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

Hong, Z.; Jiang, H.-J.; Zhuang, Y.-G.; Guo, H.-C.

doi:10.1107/S1600536808009732

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o857

doi:10.1107/S1600536808009732

Open

access

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

Zhi Hong,^a ^* Hua-Jiang Jiang,^a Yu-Guo Zhuang ^a and Hai-Chang Guo ^a

^aSchool of Pharmaceutical and Chemical Engineering, Taizhou University, Linhai 317000, People's Republic of China
^*Correspondence e-mail: hongxiuzhi@yahoo.com.cn

(Received 29 March 2008; accepted 8 April 2008; online 16 April 2008)

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 ); Ghoneim et al. (2007 ); Da Re (1960 , 1968 ); Sianesi (1972 ).

Experimental

Crystal data

C₁₇H₁₂O₄
M_r = 280.27
Triclinic, $[P \overline 1]$
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 ) 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[F² > 2σ(F²)] = 0.058
wR(F²) = 0.144
S = 1.10
2354 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: SMART (Bruker, 2002); cell refinement: 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

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: 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).

Figures top

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

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

Crystal data top

C₁₇H₁₂O₄	Z = 2
M_r = 280.27	F(000) = 292
Triclinic, P1	D_x = 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

Data collection top

Bruker APEX area-detector diffractometer	2354 independent reflections
Radiation source: fine-focus sealed tube	2086 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −8→8
T_min = 0.969, T_max = 0.989	k = −11→11
3569 measured reflections	l = −13→12

Refinement top

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(F_o²) + (0.0631P)² + 0.2396P] where P = (F_o² + 2F_c²)/3
2354 reflections	(Δ/σ)_max = 0.004
192 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₇H₁₂O₄	γ = 68.286 (2)°
M_r = 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)°

Data collection top

Bruker APEX area-detector diffractometer	2354 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	2086 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.989	R_int = 0.015
3569 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.144	H-atom parameters constrained
S = 1.10	Δρ_max = 0.20 e Å⁻³
2354 reflections	Δρ_min = −0.25 e Å⁻³
192 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.969, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	3569, 2354, 2086
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.25

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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