2-(4-Chloro­phen­yl)-2-oxoethyl benzoate

Abstract

In the title compound, C₁₅H₁₁ClO₃, the dihedral angle between the aromatic rings is 84.29 (8)°. In the crystal, mol­ecules are linked by weak C—H⋯π inter­actions.

Related literature

For applications of phenacyl benzoate derivatives, see: Rather & Reid (1919 ▶); Litera et al. (2006 ▶); Huang et al. (1996 ▶); Gandhi et al. (1995 ▶). For related structures, see: Ogata et al. (1987 ▶); Wan et al. (2006 ▶); Zhang et al. (2006 ▶). For reported melting-point details, see: Le et al. (2009 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

• C₁₅H₁₁ClO₃

• M _r = 274.69

• Monoclinic,

• a = 8.1955 (9) Å

• b = 10.8717 (12) Å

• c = 16.5420 (15) Å

• β = 117.816 (4)°

• V = 1303.6 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 0.29 mm⁻¹

• T = 296 K

• 0.34 × 0.19 × 0.19 mm

Data collection

• Bruker SMART APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.908, T _max = 0.948

• 11201 measured reflections

• 4052 independent reflections

• 2720 reflections with I > 2σ(I)

• R _int = 0.021

Refinement

• R[F ² > 2σ(F ²)] = 0.044

• wR(F ²) = 0.126

• S = 1.03

• 4052 reflections

• 172 parameters

• H-atom parameters constrained

• Δρ_max = 0.31 e Å⁻³

• Δρ_min = −0.49 e Å⁻³

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 and PLATON (Spek, 2009 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S160053681102383X/hb5918Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg2 is the centroid of the C10–C15 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯Cg2i	0.97	2.96	3.4952 (17)	116

Symmetry code: (i) .

supplementary crystallographic information

Comment

Phenacyl benzoate derivatives are very important in identification of organic acids (Rather & Reid, 1919) as they undergo photolysis in neutral and mild conditions (Litera et al., 2006). They find applications in the field of synthetic chemistry for the synthesis of oxazoles, imidazoles (Huang et al., 1996) and benzoxazepine (Gandhi et al., 1995). We hereby report the crystal structure of the title compound, (I).

The asymmetric unit of title compound is shown in Fig. 1. The dihedral angle between the phenyl (C10–C15) ring and the chloro-substituted phenyl (C1–C6) ring is 84.29 (8)°. The bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to those closely related structures (Ogata et al., 1987; Wan et al., 2006; Zhang et al., 2006).

In the crystal (Fig. 2), there are no classical hydrogen bonds but stabilization is provided by weak C—H···π (Table 1) interactions, involving the Cg2 (C10–C15) ring.

Experimental

A mixture of benzoic acid (1.0 g, 0.0081 mol), potassium carbonate (1.23 g, 0.0089 mol) and 2-bromo-1-(4-chlorophenyl) ethanone (1.81 g, 0.0081 mol) in dimethylformamide (10 ml) was stirred at room temperature for 2 h. On cooling, colorless needle-shaped crystals of 2-(4-chlorophenyl)-2-oxoethyl benzoate begin to separate out. These were collected by filtration and recrystallized from ethanol to yield colourless blocks of (I). Yield: 2.10 g, 93.7%, Mp: 119–120 °C (Le et al., 2009).

Refinement

All the H atoms were positioned geometrically [C–H = 0.93–0.97 Å] and were refined using a riding model, with U_iso(H) =1.2. U_eq(C).

Figures

Fig. 1.

The molecular structure of the title compound, showing 30% probability displacement ellipsoids.

Fig. 2.

The crystal packing of the title compound (I).

Crystal data

C15H11ClO3	F(000) = 568
Mr = 274.69	Dx = 1.400 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2797 reflections
a = 8.1955 (9) Å	θ = 2.3–27.1°
b = 10.8717 (12) Å	µ = 0.29 mm−1
c = 16.5420 (15) Å	T = 296 K
β = 117.816 (4)°	Block, colourless
V = 1303.6 (2) Å3	0.34 × 0.19 × 0.19 mm
Z = 4

Data collection

Bruker SMART APEXII CCD diffractometer	4052 independent reflections
Radiation source: fine-focus sealed tube	2720 reflections with I > 2σ(I)
graphite	Rint = 0.021
φ and ω scans	θmax = 30.8°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.908, Tmax = 0.948	k = −15→15
11201 measured reflections	l = −20→23

