supplementary materials


bt6913 scheme

Acta Cryst. (2013). E69, o1089    [ doi:10.1107/S1600536813015675 ]

2-Methoxy-4-(prop-2-en-1-yl)phenyl 2,4-dichlorobenzoate

M. R. Pichika, Y. B. Kang and S. W. Ng

Abstract top

In the title compound, C17H14Cl2O3, the two benzene rings are twisted by 73.6 (2)°. The twist is similar to that found in the unsubstituted compound, viz. phenyl benzoate. In the crystal, inversion dimers are linked by pairs of C-H...O interactions.

Comment top

The title phenyl benzoate (Scheme I, Fig. 1), which possesses an allyl and a methoxy substituent, was synthesized for an evaluation of its pharmaceutical properties as it is an ester derivative of eugenol. The two benzene rings are approximately perpendicular [dihedral angle 73.6 (25) °]. The twist is similar to that found in the unsubstituted compound, phenyl benzoate (Shibakami & Sekiya, 1995).

Related literature top

For the structure of phenyl benzoate, see: Shibakami & Sekiya (1995).

Experimental top

4-Allyl-2-methoxyphenol (1 mmol), 2,4-dichlorobenzoic acid (1 mmol), diethylazodicarboxylate (2 mmol) and triphenylphosphine (2 mmol) were heated in THF (10 ml) for 2 h. The solid material extracted with dichloromethane. The dichloromethane solution was eluted through a silica gel column by using an n-hexane–ethyl acetate (95: 5 v/v) solvent system. Slow evaporation of the solution yielded large colorless crystals.

Refinement top

H-atoms were placed in calculated positions [C–H 0.95 to 0.98 Å, Uiso(H) 1.2 to 1.5Ueq(C)] and were included in the refinement in the riding model approximation.

