | O4—C11—C9 | 123.31 (19) |
C2—C3—C4 | 121.87 (19) | O4—C11—C6 | 120.0 (2) |
C2—C3—H3 | 119.1 | C9—C11—C6 | 116.63 (17) |
C4—C3—H3 | 119.1 | C13—C12—C17 | 118.9 (2) |
C5—C4—C3 | 120.06 (19) | C13—C12—C8 | 119.9 (2) |
C5—C4—H4 | 120.0 | C17—C12—C8 | 121.1 (2) |
C3—C4—H4 | 120.0 | C12—C13—C14 | 120.3 (3) |
C4—C5—C6 | 120.32 (17) | C12—C13—H13 | 119.9 |
C4—C5—H5 | 119.8 | C14—C13—H13 | 119.9 |
C6—C5—H5 | 119.8 | C15—C14—C13 | 120.3 (3) |
C7—C6—C5 | 119.23 (17) | C15—C14—H14 | 119.8 |
C7—C6—C11 | 119.48 (18) | C13—C14—H14 | 119.8 |
C5—C6—C11 | 121.28 (17) | C14—C15—C16 | 120.2 (3) |
O3—C7—C6 | 120.94 (17) | C14—C15—H15 | 119.9 |
O3—C7—C2 | 118.04 (16) | C16—C15—H15 | 119.9 |
C6—C7—C2 | 121.02 (18) | C15—C16—C17 | 120.1 (3) |
C9—C8—O3 | 123.39 (19) | C15—C16—H16 | 119.9 |
C9—C8—C12 | 127.06 (18) | C17—C16—H16 | 119.9 |
O3—C8—C12 | 109.53 (16) | C12—C17—C16 | 120.1 (3) |
C8—C9—C11 | 119.07 (18) | C12—C17—H17 | 120.0 |
C8—C9—C10 | 123.1 (2) | C16—C17—H17 | 120.0 |
O2—C1—C2—C3 | 164.8 (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—C10 | 3.7 (4) |
O1—C1—C2—C7 | 168.23 (18) | C8—C9—C11—O4 | 177.9 (2) |
C7—C2—C3—C4 | 1.4 (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—C6 | 174.40 (19) |
C3—C4—C5—C6 | −0.3 (3) | C7—C6—C11—O4 | 179.63 (19) |
C4—C5—C6—C7 | 0.2 (3) | C5—C6—C11—O4 | 0.6 (3) |
C4—C5—C6—C11 | 179.2 (2) | C7—C6—C11—C9 | 0.8 (3) |
C8—O3—C7—C6 | −2.2 (3) | C5—C6—C11—C9 | −178.21 (18) |
C8—O3—C7—C2 | 178.03 (17) | C9—C8—C12—C13 | −125.6 (2) |
C5—C6—C7—O3 | −179.03 (17) | O3—C8—C12—C13 | 52.7 (3) |
C11—C6—C7—O3 | 1.9 (3) | C9—C8—C12—C17 | 56.1 (3) |
C5—C6—C7—C2 | 0.7 (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—O3 | 178.24 (17) | C8—C12—C13—C14 | −179.5 (2) |
C1—C2—C7—O3 | −4.5 (3) | C12—C13—C14—C15 | 1.0 (4) |
C3—C2—C7—C6 | −1.5 (3) | C13—C14—C15—C16 | 0.6 (4) |
C1—C2—C7—C6 | 175.80 (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—C16 | 178.2 (2) |
O3—C8—C9—C11 | 3.2 (3) | C15—C16—C17—C12 | 1.7 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4i | 0.82 | 1.86 | 2.615 (3) | 154 |
C3—H3···O1 | 0.93 | 2.35 | 2.683 (3) | 101 |
C14—H14···O2ii | 0.93 | 2.57 | 3.347 (4) | 141 |
C16—H16···O2iii | 0.93 | 2.57 | 3.473 (5) | 163 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z; (iii) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C17H12O4 |
Mr | 280.27 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 7.2760 (8), 9.6551 (10), 11.3095 (12) |
α, β, γ (°) | 65.965 (2), 79.748 (2), 68.286 (2) |
V (Å3) | 673.78 (12) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.35 × 0.27 × 0.18 |
Data collection | |
Diffractometer | Bruker APEX area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.969, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3569, 2354, 2086 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.144, 1.10 |
No. of reflections | 2354 |
No. of parameters | 192 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.25 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4i | 0.82 | 1.86 | 2.615 (3) | 154 |
C3—H3···O1 | 0.93 | 2.35 | 2.683 (3) | 101 |
C14—H14···O2ii | 0.93 | 2.57 | 3.347 (4) | 141 |
C16—H16···O2iii | 0.93 | 2.57 | 3.473 (5) | 163 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z; (iii) −x, −y+1, −z. |
Acknowledgements
The authors thank the Materia Medica Institute of Taizhou University for supporting this work.
References
Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Winsonsin, USA. Google Scholar
Da Re, P. (1960). US Patent 2921070. Google Scholar
Da Re, P. (1968). US Patent 3350411. Google Scholar
Ghoneim, M. M., El-Attar, M. A. & Razeq, S. A. (2007). Cent. Eur. J. Chem. 5, 496–507. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sianesi, E. (1972). Ger. Patent 2059296. Google Scholar
Uneyama, K., Masatsugu, Y. & Torll, S. (1985). Bull. Chem. Soc. Jpn, 58, 2361–2365. CrossRef CAS Web of Science Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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.