2-(4-Chloro­phen­yl)-2-oxoethyl 4-methyl­benzoate

Fun, H.-K.; Loh, W.-S.; Garudachari, B.; Isloor, A.M.; Satyanarayana, M.N.

doi:10.1107/S1600536811042851

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3030

doi:10.1107/S1600536811042851

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2-(4-Chlorophenyl)-2-oxoethyl 4-methylbenzoate

Hoong-Kun Fun,^a ^*‡ Wan-Sin Loh,^a § B. Garudachari,^b Arun M. Isloor ^b and M. N. Satyanarayana ^c

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bOrganic Electronics Division, Department of Chemistry, National Institute of Technology-Karnataka, Surathkal, Mangalore 575 025, India, and ^cDepartment of Physics, National Institute of Technology-Karnataka, Surathkal, Mangalore 575 025, India
^*Correspondence e-mail: hkfun@usm.my

(Received 14 October 2011; accepted 16 October 2011; online 22 October 2011)

In the title compound, C₁₆H₁₃ClO₃, the dihedral angle between the benzene rings is 80.74 (8)°. In the crystal, C—H⋯O hydrogen bonds link the molecules to form C(11) chains propagating in [010].

Related literature

For a related structure and background references to phenacyl benzoates, see: Fun et al. (2011 ).

Experimental

Crystal data

C₁₆H₁₃ClO₃
M_r = 288.71
Monoclinic, P 2₁ /c
a = 5.9132 (4) Å
b = 8.5044 (6) Å
c = 27.8767 (18) Å
β = 95.880 (1)°
V = 1394.49 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 297 K
0.51 × 0.30 × 0.06 mm

Data collection

Bruker SMART APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.871, T_max = 0.983
21275 measured reflections
4070 independent reflections
2628 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.144
S = 1.05
4070 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16C⋯O1ⁱ	0.96	2.46	3.383 (2)	162
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811042851/hb6454sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811042851/hb6454Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811042851/hb6454Isup3.cml

checkCIF report

Comment top

As part of our ongoing studies of phenacyl benzoates (Fun et al., 2011), we now report the synthesis and sturcture of the title compound, (I).

In the title compound (Fig. 1), the dihedral angle formed between the chloro-substituted (C1–C6) and the methyl-substituted (C10–C15) benzene rings is 80.74 (8)°. Bond lengths and angles are within the normal ranges and are comparable to a related structure (Fun et al., 2011).

In the crystal (Fig. 2), intermolecular C16—H16C···O1 hydrogen bonds (Table 1) link the molecules to form chains along the b axis.

Related literature top

For a related structure and background references to phenacyl benzoates, see: Fun et al. (2011).

Experimental top

A mixture of 4-methylbenzoic acid (1.0 g, 0.0073 mol), potassium carbonate (1.10 g, 0.0080 mol) and 2-bromo-1-(4-chlorophenyl)ethanone (1.70 g, 0.0073 mol) in dimethylformamide (10 ml) was stirred at room temperature for 2 h. On cooling, colourless needle-shaped crystals of the title compound began to separate out. They were collected by filtration and recrystallized from ethanol to yield colourless plates of (I). Yield: 1.95 g, 92.8%. M. p: 405–406 K.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. The crystal packing of the title compound, viewed along the showing the a axis. H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity.

2-(4-Chlorophenyl)-2-oxoethyl 4-methylbenzoate top

Crystal data top

C₁₆H₁₃ClO₃	F(000) = 600
M_r = 288.71	D_x = 1.375 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4428 reflections
a = 5.9132 (4) Å	θ = 2.8–28.1°
b = 8.5044 (6) Å	µ = 0.28 mm⁻¹
c = 27.8767 (18) Å	T = 297 K
β = 95.880 (1)°	Plate, colourless
V = 1394.49 (16) Å³	0.51 × 0.30 × 0.06 mm
Z = 4

Data collection top

Bruker SMART APEXII DUO CCD diffractometer	4070 independent reflections
Radiation source: fine-focus sealed tube	2628 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 30.1°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
T_min = 0.871, T_max = 0.983	k = −11→12
21275 measured reflections	l = −39→39

