2-(4-Chloro­phen­yl)-2-oxoethyl 4-hy­droxy­benzoate

The title compound, C₁₅H₁₁ClO₄, consists of a chloro­benzene ring and a phenol ring which are linked together by a 1,4-dioxo-2-oxabutane-1,4-diyl group. The dihedral angle between the chloro­benzene and phenol rings is 65.70 (11)°. In the crystal, inter­molecular O—H...O hydrogen bonds link the mol­ecules into chains along [010].

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.044
• wR factor = 0.106
• Data-to-parameter ratio = 19.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          8
PLAT915_ALERT_3_C Low Friedel Pair Coverage ......................         83 Perc.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           30.00
           From the CIF: _reflns_number_total               3571
           Count of symmetry unique reflns         2069
           Completeness (_total/calc)            172.60%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1502
           Fraction of Friedel pairs measured     0.726
           Are heavy atom types Z>Si present        yes
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          1

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Phenacyl benzoate is a derivative of an acid formed by reaction between an acid and phenacyl bromide. These compounds find applications in the field of synthetic chemistry (Huang et al., 1996; Gandhi et al., 1995) such as in the synthesis of oxazoles, imidazoles, and benzoxazepines. They are also useful for photo-removable protecting groups for carboxylic acids in organic synthesis and biochemistry (Ruzicka et al., 2002; Litera et al., 2006; Sheehan & Umezaw, 1973). Keeping this in view, the title compound was synthesized to study its crystal structure.

The title compound, (Fig. 1), consists of a chlorobenzene (Cl1/C1–C6) ring and a phenol(O4/C10–C15) ring which are linked together by a 2-oxopropyl acetate (C7–C9/O1–O3) group. The dihedral angle formed between the chlorobenzene and a phenol ring is 65.70 (11) °. The bond lengths (Allen et al., 1987) and angles are within normal ranges.

In the crystal packing (Fig. 2), intermolecular O4—H1O4···O3 hydrogen bonds (Table 1) link the molecules in one-dimensional chains along [010].

Related literature

For background to phenacyl benzoate, see: Sheehan & Umezaw (1973); Gandhi et al. (1995); Huang et al. (1996); Ruzicka et al. (2002); Litera et al. (2006). For bond-length data, see: Allen et al. (1987).

S2. Experimental

The mixture of 4-hydroxybenzoic acid (1.0 g, 0.0072 mol), potassium carbonate (1.10 g, 0.0079 mol) and 2-bromo-1-(4-chlorophenyl)ethanone (1.68 g, 0.0072 mol) in dimethylformamide (10 ml) was stirred at room temperature for 2 h. On cooling, colorless needle-shaped 2-(4-chlorophenyl)-2-oxoethyl 4-hydroxybenzoate begin to separate out. It was collected by filtration and recrystallized from ethanol. Yield: 1.95 g, 92.8%, M.p: 453–454 K.

S3. Refinement

The hydrogen atoms bound to C atoms were positioned geometrically [C–H = 0.9300–0.9700 Å] with U_iso(H) = 1.2. The hydrogen atoms attached to the O atom was located from the difference map and refined freely, [O–H = 0.79 (3) Å].

Computing details

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) and PLATON (Spek, 2009).

Figures

	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 a axis, showing a one-dimensional chain along [010].

2-(4-Chlorophenyl)-2-oxoethyl 4-hydroxybenzoate

Crystal data

C15H11ClO4	F(000) = 300
Mr = 290.69	Dx = 1.450 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1832 reflections
a = 5.5307 (10) Å	θ = 3.7–24.1°
b = 8.1324 (15) Å	µ = 0.30 mm^−1
c = 14.857 (2) Å	T = 296 K
β = 95.120 (4)°	Plate, colourless
V = 665.57 (19) Å^3	0.56 × 0.23 × 0.07 mm
Z = 2

Data collection

Bruker APEXII DUO CCD area-detector diffractometer	3571 independent reflections
Radiation source: fine-focus sealed tube	2457 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
φ and ω scans	θmax = 30.0°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −5→7
Tmin = 0.852, Tmax = 0.981	k = −11→11
6399 measured reflections	l = −20→20

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.0346P)^2 + 0.0709P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
3571 reflections	Δρmax = 0.20 e Å^−3
186 parameters	Δρmin = −0.21 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1511 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.20 (8)