Refinement

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0504P)2 + 0.2649P] where P = (Fo2 + 2Fc2)/3
4052 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.49 e Å−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
Cl1	0.98407 (8)	1.29129 (4)	1.01748 (4)	0.07410 (18)
O1	0.41826 (16)	0.81706 (12)	0.81726 (7)	0.0648 (3)
O2	0.41542 (15)	0.64299 (10)	0.93059 (7)	0.0544 (3)
O3	0.59892 (16)	0.55553 (13)	0.87990 (9)	0.0722 (4)
C1	0.6218 (2)	1.03708 (15)	0.86536 (10)	0.0509 (3)
H1A	0.5394	1.0250	0.8040	0.061*
C2	0.7272 (2)	1.14249 (14)	0.89170 (12)	0.0545 (4)
H2A	0.7170	1.2011	0.8486	0.065*
C3	0.8484 (2)	1.15975 (14)	0.98327 (11)	0.0507 (3)
C4	0.8651 (2)	1.07434 (15)	1.04787 (11)	0.0555 (4)
H4A	0.9469	1.0874	1.1092	0.067*
C5	0.7593 (2)	0.96902 (14)	1.02070 (10)	0.0505 (3)
H5A	0.7701	0.9109	1.0642	0.061*
C6	0.63658 (18)	0.94852 (13)	0.92902 (9)	0.0435 (3)
C7	0.52322 (18)	0.83503 (14)	0.89703 (10)	0.0458 (3)
C8	0.5435 (2)	0.74141 (15)	0.96859 (10)	0.0524 (4)
H8A	0.6680	0.7087	0.9967	0.063*
H8B	0.5243	0.7814	1.0159	0.063*
C9	0.4586 (2)	0.55549 (15)	0.88590 (10)	0.0510 (3)
C10	0.3128 (2)	0.46016 (14)	0.84710 (9)	0.0473 (3)
C11	0.1476 (2)	0.47129 (15)	0.85064 (10)	0.0520 (3)
H11A	0.1261	0.5397	0.8781	0.062*
C12	0.0150 (2)	0.38051 (17)	0.81327 (11)	0.0622 (4)
H12A	−0.0966	0.3888	0.8147	0.075*
C13	0.0468 (3)	0.27865 (18)	0.77419 (12)	0.0688 (5)
H13A	−0.0424	0.2174	0.7498	0.083*
C14	0.2104 (3)	0.26665 (17)	0.77089 (12)	0.0706 (5)
H14A	0.2317	0.1970	0.7445	0.085*
C15	0.3436 (3)	0.35746 (15)	0.80651 (11)	0.0587 (4)
H15A	0.4534	0.3496	0.8032	0.070*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0961 (4)	0.0549 (3)	0.0902 (4)	−0.0203 (2)	0.0593 (3)	−0.0167 (2)
O1	0.0575 (7)	0.0764 (8)	0.0440 (6)	−0.0114 (6)	0.0100 (5)	0.0018 (5)
O2	0.0573 (6)	0.0533 (6)	0.0590 (6)	−0.0116 (5)	0.0325 (5)	−0.0065 (5)
O3	0.0551 (7)	0.0808 (9)	0.0885 (9)	−0.0061 (6)	0.0399 (7)	−0.0124 (7)
C1	0.0525 (8)	0.0567 (9)	0.0423 (7)	0.0060 (7)	0.0212 (6)	0.0066 (6)
C2	0.0646 (9)	0.0483 (8)	0.0593 (9)	0.0064 (7)	0.0361 (8)	0.0109 (7)
C3	0.0559 (8)	0.0453 (7)	0.0615 (9)	−0.0017 (6)	0.0362 (7)	−0.0066 (7)
C4	0.0624 (9)	0.0564 (9)	0.0471 (8)	−0.0057 (7)	0.0251 (7)	−0.0062 (7)
C5	0.0583 (8)	0.0518 (8)	0.0404 (7)	−0.0027 (7)	0.0222 (6)	0.0035 (6)
C6	0.0434 (7)	0.0475 (7)	0.0411 (7)	0.0036 (6)	0.0210 (6)	0.0020 (6)
C7	0.0404 (7)	0.0535 (8)	0.0419 (7)	0.0010 (6)	0.0179 (6)	0.0008 (6)
C8	0.0554 (8)	0.0541 (8)	0.0462 (8)	−0.0102 (7)	0.0224 (7)	−0.0010 (7)
C9	0.0506 (8)	0.0537 (8)	0.0485 (8)	0.0010 (7)	0.0229 (7)	0.0053 (7)
C10	0.0526 (8)	0.0463 (7)	0.0405 (7)	0.0016 (6)	0.0196 (6)	0.0066 (6)
C11	0.0545 (8)	0.0520 (8)	0.0486 (8)	−0.0029 (7)	0.0233 (7)	0.0030 (7)
C12	0.0579 (9)	0.0679 (10)	0.0539 (9)	−0.0110 (8)	0.0203 (8)	0.0042 (8)
C13	0.0739 (12)	0.0609 (10)	0.0541 (10)	−0.0154 (9)	0.0151 (9)	0.0009 (8)
C14	0.0960 (14)	0.0496 (9)	0.0526 (10)	0.0016 (9)	0.0233 (10)	−0.0037 (8)
C15	0.0692 (10)	0.0547 (9)	0.0520 (9)	0.0092 (8)	0.0282 (8)	0.0051 (7)