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.144	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0587P)² + 0.3124P] where P = (F_o² + 2F_c²)/3
4070 reflections	(Δ/σ)_max = 0.002
182 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₁₆H₁₃ClO₃	V = 1394.49 (16) Å³
M_r = 288.71	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.9132 (4) Å	µ = 0.28 mm⁻¹
b = 8.5044 (6) Å	T = 297 K
c = 27.8767 (18) Å	0.51 × 0.30 × 0.06 mm
β = 95.880 (1)°

Data collection top

Bruker SMART APEXII DUO CCD diffractometer	4070 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2628 reflections with I > 2σ(I)
T_min = 0.871, T_max = 0.983	R_int = 0.027
21275 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.144	H-atom parameters constrained
S = 1.05	Δρ_max = 0.20 e Å⁻³
4070 reflections	Δρ_min = −0.42 e Å⁻³
182 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	1.34410 (11)	0.75388 (9)	1.047675 (19)	0.0935 (2)
O1	0.5306 (2)	0.69016 (17)	0.86404 (5)	0.0739 (4)
O2	0.6246 (2)	0.50027 (17)	0.79276 (4)	0.0612 (3)
O3	0.3791 (2)	0.35541 (15)	0.83027 (4)	0.0643 (3)
C1	0.8059 (3)	0.7539 (2)	0.94970 (7)	0.0569 (4)
H1A	0.6646	0.8027	0.9453	0.068*
C2	0.9496 (4)	0.7851 (2)	0.99053 (7)	0.0646 (5)
H2A	0.9056	0.8539	1.0138	0.078*
C3	1.1586 (3)	0.7138 (2)	0.99658 (6)	0.0589 (4)
C4	1.2267 (3)	0.6099 (2)	0.96302 (6)	0.0598 (4)
H4A	1.3684	0.5617	0.9678	0.072*
C5	1.0808 (3)	0.5784 (2)	0.92215 (6)	0.0530 (4)
H5A	1.1248	0.5083	0.8992	0.064*
C6	0.8693 (3)	0.65035 (18)	0.91501 (5)	0.0462 (3)
C7	0.7093 (3)	0.62133 (19)	0.87099 (6)	0.0487 (4)
C8	0.7785 (3)	0.5032 (2)	0.83558 (6)	0.0579 (4)
H8A	0.9298	0.5283	0.8273	0.070*
H8B	0.7842	0.3997	0.8503	0.070*
C9	0.4256 (3)	0.42441 (19)	0.79494 (6)	0.0484 (4)
C10	0.2774 (3)	0.43770 (17)	0.74889 (5)	0.0438 (3)
C11	0.3350 (3)	0.53418 (19)	0.71169 (6)	0.0496 (4)
H11A	0.4730	0.5876	0.7146	0.060*
C12	0.1863 (3)	0.55014 (19)	0.67042 (6)	0.0523 (4)
