4-Chloro­phenyl 2-oxo-2H-chromene-3-carboxyl­ate

Guo, X.-Q.; Yan, J.; Gan, Y.; Song, Q.; Gou, X.-J.

doi:10.1107/S1600536812003376

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o574

doi:10.1107/S1600536812003376

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4-Chlorophenyl 2-oxo-2H-chromene-3-carboxylate

Xiao-Qiang Guo,^a Jun Yan,^a Ya Gan,^a Qin Song ^a and Xiao-Jun Gou ^a ^*

^aFaculty of Biotechnology Industry, Chengdu University, Chengdu 610106, People's Republic of China
^*Correspondence e-mail: guokedian@yahoo.cn

(Received 21 January 2012; accepted 26 January 2012; online 4 February 2012)

In title compound, C₁₆H₉ClO₄, the coumarin ring system is approximately planar [maximum deviation = 0.056 (1) Å] and is oriented with respect to the benzene ring at an angle of 22.60 (7)°. Intermolecular C—H⋯O hydrogen bonding is present in the crystal.

Related literature

For the biochemical properties of related compounds, see: Kontogiorgis & Hadjipavlou-Litina (2005 ); Finn et al. (2002 ); Gursoy & Karali (2003 ); Borges et al. (2005 ). For the synthesis, see: Zhou et al. (2008 ).

Experimental

Crystal data

C₁₆H₉ClO₄
M_r = 300.68
Monoclinic, P 2₁ /c
a = 15.7586 (6) Å
b = 7.0694 (2) Å
c = 12.7167 (6) Å
β = 113.037 (5)°
V = 1303.70 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 135 K
0.35 × 0.30 × 0.25 mm

Data collection

Agilent Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.99, T_max = 1.00
5907 measured reflections
2662 independent reflections
2059 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.092
S = 1.04
2662 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.22 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
C3—H3⋯O2ⁱ	0.95	2.34	3.061 (2)	133
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812003376/xu5453sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812003376/xu5453Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812003376/xu5453Isup3.cml

checkCIF report

Comment top

The coumarins and derivatives have demonstrated an ever-increasing variety of uses, including platelet anti-aggregating activity, anti-inflammatory activity (Kontogiorgis & Hadjipavlou-Litina, 2005), anti-tumor activity (Finn et al., 2002), anti-bacterials (Gursoy & Karali, 2003), and antiviral effect (Borges et al., 2005). So the title compound was synthesized according to the published method (Zhou et al., 2008). We report here the crystal structure of the title compound. In the title compound (Fig. 1), the dihedral angle between the planes of coumarin and benzene ring is 22.60 (7)°. The packing view of the title compound is shown in Fig. 2, weak intermolecular C—H···O hydrogen bonding is present in the crystal (Table 1).

Related literature top

For the biochemical properties of related compounds, see: Kontogiorgis & Hadjipavlou-Litina (2005); Finn et al. (2002); Gursoy & Karali (2003); Borges et al. (2005). For the synthesis, see: Zhou et al. (2008).

Experimental top

2-Oxo-2H-chromene-3-carboxylic acid (0.02 mol) was added to 10 ml sulfurous oxychloride. The mixture was refluxed for 3 h, and then the resultant was removed with simple distillation to give 2-oxo-2H-chromene-3-carbonyl chloride (3.95 g). The compound can be used directly without purification. The solution of 4-chlorophenol (0.0165 mol) dissolved in dried methyl dichloride (15 ml) was added dropwise to a solution of 2-oxo-2H-chromene-3-acyl chloride (0.015 mol) dissolved in methyl dichloride (20 ml) and triethylamine (2.5 ml) at room temperature. The reaction mixture was refluxed for 6 h, (mornitored by TLC). The mixture was then neutralized with 5% HCl and washed with saturated NaHCO₃ and brine respectively. The organic phase was dried over Na₂SO₄ and evaporated under the reduced pressure. The resulting residue was purified by column chromatography (ethyl acetate: petroleum ether) to give the pure compound. Single crystals suitable for X-ray analysis were obtained by slow evaporation of a mixed solvent (methyl dichloride: methanol) at room temperature.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering, showing displacement ellipsoids at the 30% probability level.
	Fig. 2. A packing diagram of the title compound.