Geometric parameters (Å, °)

Cl1—C3	1.7362 (16)	C7—C8	1.510 (2)
O1—C7	1.2083 (17)	C8—H8A	0.9700
O2—C9	1.3492 (19)	C8—H8B	0.9700
O2—C8	1.4235 (18)	C9—C10	1.482 (2)
O3—C9	1.1996 (18)	C10—C15	1.385 (2)
C1—C2	1.378 (2)	C10—C11	1.388 (2)
C1—C6	1.390 (2)	C11—C12	1.382 (2)
C1—H1A	0.9300	C11—H11A	0.9300
C2—C3	1.383 (2)	C12—C13	1.367 (3)
C2—H2A	0.9300	C12—H12A	0.9300
C3—C4	1.373 (2)	C13—C14	1.373 (3)
C4—C5	1.379 (2)	C13—H13A	0.9300
C4—H4A	0.9300	C14—C15	1.384 (3)
C5—C6	1.3920 (19)	C14—H14A	0.9300
C5—H5A	0.9300	C15—H15A	0.9300
C6—C7	1.486 (2)
C9—O2—C8	116.36 (12)	O2—C8—H8B	109.3
C2—C1—C6	121.10 (14)	C7—C8—H8B	109.3
C2—C1—H1A	119.5	H8A—C8—H8B	107.9
C6—C1—H1A	119.5	O3—C9—O2	123.48 (15)
C1—C2—C3	118.90 (14)	O3—C9—C10	125.06 (15)
C1—C2—H2A	120.6	O2—C9—C10	111.46 (13)
C3—C2—H2A	120.6	C15—C10—C11	119.52 (15)
C4—C3—C2	121.36 (15)	C15—C10—C9	118.75 (14)
C4—C3—Cl1	119.15 (13)	C11—C10—C9	121.72 (14)
C2—C3—Cl1	119.49 (13)	C12—C11—C10	119.86 (16)
C3—C4—C5	119.25 (15)	C12—C11—H11A	120.1
C3—C4—H4A	120.4	C10—C11—H11A	120.1
C5—C4—H4A	120.4	C13—C12—C11	120.41 (18)
C4—C5—C6	120.85 (14)	C13—C12—H12A	119.8
C4—C5—H5A	119.6	C11—C12—H12A	119.8
C6—C5—H5A	119.6	C12—C13—C14	120.06 (17)
C1—C6—C5	118.54 (14)	C12—C13—H13A	120.0
C1—C6—C7	119.12 (13)	C14—C13—H13A	120.0
C5—C6—C7	122.34 (13)	C13—C14—C15	120.43 (17)
O1—C7—C6	122.11 (14)	C13—C14—H14A	119.8
O1—C7—C8	120.59 (14)	C15—C14—H14A	119.8
C6—C7—C8	117.30 (12)	C14—C15—C10	119.69 (17)
O2—C8—C7	111.81 (12)	C14—C15—H15A	120.2
O2—C8—H8A	109.3	C10—C15—H15A	120.2
C7—C8—H8A	109.3
C6—C1—C2—C3	−0.4 (2)	C6—C7—C8—O2	174.36 (12)
C1—C2—C3—C4	−0.1 (2)	C8—O2—C9—O3	2.5 (2)
C1—C2—C3—Cl1	179.31 (11)	C8—O2—C9—C10	−178.30 (12)
C2—C3—C4—C5	0.3 (2)	O3—C9—C10—C15	5.2 (2)
Cl1—C3—C4—C5	−179.14 (12)	O2—C9—C10—C15	−173.94 (13)
C3—C4—C5—C6	0.0 (2)	O3—C9—C10—C11	−174.87 (16)
C2—C1—C6—C5	0.7 (2)	O2—C9—C10—C11	5.9 (2)
C2—C1—C6—C7	−178.58 (13)	C15—C10—C11—C12	−0.4 (2)
C4—C5—C6—C1	−0.5 (2)	C9—C10—C11—C12	179.72 (14)
C4—C5—C6—C7	178.73 (14)	C10—C11—C12—C13	1.1 (2)
C1—C6—C7—O1	0.0 (2)	C11—C12—C13—C14	−0.8 (3)
C5—C6—C7—O1	−179.21 (15)	C12—C13—C14—C15	−0.3 (3)
C1—C6—C7—C8	−179.92 (13)	C13—C14—C15—C10	1.1 (3)
C5—C6—C7—C8	0.9 (2)	C11—C10—C15—C14	−0.7 (2)
C9—O2—C8—C7	79.04 (17)	C9—C10—C15—C14	179.19 (15)
O1—C7—C8—O2	−5.6 (2)

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C10–C15 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···Cg2i	0.97	2.96	3.4952 (17)	116

Symmetry codes: (i) −x+1, −y+1, −z+2.