H12A	0.2264	0.6144	0.6456	0.063*
C13	−0.0210 (3)	0.47287 (18)	0.66499 (5)	0.0482 (4)
C14	−0.0734 (3)	0.3726 (2)	0.70156 (6)	0.0531 (4)
H14A	−0.2093	0.3166	0.6982	0.064*
C15	0.0749 (3)	0.3551 (2)	0.74308 (6)	0.0505 (4)
H15A	0.0379	0.2873	0.7672	0.061*
C16	−0.1878 (3)	0.5006 (2)	0.62043 (6)	0.0604 (4)
H16A	−0.1102	0.4892	0.5920	0.091*
H16B	−0.2492	0.6049	0.6215	0.091*
H16C	−0.3089	0.4252	0.6197	0.091*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0873 (4)	0.1316 (6)	0.0578 (3)	−0.0190 (4)	−0.0114 (3)	−0.0225 (3)
O1	0.0601 (8)	0.0737 (8)	0.0831 (9)	0.0200 (7)	−0.0156 (7)	−0.0148 (7)
O2	0.0487 (6)	0.0890 (9)	0.0452 (6)	−0.0116 (6)	0.0008 (5)	−0.0060 (6)
O3	0.0746 (8)	0.0656 (8)	0.0513 (7)	−0.0104 (7)	−0.0006 (6)	0.0087 (6)
C1	0.0517 (9)	0.0576 (10)	0.0617 (10)	0.0007 (8)	0.0071 (8)	−0.0088 (8)
C2	0.0714 (12)	0.0683 (11)	0.0555 (10)	−0.0103 (10)	0.0130 (9)	−0.0163 (8)
C3	0.0615 (10)	0.0705 (11)	0.0438 (8)	−0.0165 (9)	0.0011 (7)	−0.0034 (8)
C4	0.0510 (9)	0.0736 (11)	0.0526 (9)	0.0014 (8)	−0.0044 (7)	−0.0015 (8)
C5	0.0518 (9)	0.0582 (9)	0.0480 (8)	0.0033 (7)	0.0011 (7)	−0.0065 (7)
C6	0.0466 (8)	0.0462 (8)	0.0457 (8)	−0.0043 (6)	0.0039 (6)	−0.0001 (6)
C7	0.0452 (8)	0.0482 (8)	0.0518 (8)	−0.0021 (7)	−0.0002 (7)	0.0017 (7)
C8	0.0470 (9)	0.0747 (11)	0.0503 (9)	0.0005 (8)	−0.0042 (7)	−0.0102 (8)
C9	0.0497 (8)	0.0485 (8)	0.0469 (8)	0.0006 (7)	0.0046 (7)	−0.0075 (7)
C10	0.0455 (8)	0.0443 (7)	0.0418 (7)	−0.0007 (6)	0.0059 (6)	−0.0054 (6)
C11	0.0483 (8)	0.0488 (8)	0.0522 (8)	−0.0082 (7)	0.0071 (7)	0.0001 (7)
C12	0.0617 (10)	0.0492 (8)	0.0467 (8)	−0.0037 (7)	0.0081 (7)	0.0046 (7)
C13	0.0532 (9)	0.0478 (8)	0.0431 (8)	0.0039 (7)	0.0030 (6)	−0.0083 (6)
C14	0.0483 (8)	0.0598 (10)	0.0508 (8)	−0.0109 (7)	0.0040 (7)	−0.0052 (7)
C15	0.0518 (9)	0.0555 (9)	0.0449 (8)	−0.0097 (7)	0.0082 (7)	0.0004 (7)
C16	0.0638 (11)	0.0631 (10)	0.0524 (9)	0.0048 (9)	−0.0030 (8)	−0.0047 (8)