4-Chlorophenyl 2-oxo-2H-chromene-3-carboxylate top

Crystal data top

C₁₆H₉ClO₄	F(000) = 616
M_r = 300.68	D_x = 1.532 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.7107 Å
a = 15.7586 (6) Å	Cell parameters from 1865 reflections
b = 7.0694 (2) Å	θ = 3.2–29.0°
c = 12.7167 (6) Å	µ = 0.31 mm⁻¹
β = 113.037 (5)°	T = 135 K
V = 1303.70 (9) Å³	Block, colorless
Z = 4	0.35 × 0.30 × 0.25 mm

Data collection top

Agilent Xcalibur Eos diffractometer	2662 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2059 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 16.0874 pixels mm^-1	θ_max = 26.4°, θ_min = 3.2°
ω scans	h = −19→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −8→8
T_min = 0.99, T_max = 1.00	l = −15→15
5907 measured reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0338P)² + 0.3053P] where P = (F_o² + 2F_c²)/3
2662 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₆H₉ClO₄	V = 1303.70 (9) Å³
M_r = 300.68	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.7586 (6) Å	µ = 0.31 mm⁻¹
b = 7.0694 (2) Å	T = 135 K
c = 12.7167 (6) Å	0.35 × 0.30 × 0.25 mm
β = 113.037 (5)°

Data collection top

Agilent Xcalibur Eos diffractometer	2662 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	2059 reflections with I > 2σ(I)
T_min = 0.99, T_max = 1.00	R_int = 0.025
5907 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.04	Δρ_max = 0.22 e Å⁻³
2662 reflections	Δρ_min = −0.25 e Å⁻³
190 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
Cl1	0.43760 (4)	0.34411 (8)	0.78566 (6)	0.04706 (19)
O1	0.06760 (8)	0.42742 (17)	0.78729 (10)	0.0207 (3)
O2	0.08852 (9)	0.22946 (18)	0.93513 (11)	0.0261 (3)
O3	−0.19477 (9)	0.33623 (17)	0.87422 (11)	0.0257 (3)
O4	−0.05715 (9)	0.31077 (18)	1.01368 (11)	0.0282 (3)
C1	0.32829 (13)	0.3605 (3)	0.78930 (18)	0.0278 (5)
C2	0.25165 (13)	0.3316 (3)	0.69014 (17)	0.0268 (4)
H2	0.2583	0.2995	0.6212	0.032*
C3	0.16458 (13)	0.3502 (2)	0.69216 (16)	0.0224 (4)
H3	0.1108	0.3305	0.6249	0.027*
C4	0.15761 (12)	0.3978 (2)	0.79363 (15)	0.0198 (4)
C5	0.23437 (13)	0.4279 (3)	0.89344 (15)	0.0233 (4)
H5	0.2278	0.4620	0.9621	0.028*
C6	0.32111 (13)	0.4072 (3)	0.89098 (17)	0.0281 (4)
H6	0.3750	0.4249	0.9585	0.034*
C7	0.03900 (13)	0.3290 (2)	0.85939 (15)	0.0194 (4)
C8	−0.06155 (12)	0.3544 (2)	0.82490 (15)	0.0189 (4)
C9	−0.09937 (13)	0.3309 (2)	0.91268 (16)	0.0216 (4)
C10	−0.25169 (13)	0.3560 (2)	0.76084 (16)	0.0235 (4)
C11	−0.21523 (13)	0.3850 (2)	0.67830 (16)	0.0218 (4)
C12	−0.11740 (13)	0.3840 (2)	0.71464 (15)	0.0199 (4)
H12	−0.0910	0.4045	0.6600	0.024*
C13	−0.27666 (14)	0.4046 (3)	0.56409 (17)	0.0276 (4)
H13	−0.2535	0.4265	0.5065	0.033*
C14	−0.37008 (14)	0.3924 (3)	0.53509 (18)	0.0338 (5)
H14	−0.4114	0.4052	0.4575	0.041*
C15	−0.40409 (14)	0.3612 (3)	0.6193 (2)	0.0352 (5)
H15	−0.4688	0.3515	0.5985	0.042*
C16	−0.34558 (14)	0.3440 (3)	0.73263 (19)	0.0305 (5)
H16	−0.3692	0.3243	0.7900	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0280 (3)	0.0510 (4)	0.0715 (4)	0.0092 (3)	0.0296 (3)	0.0160 (3)
O1	0.0195 (7)	0.0249 (7)	0.0200 (7)	0.0019 (6)	0.0102 (5)	0.0047 (5)
O2	0.0250 (7)	0.0309 (7)	0.0226 (7)	0.0051 (6)	0.0096 (6)	0.0066 (6)
O3	0.0240 (7)	0.0298 (7)	0.0276 (7)	−0.0018 (6)	0.0147 (6)	−0.0031 (6)
O4	0.0325 (8)	0.0361 (8)	0.0192 (7)	−0.0040 (7)	0.0134 (6)	−0.0015 (6)
C1	0.0216 (10)	0.0223 (10)	0.0436 (12)	0.0038 (8)	0.0173 (9)	0.0083 (9)
C2	0.0328 (11)	0.0231 (10)	0.0310 (11)	0.0017 (9)	0.0196 (9)	0.0028 (8)
C3	0.0259 (10)	0.0196 (9)	0.0216 (10)	−0.0023 (8)	0.0093 (8)	0.0005 (7)
C4	0.0201 (9)	0.0168 (8)	0.0244 (10)	0.0017 (8)	0.0107 (8)	0.0038 (7)
C5	0.0257 (10)	0.0230 (10)	0.0208 (10)	−0.0012 (8)	0.0086 (8)	0.0015 (7)
C6	0.0210 (10)	0.0264 (10)	0.0318 (11)	−0.0004 (9)	0.0049 (9)	0.0061 (8)
C7	0.0256 (10)	0.0195 (9)	0.0149 (9)	−0.0018 (8)	0.0099 (8)	−0.0030 (7)
C8	0.0222 (9)	0.0155 (9)	0.0222 (9)	−0.0010 (8)	0.0122 (8)	−0.0020 (7)
C9	0.0241 (10)	0.0180 (9)	0.0265 (11)	−0.0027 (8)	0.0140 (8)	−0.0034 (8)
C10	0.0228 (10)	0.0181 (9)	0.0297 (11)	−0.0006 (8)	0.0105 (8)	−0.0037 (8)
C11	0.0223 (10)	0.0167 (9)	0.0267 (10)	0.0012 (8)	0.0098 (8)	−0.0018 (7)
C12	0.0253 (10)	0.0156 (8)	0.0216 (9)	−0.0006 (8)	0.0123 (8)	−0.0017 (7)
C13	0.0285 (11)	0.0224 (10)	0.0292 (11)	0.0039 (9)	0.0083 (9)	0.0004 (8)
C14	0.0257 (11)	0.0289 (11)	0.0376 (12)	0.0066 (9)	0.0025 (9)	0.0002 (9)
C15	0.0192 (10)	0.0266 (11)	0.0554 (14)	0.0038 (9)	0.0098 (10)	−0.0021 (10)
C16	0.0249 (11)	0.0255 (10)	0.0450 (13)	0.0011 (9)	0.0178 (10)	−0.0019 (9)

