Benzoyl­methyl 4-methoxy­benzoate

The title compound, C₁₆H₁₄O₄, was obtained by the reaction of 4-methoxy­benzoic acid and phenacyl bromide. The dihedral angle between the two aromatic rings is 71.21 (6)°. The mol­ecules are linked into a two-dimensional network parallel to the ab plane by C—H...O and C—H...π inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.035
• wR factor = 0.092
• Data-to-parameter ratio = 14.4

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S1. Comment

The title compound was synthesized for a study of protection of carboxyl group. The phenacyl group has proved to be an important reagent for protecting carboxyl functions during organic synthesis in presence of other esters (Hendrickson & Kandall, 1970).

The molecular structure of the title compound is shown in Fig. 1. The dihedral angle between the two aromatic rings is 71.21 (6)°. Weak C—H···O hydrogen bonds and C—H···π interactions help to stabilize the crystal structure (Table 1). The molecules are linked into a two-dimensional network parallel to the ab plane by the above interactions.

Related literature

For related literature, see: Hendrickson & Kandall (1970).

S2. Experimental

4-Methoxybenzoic acid (0.76 g, 5 mmol) was dissolved in tetrahydrofuran (20 ml). Triethylamine (0.7 ml) and phenacyl bromide (0.989 g, 5 mmol) were added to the solution with stirring. The stirring was continued for overnight at room temperature. The tetrahydrofuran was removed in vacuo and the residue was recrystallized from ethyl acetate to give the title compound in 88% yield.

S3. Refinement

H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 Å (aromatic), 0.97 Å (methylene), 0.96 Å (methyl), and with U_iso(H) = 1.2U_eq(c) for aromatic and methylene H atoms or 1.5U_eq(c) for methyl H atoms.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids.

Benzoylmethyl 4-methoxybenzoate

Crystal data

C16H14O4	F(000) = 568
Mr = 270.27	Dx = 1.341 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3973 reflections
a = 8.0618 (2) Å	θ = 2.4–32.5°
b = 9.6671 (3) Å	µ = 0.10 mm^−1
c = 17.1819 (5) Å	T = 298 K
β = 91.535 (3)°	Plate, colourless
V = 1338.58 (7) Å^3	0.40 × 0.27 × 0.17 mm
Z = 4

Data collection

Bruker APEX area-detector diffractometer	2615 independent reflections
Radiation source: fine-focus sealed tube	1873 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ϕ and ω scans	θmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
Tmin = 0.962, Tmax = 0.984	k = −11→11
9851 measured reflections	l = −20→21