The final difference Fourier map had a peak at 1 Å from Cl1.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C17H14Cl2O3 at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
2-Methoxy-4-(prop-2-en-1-yl)phenyl 2,4-dichlorobenzoate top
Crystal data top
C17H14Cl2O3Z = 2
Mr = 337.18F(000) = 348
Triclinic, P1Dx = 1.456 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.8805 (8) ÅCell parameters from 1164 reflections
b = 8.4673 (12) Åθ = 3.0–25.0°
c = 12.3973 (14) ŵ = 0.43 mm1
α = 104.166 (11)°T = 100 K
β = 94.502 (9)°Prism, colourless
γ = 104.145 (10)°0.40 × 0.20 × 0.20 mm
V = 769.29 (16) Å3
Data collection top
Agilent SuperNova Dual
diffractometer with an Atlas detector
2703 independent reflections
Radiation source: SuperNova (Mo) X-ray Source1818 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.057
Detector resolution: 10.4041 pixels mm-1θmax = 25.0°, θmin = 3.0°
ω scanh = 99
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)
k = 910
Tmin = 0.847, Tmax = 0.919l = 149
4945 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.082Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.269H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.1481P)2 + 0.2039P]
where P = (Fo2 + 2Fc2)/3
2703 reflections(Δ/σ)max = 0.001
199 parametersΔρmax = 1.02 e Å3
0 restraintsΔρmin = 0.64 e Å3
Crystal data top
C17H14Cl2O3γ = 104.145 (10)°
Mr = 337.18V = 769.29 (16) Å3
Triclinic, P1Z = 2
a = 7.8805 (8) ÅMo Kα radiation
b = 8.4673 (12) ŵ = 0.43 mm1
c = 12.3973 (14) ÅT = 100 K
α = 104.166 (11)°0.40 × 0.20 × 0.20 mm
β = 94.502 (9)°
Data collection top
Agilent SuperNova Dual
diffractometer with an Atlas detector
2703 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)
1818 reflections with I > 2σ(I)
Tmin = 0.847, Tmax = 0.919Rint = 0.057
4945 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.082H-atom parameters constrained
wR(F2) = 0.269Δρmax = 1.02 e Å3
S = 1.09Δρmin = 0.64 e Å3
2703 reflectionsAbsolute structure: ?
199 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.61313 (17)0.1630 (2)0.41224 (12)0.0305 (5)
Cl21.30151 (17)0.3673 (2)0.56261 (11)0.0286 (5)
O10.5171 (5)0.5487 (5)0.1955 (3)0.0248 (10)
O20.5571 (5)0.2458 (5)0.2059 (3)0.0247 (10)
O30.7704 (5)0.3027 (5)0.0993 (3)0.0244 (10)
C10.4077 (7)0.4099 (7)0.1176 (4)0.0196 (12)
C20.2748 (7)0.4127 (7)0.0377 (4)0.0210 (13)
H20.25800.51840.03330.025*
C30.1662 (7)0.2644 (8)0.0358 (4)0.0225 (13)
C40.1948 (7)0.1095 (7)0.0313 (5)0.0232 (13)
H40.12310.00720.08200.028*
C50.3276 (7)0.1049 (8)0.0470 (5)0.0252 (14)
H50.34640.00050.05040.030*
C60.4327 (7)0.2539 (7)0.1202 (4)0.0205 (13)
C70.4783 (8)0.7069 (7)0.1996 (5)0.0297 (15)
H7A0.56280.79760.25810.045*
H7B0.35790.70010.21700.045*
H7C0.48760.73110.12660.045*
C80.0147 (7)0.2725 (8)0.1161 (4)0.0258 (14)
H8A0.09810.22700.09020.031*
H8B0.02510.39270.11230.031*
C90.0062 (8)0.1778 (8)0.2361 (5)0.0286 (15)
H90.10730.20720.27160.034*
C100.1295 (9)0.0577 (8)0.2954 (5)0.0335 (15)
H10A0.23290.02480.26270.040*
H10B0.12500.00320.37140.040*
C110.7283 (7)0.2824 (7)0.1879 (5)0.0218 (13)
C120.8567 (7)0.2914 (7)0.2851 (4)0.0218 (13)
C130.8232 (7)0.2503 (7)0.3850 (5)0.0209 (13)
C140.9597 (7)0.2728 (7)0.4692 (4)0.0216 (13)
H140.93520.24230.53630.026*
C151.1335 (7)0.3406 (8)0.4549 (4)0.0222 (13)
C161.1726 (7)0.3802 (7)0.3571 (4)0.0237 (13)
H161.29170.42280.34690.028*
C171.0337 (7)0.3565 (8)0.2737 (4)0.0245 (13)
H171.05950.38550.20630.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0151 (8)0.0452 (11)0.0321 (9)0.0026 (7)0.0048 (6)0.0172 (7)
Cl20.0183 (8)0.0381 (10)0.0272 (9)0.0058 (7)0.0021 (6)0.0082 (7)
O10.018 (2)0.026 (2)0.027 (2)0.0043 (18)0.0019 (16)0.0035 (18)
