4-Allyl-2-meth­oxy­phenyl 2-acet­oxy­benzoate

Abstract

In the title compound, C₁₉H₁₈O₅, the ester group is twisted with respect to the acetyl­salicylic acid and eugenol rings at dihedral angles of 22.48 (2) and 81.07 (1)°, respectively. The dihedral angle between the two benzene rings is 60.72 (1)°. The crystal packing exhibits no significantly short inter­molecular contacts.

Related literature

For background regarding the medicinal properties of eugenol, see: Feng & Lipton (1987 ▶); Dohi et al. (1989 ▶). For the synthesis of the aspirin eugenol ester and its biological activity, see: Li et al. (2011 ▶).

Experimental

Crystal data

• C₁₉H₁₈O₅

• M _r = 326.33

• Monoclinic,

• a = 10.60 (2) Å

• b = 12.58 (2) Å

• c = 13.23 (2) Å

• β = 109.020 (17)°

• V = 1667 (5) ų

• Z = 4

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 296 K

• 0.26 × 0.24 × 0.22 mm

Data collection

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.976, T _max = 0.980

• 8695 measured reflections

• 3089 independent reflections

• 1786 reflections with I > 2σ(I)

• R _int = 0.054

Refinement

• R[F ² > 2σ(F ²)] = 0.051

• wR(F ²) = 0.142

• S = 1.01

• 3089 reflections

• 220 parameters

• H-atom parameters constrained

• Δρ_max = 0.49 e Å⁻³

• Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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: SHELXTL.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811021416/ez2244Isup3.cml

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

supplementary crystallographic information

Comment

Aspirin has been widely used as an analgesic and anti-inflammatory drug. As the major constituent of clove oil, eugenol also shows antipyretic activity (Feng & Lipton, 1987) and anti-inflammatory activity (Dohi et al., 1989). In this paper, we report the structure of the title compound, which was synthesized from the reaction of aspirin and eugenol in sodium hydroxide solution.

Experimental

The title compound was obtained according to the literature method (Li et al., 2011). Acetylsalicylic acid (0.025 mol) and thionyl chloride (2.5 ml) were mixed in 10 ml tetrahydrofuran (THF), and refluxed at 343 K for 2 h. The surplus thionyl chloride and THF were removed under reduced pressure. The target O-Acetylsalicylyl chloride was dissolved in 5 ml THF, added dropwise to an iced solution of eugenol (0.025 mol) and sodium hydroxide (0.04 mol) in 40 ml water. After stirring at room temprature for 3 h, the crude product was obtained by filtration. The crystals were obtained by recrystalization from methanol. Elemental analysis: calculated for C₁₉ H₁₈O₅: C 69.93%, H 5.56%, O 24.51%; found: C 69.93%, H 5.53%, O 24.54%.

Refinement

The positions of all H atoms were determined geometrically and refined using a riding model with C—H = 0.93–0.97 Å and U_iso(methyl H) = 1.5U_eq(C) and 1.2U_eq for other H atoms.

Figures

Fig. 1.

The molecular structure of (I), with atom labels and displacement ellipsoids drawn at the 30% probability level.

Crystal data

C19H18O5	F(000) = 688
Mr = 326.33	Dx = 1.300 Mg m−3
Monoclinic, P21/n	Melting point = 344–345 K
Hall symbol: P 21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.60 (2) Å	Cell parameters from 2334 reflections
b = 12.58 (2) Å	θ = 2.3–23.9°
c = 13.23 (2) Å	µ = 0.09 mm−1
β = 109.020 (17)°	T = 296 K
V = 1667 (5) Å3	Block, colorless
Z = 4	0.26 × 0.24 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer	3089 independent reflections
Radiation source: fine-focus sealed tube	1786 reflections with I > 2σ(I)
graphite	Rint = 0.054
φ and ω scans	θmax = 25.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→12
Tmin = 0.976, Tmax = 0.980	k = −15→15
8695 measured reflections	l = −16→15

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051	H-atom parameters constrained
wR(F2) = 0.142	w = 1/[σ2(Fo2) + (0.0532P)2 + 0.6544P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
3089 reflections	Δρmax = 0.49 e Å−3
220 parameters	Δρmin = −0.25 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.044 (3)