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0534P)^2] where P = (Fo^2 + 2Fc^2)/3
2615 reflections	(Δ/σ)max = 0.001
181 parameters	Δρmax = 0.11 e Å^−3
0 restraints	Δρmin = −0.17 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
O1	0.06068 (12)	0.25236 (10)	0.22525 (6)	0.0523 (3)
O2	0.06074 (10)	0.02414 (9)	0.24485 (6)	0.0428 (3)
O3	0.10480 (11)	0.11666 (13)	0.39171 (6)	0.0625 (3)
O4	−0.64971 (11)	0.09532 (10)	0.08808 (6)	0.0478 (3)
C1	−0.00852 (15)	0.14235 (13)	0.21933 (7)	0.0350 (3)
C2	−0.17527 (15)	0.12207 (12)	0.18382 (7)	0.0318 (3)
C3	−0.26981 (16)	0.23871 (13)	0.16601 (8)	0.0366 (3)
H3	−0.2260	0.3262	0.1758	0.044*
C4	−0.42681 (16)	0.22643 (14)	0.13417 (8)	0.0389 (3)
H4	−0.4891	0.3051	0.1227	0.047*
C5	−0.49259 (15)	0.09587 (13)	0.11908 (7)	0.0343 (3)
C6	−0.39972 (16)	−0.02145 (13)	0.13555 (8)	0.0368 (3)
H6	−0.4431	−0.1088	0.1250	0.044*
C7	−0.24165 (15)	−0.00732 (13)	0.16797 (7)	0.0352 (3)
H7	−0.1790	−0.0859	0.1793	0.042*
C8	0.22653 (15)	0.03720 (15)	0.27621 (8)	0.0434 (4)
H8A	0.2892	0.0978	0.2429	0.052*
H8B	0.2795	−0.0529	0.2762	0.052*
C9	0.23180 (15)	0.09397 (14)	0.35776 (8)	0.0376 (3)
C10	0.39810 (15)	0.11977 (12)	0.39404 (7)	0.0324 (3)
C11	0.54325 (15)	0.09679 (13)	0.35428 (8)	0.0359 (3)
H11	0.5378	0.0654	0.3031	0.043*
C12	0.69576 (16)	0.12042 (14)	0.39048 (8)	0.0399 (3)
H12	0.7926	0.1042	0.3637	0.048*
C13	0.70499 (17)	0.16773 (14)	0.46575 (8)	0.0438 (4)
H13	0.8079	0.1839	0.4898	0.053*
C14	0.56132 (17)	0.19132 (15)	0.50589 (8)	0.0438 (3)
H14	0.5676	0.2239	0.5568	0.053*
C15	0.40934 (16)	0.16673 (13)	0.47056 (8)	0.0391 (3)
H15	0.3131	0.1816	0.4980	0.047*
C16	−0.72513 (18)	−0.03507 (16)	0.07032 (9)	0.0534 (4)
H16A	−0.8352	−0.0203	0.0492	0.080*
H16B	−0.7306	−0.0894	0.1169	0.080*
H16C	−0.6602	−0.0831	0.0328	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0448 (6)	0.0426 (6)	0.0688 (7)	−0.0108 (4)	−0.0098 (5)	0.0053 (5)
O2	0.0345 (5)	0.0390 (5)	0.0544 (6)	0.0035 (4)	−0.0112 (4)	−0.0043 (5)
O3	0.0300 (6)	0.1046 (9)	0.0532 (7)	0.0026 (5)	0.0080 (5)	−0.0067 (6)
O4	0.0396 (5)	0.0473 (6)	0.0557 (6)	−0.0031 (4)	−0.0139 (5)	0.0018 (5)
C1	0.0340 (7)	0.0357 (7)	0.0353 (7)	−0.0011 (6)	0.0030 (6)	−0.0010 (6)
C2	0.0323 (7)	0.0335 (7)	0.0296 (6)	−0.0013 (5)	0.0029 (5)	0.0011 (6)
C3	0.0410 (7)	0.0294 (7)	0.0394 (8)	−0.0027 (5)	−0.0012 (6)	0.0010 (6)
C4	0.0406 (7)	0.0335 (7)	0.0425 (8)	0.0045 (6)	−0.0026 (6)	0.0038 (6)
C5	0.0332 (7)	0.0403 (7)	0.0294 (6)	−0.0012 (5)	−0.0015 (5)	0.0018 (6)
C6	0.0414 (7)	0.0310 (7)	0.0379 (7)	−0.0040 (5)	−0.0012 (6)	−0.0020 (6)
C7	0.0382 (7)	0.0305 (7)	0.0368 (7)	0.0029 (5)	0.0002 (6)	0.0012 (6)
C8	0.0292 (7)	0.0498 (9)	0.0509 (9)	0.0062 (6)	−0.0061 (6)	−0.0086 (7)
C9	0.0311 (7)	0.0400 (8)	0.0418 (8)	0.0028 (5)	0.0025 (6)	0.0039 (6)
C10	0.0307 (6)	0.0311 (7)	0.0354 (7)	0.0021 (5)	0.0020 (5)	0.0031 (6)
C11	0.0326 (7)	0.0420 (8)	0.0330 (7)	0.0010 (5)	0.0016 (5)	−0.0005 (6)
C12	0.0305 (7)	0.0458 (8)	0.0435 (8)	−0.0031 (6)	0.0027 (6)	0.0015 (7)
C13	0.0375 (8)	0.0451 (8)	0.0483 (9)	−0.0053 (6)	−0.0100 (6)	0.0011 (7)
C14	0.0532 (9)	0.0424 (8)	0.0356 (8)	0.0020 (6)	−0.0044 (6)	−0.0046 (6)
C15	0.0405 (8)	0.0403 (8)	0.0366 (7)	0.0070 (6)	0.0061 (6)	0.0006 (6)
C16	0.0457 (8)	0.0581 (10)	0.0557 (9)	−0.0105 (7)	−0.0099 (7)	−0.0085 (8)

Geometric parameters (Å, º)