O20.019 (2)0.034 (2)0.023 (2)0.0072 (18)0.0033 (16)0.0102 (18)
O30.021 (2)0.028 (2)0.023 (2)0.0034 (18)0.0032 (16)0.0096 (18)
C10.016 (3)0.017 (3)0.020 (3)0.000 (2)0.003 (2)0.001 (2)
C20.019 (3)0.029 (3)0.017 (3)0.008 (3)0.003 (2)0.006 (2)
C30.019 (3)0.030 (3)0.020 (3)0.008 (3)0.009 (2)0.007 (3)
C40.020 (3)0.021 (3)0.026 (3)0.000 (3)0.003 (2)0.009 (3)
C50.020 (3)0.027 (3)0.032 (3)0.008 (3)0.007 (2)0.010 (3)
C60.016 (3)0.026 (3)0.019 (3)0.006 (2)0.002 (2)0.006 (2)
C70.024 (3)0.021 (3)0.038 (4)0.005 (3)0.001 (3)0.000 (3)
C80.018 (3)0.023 (3)0.033 (3)0.003 (3)0.000 (2)0.007 (3)
C90.021 (3)0.043 (4)0.025 (3)0.012 (3)0.004 (2)0.012 (3)
C100.038 (4)0.025 (4)0.034 (4)0.011 (3)0.004 (3)0.002 (3)
C110.017 (3)0.016 (3)0.030 (3)0.005 (2)0.007 (2)0.002 (3)
C120.018 (3)0.022 (3)0.023 (3)0.008 (2)0.001 (2)0.001 (2)
C130.012 (3)0.021 (3)0.029 (3)0.004 (2)0.002 (2)0.006 (2)
C140.021 (3)0.024 (3)0.020 (3)0.010 (3)0.001 (2)0.002 (2)
C150.019 (3)0.030 (3)0.016 (3)0.008 (3)0.001 (2)0.002 (2)
C160.014 (3)0.027 (3)0.025 (3)0.000 (2)0.002 (2)0.003 (3)
C170.027 (3)0.031 (4)0.016 (3)0.008 (3)0.005 (2)0.006 (3)
Geometric parameters (Å, º) top
Cl1—C131.736 (5)C7—H7C0.9800
Cl2—C151.736 (5)C8—C91.494 (8)
O1—C11.369 (6)C8—H8A0.9900
O1—C71.436 (7)C8—H8B0.9900
O2—C111.357 (6)C9—C101.303 (9)
O2—C61.414 (6)C9—H90.9500
O3—C111.210 (7)C10—H10A0.9500
C1—C61.390 (8)C10—H10B0.9500
C1—C21.393 (7)C11—C121.486 (8)
C2—C31.390 (8)C12—C131.393 (8)
C2—H20.9500C12—C171.401 (8)
C3—C41.397 (8)C13—C141.382 (7)
C3—C81.520 (7)C14—C151.393 (8)
C4—C51.385 (8)C14—H140.9500
C4—H40.9500C15—C161.373 (8)
C5—C61.383 (7)C16—C171.386 (8)
C5—H50.9500C16—H160.9500
C7—H7A0.9800C17—H170.9500
C7—H7B0.9800
C1—O1—C7115.8 (4)C3—C8—H8B108.5
C11—O2—C6115.7 (4)H8A—C8—H8B107.5
O1—C1—C6116.3 (5)C10—C9—C8124.8 (6)
O1—C1—C2125.6 (5)C10—C9—H9117.6
C6—C1—C2118.1 (5)C8—C9—H9117.6
C3—C2—C1121.5 (5)C9—C10—H10A120.0
C3—C2—H2119.2C9—C10—H10B120.0
C1—C2—H2119.2H10A—C10—H10B120.0
C2—C3—C4119.1 (5)O3—C11—O2122.4 (5)
C2—C3—C8119.7 (5)O3—C11—C12123.7 (5)
C4—C3—C8121.2 (5)O2—C11—C12114.0 (5)
C5—C4—C3120.0 (5)C13—C12—C17117.4 (5)
C5—C4—H4120.0C13—C12—C11128.7 (5)
C3—C4—H4120.0C17—C12—C11113.8 (5)
C6—C5—C4119.9 (5)C14—C13—C12121.1 (5)
C6—C5—H5120.0C14—C13—Cl1115.1 (4)
C4—C5—H5120.0C12—C13—Cl1123.8 (4)
C5—C6—C1121.4 (5)C13—C14—C15119.5 (5)
C5—C6—O2119.1 (5)C13—C14—H14120.3
C1—C6—O2119.3 (5)C15—C14—H14120.3
O1—C7—H7A109.5C16—C15—C14121.3 (5)
O1—C7—H7B109.5C16—C15—Cl2120.5 (4)
H7A—C7—H7B109.5C14—C15—Cl2118.2 (4)
O1—C7—H7C109.5C15—C16—C17118.2 (5)
H7A—C7—H7C109.5C15—C16—H16120.9
H7B—C7—H7C109.5C17—C16—H16120.9
C9—C8—C3114.9 (4)C16—C17—C12122.4 (5)
C9—C8—H8A108.5C16—C17—H17118.8
C3—C8—H8A108.5C12—C17—H17118.8
C9—C8—H8B108.5
C7—O1—C1—C6173.9 (5)C6—O2—C11—O37.7 (7)
C7—O1—C1—C25.8 (7)C6—O2—C11—C12173.5 (4)
O1—C1—C2—C3177.9 (5)O3—C11—C12—C13171.3 (6)
C6—C1—C2—C31.7 (8)O2—C11—C12—C137.5 (8)
C1—C2—C3—C41.9 (8)O3—C11—C12—C1711.4 (8)
C1—C2—C3—C8175.7 (5)O2—C11—C12—C17169.9 (4)
C2—C3—C4—C51.2 (8)C17—C12—C13—C140.1 (8)
C8—C3—C4—C5176.3 (5)C11—C12—C13—C14177.4 (5)
C3—C4—C5—C60.5 (8)C17—C12—C13—Cl1178.2 (4)
C4—C5—C6—C10.4 (8)C11—C12—C13—Cl14.6 (9)
C4—C5—C6—O2174.5 (4)C12—C13—C14—C151.2 (8)
O1—C1—C6—C5178.7 (5)Cl1—C13—C14—C15179.4 (4)
C2—C1—C6—C51.0 (8)C13—C14—C15—C162.3 (9)
O1—C1—C6—O24.6 (7)C13—C14—C15—Cl2179.9 (4)
C2—C1—C6—O2175.1 (4)C14—C15—C16—C172.2 (9)
C11—O2—C6—C5103.7 (6)Cl2—C15—C16—C17180.0 (4)
C11—O2—C6—C182.0 (6)C15—C16—C17—C121.1 (9)
C2—C3—C8—C9130.2 (6)C13—C12—C17—C160.1 (8)
C4—C3—C8—C952.2 (7)C11—C12—C17—C16177.8 (5)
C3—C8—C9—C10122.7 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O3i0.952.523.339 (7)144
C17—H17···O30.952.392.746 (6)101
Symmetry code: (i) x+1, y+1, z.