Geometric parameters (Å, º) top

Cl1—C1	1.7450 (19)	C6—H6	0.9500
O1—C4	1.404 (2)	C7—C8	1.480 (2)
O1—C7	1.361 (2)	C8—C9	1.466 (2)
O2—C7	1.201 (2)	C8—C12	1.349 (2)
O3—C9	1.388 (2)	C10—C11	1.395 (3)
O3—C10	1.375 (2)	C10—C16	1.382 (3)
O4—C9	1.202 (2)	C11—C12	1.426 (3)
C1—C2	1.378 (3)	C11—C13	1.402 (3)
C1—C6	1.381 (3)	C12—H12	0.9500
C2—H2	0.9500	C13—H13	0.9500
C2—C3	1.388 (3)	C13—C14	1.373 (3)
C3—H3	0.9500	C14—H14	0.9500
C3—C4	1.379 (2)	C14—C15	1.390 (3)
C4—C5	1.385 (2)	C15—H15	0.9500
C5—H5	0.9500	C15—C16	1.379 (3)
C5—C6	1.387 (3)	C16—H16	0.9500

C7—O1—C4	118.58 (13)	C12—C8—C9	120.99 (17)
C10—O3—C9	122.99 (14)	O3—C9—C8	115.83 (16)
C2—C1—Cl1	119.13 (16)	O4—C9—O3	116.77 (16)
C2—C1—C6	121.90 (18)	O4—C9—C8	127.39 (18)
C6—C1—Cl1	118.94 (16)	O3—C10—C11	120.82 (17)
C1—C2—H2	120.4	O3—C10—C16	117.30 (17)
C1—C2—C3	119.20 (18)	C16—C10—C11	121.88 (19)
C3—C2—H2	120.4	C10—C11—C12	117.83 (17)
C2—C3—H3	120.6	C10—C11—C13	118.25 (18)
C4—C3—C2	118.79 (17)	C13—C11—C12	123.85 (18)
C4—C3—H3	120.6	C8—C12—C11	121.38 (17)
C3—C4—O1	115.54 (16)	C8—C12—H12	119.3
C3—C4—C5	122.29 (17)	C11—C12—H12	119.3
C5—C4—O1	122.01 (16)	C11—C13—H13	119.8
C4—C5—H5	120.7	C14—C13—C11	120.33 (19)
C4—C5—C6	118.56 (17)	C14—C13—H13	119.8
C6—C5—H5	120.7	C13—C14—H14	120.0
C1—C6—C5	119.26 (18)	C13—C14—C15	119.9 (2)
C1—C6—H6	120.4	C15—C14—H14	120.0
C5—C6—H6	120.4	C14—C15—H15	119.4
O1—C7—C8	109.68 (15)	C16—C15—C14	121.15 (19)
O2—C7—O1	123.86 (17)	C16—C15—H15	119.4
O2—C7—C8	126.34 (17)	C10—C16—H16	120.8
C9—C8—C7	117.88 (16)	C15—C16—C10	118.43 (19)
C12—C8—C7	120.95 (16)	C15—C16—H16	120.8