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.5429 (3)	0.8815 (2)	1.1109 (2)	0.0552 (7)
H1	0.5154	0.9490	1.0842	0.066*
C2	0.6740 (3)	0.8662 (3)	1.1758 (3)	0.0651 (9)
H2	0.7329	0.9233	1.1933	0.078*
C3	0.7161 (3)	0.7671 (3)	1.2139 (2)	0.0667 (9)
H3	0.8038	0.7566	1.2575	0.080*
C4	0.6290 (3)	0.6826 (3)	1.1880 (2)	0.0589 (8)
H4	0.6582	0.6150	1.2135	0.071*
C5	0.4980 (2)	0.6979 (2)	1.1242 (2)	0.0454 (6)
C6	0.4519 (2)	0.7981 (2)	1.0850 (2)	0.0445 (6)
C7	0.3121 (3)	0.8251 (2)	1.0192 (2)	0.0460 (6)
C8	0.0856 (2)	0.7755 (2)	0.9839 (2)	0.0457 (7)
C9	0.0242 (2)	0.8431 (2)	1.0363 (2)	0.0451 (6)
C10	−0.1134 (3)	0.8549 (2)	0.9951 (2)	0.0522 (7)
H10	−0.1563	0.8996	1.0295	0.063*
C11	−0.1880 (3)	0.8015 (2)	0.9038 (2)	0.0563 (7)
C12	−0.1244 (3)	0.7362 (2)	0.8531 (2)	0.0619 (8)
H12	−0.1735	0.7007	0.7911	0.074*
C13	0.0134 (3)	0.7226 (2)	0.8936 (2)	0.0563 (8)
H13	0.0560	0.6776	0.8593	0.068*
C14	0.3662 (3)	0.5694 (2)	1.0060 (3)	0.0523 (7)
C15	0.2725 (3)	0.4813 (3)	1.0018 (3)	0.0784 (10)
H15A	0.2235	0.4650	0.9286	0.118*
H15B	0.2114	0.5019	1.0382	0.118*
H15C	0.3216	0.4197	1.0359	0.118*
C16	0.0468 (3)	0.9576 (2)	1.1848 (2)	0.0664 (8)
H16A	−0.0043	1.0124	1.1391	0.100*
H16B	0.1152	0.9894	1.2436	0.100*
H16C	−0.0109	0.9156	1.2118	0.100*
C17	−0.3382 (3)	0.8185 (3)	0.8597 (3)	0.0794 (10)
H17A	−0.3803	0.7545	0.8231	0.095*
H17B	−0.3719	0.8312	0.9186	0.095*
C18	−0.3746 (4)	0.9083 (4)	0.7853 (5)	0.1113 (15)
H18	−0.3360	0.9723	0.8151	0.134*
C19	−0.4456 (4)	0.9161 (4)	0.6917 (4)	0.1173 (16)
H19A	−0.4886	0.8564	0.6548	0.141*
H19B	−0.4565	0.9817	0.6575	0.141*
O1	0.41425 (17)	0.60944 (14)	1.10660 (15)	0.0517 (5)
O4	0.22313 (15)	0.75382 (14)	1.03094 (14)	0.0512 (5)
O2	0.3986 (2)	0.60219 (17)	0.93385 (16)	0.0684 (6)
O3	0.28083 (19)	0.90274 (16)	0.96467 (17)	0.0681 (6)