Experimental details

Crystal data
Chemical formulaC17H14Cl2O3
Mr337.18
Crystal system, space groupTriclinic, P1
Temperature (K)100
a, b, c (Å)7.8805 (8), 8.4673 (12), 12.3973 (14)
α, β, γ (°)104.166 (11), 94.502 (9), 104.145 (10)
V3)769.29 (16)
Z2
Radiation typeMo Kα
µ (mm1)0.43
Crystal size (mm)0.40 × 0.20 × 0.20
Data collection
DiffractometerAgilent SuperNova Dual
diffractometer with an Atlas detector
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2013)
Tmin, Tmax0.847, 0.919
No. of measured, independent and
observed [I > 2σ(I)] reflections
4945, 2703, 1818
Rint0.057
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.082, 0.269, 1.09
No. of reflections2703
No. of parameters199
No. of restraints0
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.02, 0.64

Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O3i0.95002.52003.339 (7)144.00
C17—H17···O30.95002.39002.746 (6)101.00
Symmetry code: (i) x+1, y+1, z.
Acknowledgements top

We thank the International Medical University and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR-MOHE/SC/03) for supporting this study. We would also like to thank the Ministry of Higher Education, Malaysia, for financing the project (ERGS/1/2012/STG01/IMU/02/1) and the International Medical University for providing the laboratory facilities.

references
References top

Agilent (2013). CrysAlis PRO. Agilent Technologies Inc., Santa Clara, CA, USA.

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Shibakami, M. & Sekiya, A. (1995). Acta Cryst. C51, 326–330.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.