Cl1—C1—C2—C3	−178.09 (13)	C7—C8—C9—O3	−173.49 (15)
Cl1—C1—C6—C5	177.43 (14)	C7—C8—C9—O4	7.9 (3)
O1—C4—C5—C6	−175.94 (16)	C7—C8—C12—C11	172.06 (16)
O1—C7—C8—C9	−154.96 (14)	C9—O3—C10—C11	−4.4 (2)
O1—C7—C8—C12	29.9 (2)	C9—O3—C10—C16	174.89 (16)
O2—C7—C8—C9	28.8 (3)	C9—C8—C12—C11	−2.9 (3)
O2—C7—C8—C12	−146.26 (18)	C10—O3—C9—O4	−179.14 (15)
O3—C10—C11—C12	3.0 (2)	C10—O3—C9—C8	2.1 (2)
O3—C10—C11—C13	−179.87 (15)	C10—C11—C12—C8	0.6 (3)
O3—C10—C16—C15	−179.25 (16)	C10—C11—C13—C14	−1.0 (3)
C1—C2—C3—C4	0.3 (3)	C11—C10—C16—C15	0.1 (3)
C2—C1—C6—C5	−0.8 (3)	C11—C13—C14—C15	0.3 (3)
C2—C3—C4—O1	175.57 (15)	C12—C8—C9—O3	1.6 (2)
C2—C3—C4—C5	0.1 (3)	C12—C8—C9—O4	−177.06 (18)
C3—C4—C5—C6	−0.7 (3)	C12—C11—C13—C14	175.89 (18)
C4—O1—C7—O2	6.5 (2)	C13—C11—C12—C8	−176.34 (16)
C4—O1—C7—C8	−169.80 (14)	C13—C14—C15—C16	0.7 (3)
C4—C5—C6—C1	1.0 (3)	C14—C15—C16—C10	−0.8 (3)
C6—C1—C2—C3	0.1 (3)	C16—C10—C11—C12	−176.25 (17)
C7—O1—C4—C3	126.23 (16)	C16—C10—C11—C13	0.8 (3)
C7—O1—C4—C5	−58.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱ	0.95	2.34	3.061 (2)	133

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₉ClO₄
M_r	300.68
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	135
a, b, c (Å)	15.7586 (6), 7.0694 (2), 12.7167 (6)
β (°)	113.037 (5)
V (Å³)	1303.70 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.35 × 0.30 × 0.25

Data collection
Diffractometer	Agilent Xcalibur Eos diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.99, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	5907, 2662, 2059
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.092, 1.04
No. of reflections	2662
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.25

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXTL (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱ	0.95	2.34	3.061 (2)	133

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

This work was supported by the Applied Basic Research Program of Sichuan Provincial Science and Technology Department, China (grant No. 2009JY0113). The authors thank Mr Z.–H. Mao and Mr D.–B. Luo of the Analytical and Testing Center, Sichuan University, for assistance with the data collection.

References

Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England. Google Scholar
Borges, F., Roleira, F., Milhazes, N., Santana, L. & Uriarte, E. (2005). Curr. Med. Chem. 12, 887–916. Web of Science CrossRef PubMed CAS Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Finn, G. J., Kenealy, E., Creaven, B. S. & Egan, D. A. (2002). Cancer Lett. 183, 61-68. Web of Science CrossRef PubMed CAS Google Scholar
Gursoy, A. & Karali, N. (2003). Turk. J. Chem. 27, 545–551. Google Scholar
Kontogiorgis, C. A. & Hadjipavlou-Litina, D. J. (2005). J. Med. Chem. 48, 6400–6408. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhou, X., Wang, X.-B., Wang, T. & Kong, L.-Y. (2008). Bioorg. Med. Chem. 16, 8011–8021. Web of Science CrossRef PubMed CAS Google Scholar