O5	0.10653 (18)	0.89150 (15)	1.12579 (15)	0.0582 (5)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0542 (17)	0.0533 (16)	0.0632 (19)	−0.0034 (13)	0.0263 (16)	−0.0015 (15)
C2	0.0491 (18)	0.076 (2)	0.073 (2)	−0.0145 (16)	0.0245 (17)	−0.0128 (18)
C3	0.0390 (16)	0.095 (3)	0.063 (2)	0.0017 (17)	0.0112 (15)	−0.0091 (19)
C4	0.0483 (17)	0.0676 (19)	0.0568 (19)	0.0101 (15)	0.0115 (15)	0.0017 (16)
C5	0.0426 (15)	0.0516 (16)	0.0420 (15)	0.0016 (12)	0.0139 (13)	−0.0015 (13)
C6	0.0431 (14)	0.0494 (15)	0.0435 (15)	0.0003 (12)	0.0177 (13)	−0.0015 (13)
C7	0.0468 (15)	0.0433 (15)	0.0506 (16)	−0.0001 (12)	0.0197 (13)	0.0004 (14)
C8	0.0382 (14)	0.0477 (15)	0.0518 (17)	0.0038 (12)	0.0153 (13)	0.0055 (13)
C9	0.0424 (15)	0.0473 (14)	0.0446 (16)	0.0017 (12)	0.0127 (13)	0.0014 (13)
C10	0.0426 (15)	0.0616 (17)	0.0552 (18)	0.0108 (13)	0.0196 (14)	0.0042 (15)
C11	0.0407 (15)	0.076 (2)	0.0493 (17)	−0.0026 (14)	0.0110 (14)	0.0006 (17)
C12	0.0541 (18)	0.075 (2)	0.0530 (18)	−0.0113 (15)	0.0126 (15)	−0.0093 (16)
C13	0.0573 (18)	0.0576 (17)	0.0596 (19)	−0.0026 (14)	0.0268 (16)	−0.0067 (15)
C14	0.0411 (15)	0.0520 (16)	0.0586 (19)	0.0105 (12)	0.0090 (15)	−0.0025 (16)
C15	0.064 (2)	0.072 (2)	0.093 (3)	−0.0104 (17)	0.0180 (19)	−0.015 (2)
C16	0.073 (2)	0.071 (2)	0.0570 (19)	0.0082 (17)	0.0236 (17)	−0.0100 (16)
C17	0.0428 (17)	0.115 (3)	0.074 (2)	−0.0002 (19)	0.0107 (17)	0.005 (2)
C18	0.048 (2)	0.131 (4)	0.138 (4)	0.020 (2)	0.009 (3)	0.003 (4)
C19	0.080 (3)	0.128 (4)	0.121 (4)	0.026 (3)	0.001 (3)	0.012 (3)
O1	0.0531 (11)	0.0474 (11)	0.0527 (12)	0.0001 (9)	0.0146 (10)	0.0027 (9)
O4	0.0372 (9)	0.0490 (10)	0.0684 (13)	0.0070 (8)	0.0188 (9)	0.0113 (9)
O2	0.0699 (14)	0.0784 (15)	0.0533 (13)	0.0034 (11)	0.0150 (12)	−0.0029 (11)
O3	0.0577 (12)	0.0600 (13)	0.0808 (15)	0.0010 (10)	0.0144 (11)	0.0244 (12)
O5	0.0482 (11)	0.0671 (13)	0.0543 (12)	0.0069 (10)	0.0097 (10)	−0.0124 (10)