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	0.97678 (16)	1.71550 (10)	0.56971 (5)	0.0916 (3)
O1	0.4790 (3)	0.9949 (3)	0.66410 (13)	0.0797 (5)
O2	0.7288 (3)	0.81404 (19)	0.79114 (12)	0.0616 (4)
O3	0.4559 (4)	0.95006 (19)	0.86448 (13)	0.0700 (5)
O4	0.2024 (3)	0.2039 (2)	0.93940 (13)	0.0633 (4)
C1	0.6002 (4)	1.3072 (3)	0.60310 (14)	0.0559 (5)
H1A	0.4508	1.2636	0.5815	0.067*
C2	0.6676 (5)	1.4603 (4)	0.57413 (16)	0.0634 (6)
H2A	0.5650	1.5196	0.5331	0.076*
C3	0.8875 (5)	1.5239 (3)	0.60661 (15)	0.0579 (6)
C4	1.0422 (4)	1.4387 (3)	0.66746 (16)	0.0587 (6)
H4A	1.1905	1.4837	0.6893	0.070*
C5	0.9738 (4)	1.2856 (3)	0.69547 (15)	0.0548 (5)
H5A	1.0778	1.2268	0.7362	0.066*
C6	0.7520 (4)	1.2176 (3)	0.66383 (12)	0.0466 (4)
C7	0.6694 (4)	1.0548 (3)	0.69417 (15)	0.0544 (5)
C8	0.8296 (4)	0.9684 (3)	0.76653 (18)	0.0609 (6)
H8A	0.9879	0.9496	0.7451	0.073*
H8B	0.8517	1.0382	0.8195	0.073*
C9	0.5374 (4)	0.8211 (3)	0.84121 (15)	0.0521 (5)
C10	0.4532 (4)	0.6572 (3)	0.86395 (13)	0.0458 (5)
C11	0.2512 (4)	0.6426 (3)	0.91413 (14)	0.0535 (5)
H11A	0.1713	0.7367	0.9312	0.064*
C12	0.1709 (4)	0.4916 (3)	0.93820 (14)	0.0565 (6)
H12A	0.0353	0.4834	0.9707	0.068*
C13	0.2901 (4)	0.3505 (3)	0.91444 (14)	0.0467 (5)
C14	0.4930 (4)	0.3639 (3)	0.86646 (15)	0.0520 (5)
H14A	0.5763	0.2698	0.8516	0.062*
C15	0.5711 (4)	0.5153 (3)	0.84087 (15)	0.0495 (5)
H15A	0.7052	0.5229	0.8075	0.059*
H1O4	0.289 (6)	0.135 (5)	0.924 (2)	0.083 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1111 (6)	0.0700 (4)	0.0958 (5)	−0.0168 (4)	0.0211 (4)	0.0258 (4)
O1	0.0787 (12)	0.0704 (12)	0.0853 (11)	−0.0250 (11)	−0.0197 (9)	0.0065 (11)
O2	0.0618 (9)	0.0398 (8)	0.0840 (10)	0.0020 (8)	0.0114 (8)	0.0072 (9)
O3	0.0857 (12)	0.0393 (9)	0.0855 (12)	0.0051 (9)	0.0107 (10)	−0.0103 (9)
O4	0.0671 (10)	0.0527 (10)	0.0728 (10)	−0.0026 (10)	0.0207 (8)	0.0070 (9)
C1	0.0540 (12)	0.0605 (15)	0.0527 (11)	0.0018 (12)	0.0012 (9)	0.0002 (12)
C2	0.0657 (14)	0.0673 (16)	0.0562 (12)	0.0059 (13)	0.0010 (11)	0.0138 (12)
C3	0.0674 (14)	0.0545 (13)	0.0546 (11)	−0.0056 (12)	0.0208 (10)	0.0081 (11)
C4	0.0508 (12)	0.0629 (15)	0.0633 (13)	−0.0090 (12)	0.0096 (10)	−0.0003 (12)
C5	0.0509 (11)	0.0545 (13)	0.0587 (12)	−0.0006 (11)	0.0032 (9)	0.0043 (11)
C6	0.0480 (10)	0.0479 (11)	0.0444 (9)	0.0032 (10)	0.0066 (8)	−0.0032 (10)
C7	0.0560 (12)	0.0485 (12)	0.0582 (12)	−0.0018 (11)	0.0018 (10)	−0.0061 (11)
C8	0.0563 (12)	0.0468 (13)	0.0788 (15)	−0.0019 (11)	0.0014 (11)	0.0101 (12)
C9	0.0566 (12)	0.0415 (12)	0.0567 (12)	0.0036 (11)	−0.0031 (10)	−0.0033 (11)
C10	0.0485 (10)	0.0385 (10)	0.0499 (11)	0.0024 (9)	0.0009 (8)	−0.0027 (9)
C11	0.0536 (12)	0.0481 (12)	0.0595 (12)	0.0093 (10)	0.0085 (10)	−0.0084 (11)
C12	0.0519 (12)	0.0622 (15)	0.0568 (12)	0.0049 (12)	0.0128 (9)	−0.0031 (12)
C13	0.0510 (11)	0.0441 (11)	0.0451 (10)	−0.0010 (10)	0.0052 (9)	0.0012 (9)
C14	0.0580 (12)	0.0401 (12)	0.0594 (12)	0.0063 (10)	0.0128 (10)	−0.0010 (10)
C15	0.0489 (11)	0.0435 (11)	0.0569 (11)	0.0025 (11)	0.0101 (9)	−0.0013 (11)