Geometric parameters (Å, º) top

Cl1—C3	1.7400 (17)	C8—H8A	0.9700
O1—C7	1.2062 (19)	C8—H8B	0.9700
O2—C9	1.349 (2)	C9—C10	1.483 (2)
O2—C8	1.4250 (18)	C10—C15	1.383 (2)
O3—C9	1.203 (2)	C10—C11	1.392 (2)
C1—C2	1.375 (2)	C11—C12	1.381 (2)
C1—C6	1.387 (2)	C11—H11A	0.9300
C1—H1A	0.9300	C12—C13	1.385 (2)
C2—C3	1.371 (3)	C12—H12A	0.9300
C2—H2A	0.9300	C13—C14	1.388 (2)
C3—C4	1.377 (3)	C13—C16	1.523 (2)
C4—C5	1.383 (2)	C14—C15	1.387 (2)
C4—H4A	0.9300	C14—H14A	0.9300
C5—C6	1.388 (2)	C15—H15A	0.9300
C5—H5A	0.9300	C16—H16A	0.9600
C6—C7	1.491 (2)	C16—H16B	0.9600
C7—C8	1.495 (2)	C16—H16C	0.9600

C9—O2—C8	117.12 (13)	O3—C9—O2	122.98 (15)
C2—C1—C6	120.75 (17)	O3—C9—C10	125.56 (15)
C2—C1—H1A	119.6	O2—C9—C10	111.46 (14)
C6—C1—H1A	119.6	C15—C10—C11	119.15 (14)
C3—C2—C1	119.28 (17)	C15—C10—C9	119.38 (14)
C3—C2—H2A	120.4	C11—C10—C9	121.45 (14)
C1—C2—H2A	120.4	C12—C11—C10	119.66 (15)
C2—C3—C4	121.52 (16)	C12—C11—H11A	120.2
C2—C3—Cl1	119.91 (15)	C10—C11—H11A	120.2
C4—C3—Cl1	118.57 (15)	C11—C12—C13	121.67 (15)
C3—C4—C5	118.90 (17)	C11—C12—H12A	119.2
C3—C4—H4A	120.5	C13—C12—H12A	119.2
C5—C4—H4A	120.5	C12—C13—C14	118.22 (14)
C4—C5—C6	120.60 (16)	C12—C13—C16	120.48 (15)
C4—C5—H5A	119.7	C14—C13—C16	121.28 (15)
C6—C5—H5A	119.7	C15—C14—C13	120.59 (15)
C1—C6—C5	118.94 (15)	C15—C14—H14A	119.7
C1—C6—C7	118.97 (15)	C13—C14—H14A	119.7
C5—C6—C7	122.08 (14)	C10—C15—C14	120.61 (15)
O1—C7—C6	121.57 (15)	C10—C15—H15A	119.7
O1—C7—C8	120.98 (15)	C14—C15—H15A	119.7
C6—C7—C8	117.46 (13)	C13—C16—H16A	109.5
O2—C8—C7	111.72 (14)	C13—C16—H16B	109.5
O2—C8—H8A	109.3	H16A—C16—H16B	109.5
C7—C8—H8A	109.3	C13—C16—H16C	109.5
O2—C8—H8B	109.3	H16A—C16—H16C	109.5
C7—C8—H8B	109.3	H16B—C16—H16C	109.5
H8A—C8—H8B	107.9

C6—C1—C2—C3	0.6 (3)	C8—O2—C9—O3	−3.1 (2)
C1—C2—C3—C4	−0.9 (3)	C8—O2—C9—C10	176.99 (14)
C1—C2—C3—Cl1	179.20 (14)	O3—C9—C10—C15	−5.7 (2)
C2—C3—C4—C5	0.6 (3)	O2—C9—C10—C15	174.20 (14)
Cl1—C3—C4—C5	−179.55 (14)	O3—C9—C10—C11	172.90 (16)
C3—C4—C5—C6	0.1 (3)	O2—C9—C10—C11	−7.2 (2)
C2—C1—C6—C5	0.0 (3)	C15—C10—C11—C12	2.2 (2)
C2—C1—C6—C7	−179.28 (16)	C9—C10—C11—C12	−176.38 (15)
C4—C5—C6—C1	−0.4 (3)	C10—C11—C12—C13	0.3 (3)
C4—C5—C6—C7	178.91 (16)	C11—C12—C13—C14	−2.6 (2)
C1—C6—C7—O1	2.9 (3)	C11—C12—C13—C16	176.20 (15)
C5—C6—C7—O1	−176.38 (18)	C12—C13—C14—C15	2.3 (2)
C1—C6—C7—C8	−177.07 (16)	C16—C13—C14—C15	−176.49 (15)
C5—C6—C7—C8	3.6 (2)	C11—C10—C15—C14	−2.5 (2)
C9—O2—C8—C7	−77.7 (2)	C9—C10—C15—C14	176.13 (15)
O1—C7—C8—O2	7.0 (3)	C13—C14—C15—C10	0.2 (3)
C6—C7—C8—O2	−173.03 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16C···O1ⁱ	0.96	2.46	3.383 (2)	162

Symmetry code: (i) −x, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₃ClO₃
M_r	288.71
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	297
a, b, c (Å)	5.9132 (4), 8.5044 (6), 27.8767 (18)
β (°)	95.880 (1)
V (Å³)	1394.49 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.51 × 0.30 × 0.06

Data collection
Diffractometer	Bruker SMART APEXII DUO CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.871, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	21275, 4070, 2628
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.706

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.144, 1.05
No. of reflections	4070
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.42

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16C···O1ⁱ	0.96	2.46	3.383 (2)	162

Symmetry code: (i) −x, y−1/2, −z+3/2.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: C-7581-2009.

Acknowledgements

HKF and WSL thank Universiti Sains Malaysia (USM) for the Research University Grant (No. 1001/PFIZIK/811160). WSL also thanks the Malaysian government and USM for the award of the post of Research Officer under the Research University Grant (No. 1001/PFIZIK/811160). AMI thanks Professor Sandeep Sanchethi, Director of the National Institute of Technology-Karnataka, India for providing the research facilities. AMI also thanks the Board for Research in Nuclear Sciences, Department of Atomic Energy, Government of India for the `Young Scientist' award. MNS thanks the Department of Information Technology, Government of India for financial support.

References

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