Geometric parameters (Å, °)

C1—C6	1.390 (4)	C11—C17	1.521 (5)
C1—C2	1.387 (4)	C12—C13	1.392 (5)
C1—H1	0.9300	C12—H12	0.9300
C2—C3	1.364 (5)	C13—H13	0.9300
C2—H2	0.9300	C14—O2	1.189 (4)
C3—C4	1.376 (5)	C14—O1	1.357 (4)
C3—H3	0.9300	C14—C15	1.477 (4)
C4—C5	1.383 (4)	C15—H15A	0.9600
C4—H4	0.9300	C15—H15B	0.9600
C5—C6	1.390 (4)	C15—H15C	0.9600
C5—O1	1.394 (4)	C16—O5	1.423 (3)
C6—C7	1.492 (4)	C16—H16A	0.9600
C7—O3	1.195 (3)	C16—H16B	0.9600
C7—O4	1.346 (3)	C16—H16C	0.9600
C8—C13	1.363 (4)	C17—C18	1.465 (6)
C8—C9	1.386 (4)	C17—H17A	0.9700
C8—O4	1.412 (4)	C17—H17B	0.9700
C9—O5	1.364 (3)	C18—C19	1.226 (6)
C9—C10	1.389 (4)	C18—H18	0.9300
C10—C11	1.382 (4)	C19—H19A	0.9300
C10—H10	0.9300	C19—H19B	0.9300
C11—C12	1.368 (4)
C6—C1—C2	121.5 (3)	C13—C12—H12	119.7
C6—C1—H1	119.3	C8—C13—C12	119.7 (3)
C2—C1—H1	119.3	C8—C13—H13	120.1
C3—C2—C1	119.8 (3)	C12—C13—H13	120.1
C3—C2—H2	120.1	O2—C14—O1	123.0 (3)
C1—C2—H2	120.1	O2—C14—C15	126.7 (3)
C2—C3—C4	120.1 (3)	O1—C14—C15	110.4 (3)
C2—C3—H3	119.9	C14—C15—H15A	109.5
C4—C3—H3	119.9	C14—C15—H15B	109.5
C3—C4—C5	120.2 (3)	H15A—C15—H15B	109.5
C3—C4—H4	119.9	C14—C15—H15C	109.5
C5—C4—H4	119.9	H15A—C15—H15C	109.5
C4—C5—C6	121.0 (3)	H15B—C15—H15C	109.5
C4—C5—O1	116.6 (3)	O5—C16—H16A	109.5
C6—C5—O1	122.3 (3)	O5—C16—H16B	109.5
C1—C6—C5	117.5 (3)	H16A—C16—H16B	109.5
C1—C6—C7	116.7 (3)	O5—C16—H16C	109.5
C5—C6—C7	125.8 (2)	H16A—C16—H16C	109.5
O3—C7—O4	123.2 (3)	H16B—C16—H16C	109.5
O3—C7—C6	124.4 (2)	C18—C17—C11	112.3 (3)
O4—C7—C6	112.4 (2)	C18—C17—H17A	109.1
C13—C8—C9	121.1 (3)	C11—C17—H17A	109.1
C13—C8—O4	119.7 (2)	C18—C17—H17B	109.1
C9—C8—O4	118.9 (3)	C11—C17—H17B	109.1
O5—C9—C8	115.9 (3)	H17A—C17—H17B	107.9
O5—C9—C10	125.9 (2)	C19—C18—C17	132.9 (5)
C8—C9—C10	118.3 (3)	C19—C18—H18	113.5
C11—C10—C9	121.3 (2)	C17—C18—H18	113.5
C11—C10—H10	119.4	C18—C19—H19A	120.0
C9—C10—H10	119.4	C18—C19—H19B	120.0
C12—C11—C10	119.1 (3)	H19A—C19—H19B	120.0
C12—C11—C17	121.2 (3)	C14—O1—C5	118.3 (2)
C10—C11—C17	119.7 (3)	C7—O4—C8	118.8 (2)
C11—C12—C13	120.5 (3)	C9—O5—C16	117.7 (2)
C11—C12—H12	119.7
C6—C1—C2—C3	1.2 (4)	C9—C10—C11—C12	−0.4 (4)
C1—C2—C3—C4	0.1 (4)	C9—C10—C11—C17	−178.6 (3)
C2—C3—C4—C5	−0.7 (4)	C10—C11—C12—C13	0.9 (4)
C3—C4—C5—C6	0.1 (4)	C17—C11—C12—C13	179.1 (3)
C3—C4—C5—O1	−176.5 (2)	C9—C8—C13—C12	−0.1 (4)
C2—C1—C6—C5	−1.7 (4)	O4—C8—C13—C12	173.8 (2)
C2—C1—C6—C7	176.9 (2)	C11—C12—C13—C8	−0.6 (4)
C4—C5—C6—C1	1.0 (4)	C12—C11—C17—C18	−90.0 (5)
O1—C5—C6—C1	177.5 (2)	C10—C11—C17—C18	88.1 (4)
C4—C5—C6—C7	−177.5 (2)	C11—C17—C18—C19	122.2 (5)
O1—C5—C6—C7	−1.0 (4)	O2—C14—O1—C5	4.8 (4)
C1—C6—C7—O3	21.1 (4)	C15—C14—O1—C5	−176.0 (2)
C5—C6—C7—O3	−160.4 (3)	C4—C5—O1—C14	−113.6 (3)
C1—C6—C7—O4	−156.7 (2)	C6—C5—O1—C14	69.8 (3)
C5—C6—C7—O4	21.8 (3)	O3—C7—O4—C8	−5.3 (4)
C13—C8—C9—O5	179.9 (2)	C6—C7—O4—C8	172.4 (2)
O4—C8—C9—O5	6.0 (3)	C13—C8—O4—C7	105.2 (3)
C13—C8—C9—C10	0.6 (4)	C9—C8—O4—C7	−80.8 (3)
O4—C8—C9—C10	−173.3 (2)	C8—C9—O5—C16	−177.1 (2)
O5—C9—C10—C11	−179.6 (2)	C10—C9—O5—C16	2.2 (4)
C8—C9—C10—C11	−0.4 (4)