Geometric parameters (Å, º)

Cl1—C3	1.738 (3)	C5—H5A	0.9300
O1—C7	1.209 (3)	C6—C7	1.483 (3)
O2—C9	1.349 (3)	C7—C8	1.505 (3)
O2—C8	1.434 (3)	C8—H8A	0.9700
O3—C9	1.204 (3)	C8—H8B	0.9700
O4—C13	1.351 (3)	C9—C10	1.461 (3)
O4—H1O4	0.79 (3)	C10—C15	1.384 (3)
C1—C2	1.380 (4)	C10—C11	1.402 (3)
C1—C6	1.383 (3)	C11—C12	1.364 (4)
C1—H1A	0.9300	C11—H11A	0.9300
C2—C3	1.369 (4)	C12—C13	1.385 (3)
C2—H2A	0.9300	C12—H12A	0.9300
C3—C4	1.375 (4)	C13—C14	1.386 (3)
C4—C5	1.376 (3)	C14—C15	1.370 (3)
C4—H4A	0.9300	C14—H14A	0.9300
C5—C6	1.389 (3)	C15—H15A	0.9300
C9—O2—C8	116.48 (19)	C7—C8—H8A	109.2
C13—O4—H1O4	108 (2)	O2—C8—H8B	109.2
C2—C1—C6	120.9 (2)	C7—C8—H8B	109.2
C2—C1—H1A	119.5	H8A—C8—H8B	107.9
C6—C1—H1A	119.5	O3—C9—O2	121.8 (2)
C3—C2—C1	119.2 (2)	O3—C9—C10	126.4 (2)
C3—C2—H2A	120.4	O2—C9—C10	111.78 (19)
C1—C2—H2A	120.4	C15—C10—C11	118.4 (2)
C2—C3—C4	121.5 (2)	C15—C10—C9	122.44 (19)
C2—C3—Cl1	119.7 (2)	C11—C10—C9	119.07 (19)
C4—C3—Cl1	118.8 (2)	C12—C11—C10	120.6 (2)
C3—C4—C5	118.9 (2)	C12—C11—H11A	119.7
C3—C4—H4A	120.5	C10—C11—H11A	119.7
C5—C4—H4A	120.5	C11—C12—C13	120.35 (19)
C4—C5—C6	121.1 (2)	C11—C12—H12A	119.8
C4—C5—H5A	119.5	C13—C12—H12A	119.8
C6—C5—H5A	119.5	O4—C13—C12	118.0 (2)
C1—C6—C5	118.5 (2)	O4—C13—C14	122.5 (2)
C1—C6—C7	118.9 (2)	C12—C13—C14	119.5 (2)
C5—C6—C7	122.6 (2)	C15—C14—C13	120.2 (2)
O1—C7—C6	122.0 (2)	C15—C14—H14A	119.9
O1—C7—C8	120.9 (2)	C13—C14—H14A	119.9
C6—C7—C8	117.15 (19)	C14—C15—C10	120.92 (19)
O2—C8—C7	111.9 (2)	C14—C15—H15A	119.5
O2—C8—H8A	109.2	C10—C15—H15A	119.5
C6—C1—C2—C3	−0.3 (3)	C8—O2—C9—O3	−0.4 (3)
C1—C2—C3—C4	−0.1 (4)	C8—O2—C9—C10	−178.72 (19)
C1—C2—C3—Cl1	179.18 (18)	O3—C9—C10—C15	−174.2 (2)
C2—C3—C4—C5	0.5 (3)	O2—C9—C10—C15	4.1 (3)
Cl1—C3—C4—C5	−178.78 (17)	O3—C9—C10—C11	3.2 (3)
C3—C4—C5—C6	−0.5 (3)	O2—C9—C10—C11	−178.51 (18)
C2—C1—C6—C5	0.3 (3)	C15—C10—C11—C12	−1.1 (3)
C2—C1—C6—C7	178.9 (2)	C9—C10—C11—C12	−178.6 (2)
C4—C5—C6—C1	0.1 (3)	C10—C11—C12—C13	0.9 (3)
C4—C5—C6—C7	−178.4 (2)	C11—C12—C13—O4	−179.6 (2)
C1—C6—C7—O1	3.7 (3)	C11—C12—C13—C14	0.4 (3)
C5—C6—C7—O1	−177.8 (2)	O4—C13—C14—C15	178.4 (2)
C1—C6—C7—C8	−174.6 (2)	C12—C13—C14—C15	−1.6 (3)
C5—C6—C7—C8	4.0 (3)	C13—C14—C15—C10	1.4 (3)
C9—O2—C8—C7	−73.7 (3)	C11—C10—C15—C14	−0.1 (3)
O1—C7—C8—O2	0.8 (3)	C9—C10—C15—C14	177.3 (2)
C6—C7—C8—O2	179.02 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1O4···O3^i	0.78 (4)	2.01 (4)	2.783 (3)	168 (3)

Symmetry code: (i) x, y−1, z.