O1—C1	1.2040 (15)	C8—H8A	0.97
O2—C1	1.3406 (15)	C8—H8B	0.97
O2—C8	1.4331 (15)	C9—C10	1.4844 (18)
O3—C9	1.2119 (15)	C10—C11	1.3886 (16)
O4—C5	1.3609 (15)	C10—C15	1.3916 (18)
O4—C16	1.4289 (17)	C11—C12	1.3820 (18)
C1—C2	1.4743 (18)	C11—H11	0.93
C2—C7	1.3847 (17)	C12—C13	1.3719 (19)
C2—C3	1.3906 (17)	C12—H12	0.93
C3—C4	1.3705 (18)	C13—C14	1.3828 (19)
C3—H3	0.93	C13—H13	0.93
C4—C5	1.3907 (18)	C14—C15	1.3735 (19)
C4—H4	0.93	C14—H14	0.93
C5—C6	1.3840 (18)	C15—H15	0.93
C6—C7	1.3838 (18)	C16—H16A	0.96
C6—H6	0.93	C16—H16B	0.96
C7—H7	0.93	C16—H16C	0.96
C8—C9	1.504 (2)
C1—O2—C8	115.09 (10)	H8A—C8—H8B	107.8
C5—O4—C16	118.25 (11)	O3—C9—C10	122.19 (13)
O1—C1—O2	122.50 (12)	O3—C9—C8	120.75 (12)
O1—C1—C2	124.59 (12)	C10—C9—C8	117.07 (10)
O2—C1—C2	112.90 (11)	C11—C10—C15	118.86 (12)
C7—C2—C3	118.85 (12)	C11—C10—C9	122.01 (12)
C7—C2—C1	123.02 (12)	C15—C10—C9	119.13 (11)
C3—C2—C1	118.13 (11)	C12—C11—C10	120.23 (12)
C4—C3—C2	120.83 (12)	C12—C11—H11	119.9
C4—C3—H3	119.6	C10—C11—H11	119.9
C2—C3—H3	119.6	C13—C12—C11	120.30 (12)
C3—C4—C5	119.77 (12)	C13—C12—H12	119.8
C3—C4—H4	120.1	C11—C12—H12	119.8
C5—C4—H4	120.1	C12—C13—C14	120.01 (13)
O4—C5—C6	124.72 (12)	C12—C13—H13	120.0
O4—C5—C4	115.01 (11)	C14—C13—H13	120.0
C6—C5—C4	120.27 (12)	C15—C14—C13	120.01 (13)
C7—C6—C5	119.26 (12)	C15—C14—H14	120.0
C7—C6—H6	120.4	C13—C14—H14	120.0
C5—C6—H6	120.4	C14—C15—C10	120.58 (12)
C6—C7—C2	121.02 (12)	C14—C15—H15	119.7
C6—C7—H7	119.5	C10—C15—H15	119.7
C2—C7—H7	119.5	O4—C16—H16A	109.5
O2—C8—C9	112.64 (10)	O4—C16—H16B	109.5
O2—C8—H8A	109.1	H16A—C16—H16B	109.5
C9—C8—H8A	109.1	O4—C16—H16C	109.5
O2—C8—H8B	109.1	H16A—C16—H16C	109.5
C9—C8—H8B	109.1	H16B—C16—H16C	109.5
C8—O2—C1—O1	−2.97 (18)	C1—C2—C7—C6	179.11 (11)
C8—O2—C1—C2	176.88 (10)	C1—O2—C8—C9	78.38 (14)
O1—C1—C2—C7	170.58 (12)	O2—C8—C9—O3	3.89 (19)
O2—C1—C2—C7	−9.26 (17)	O2—C8—C9—C10	−176.36 (11)
O1—C1—C2—C3	−9.79 (19)	O3—C9—C10—C11	−178.42 (13)
O2—C1—C2—C3	170.36 (10)	C8—C9—C10—C11	1.84 (18)
C7—C2—C3—C4	0.77 (19)	O3—C9—C10—C15	2.43 (19)
C1—C2—C3—C4	−178.87 (11)	C8—C9—C10—C15	−177.31 (12)
C2—C3—C4—C5	−0.3 (2)	C15—C10—C11—C12	−0.02 (19)
C16—O4—C5—C6	−0.60 (18)	C9—C10—C11—C12	−179.17 (12)
C16—O4—C5—C4	179.44 (11)	C10—C11—C12—C13	−0.5 (2)
C3—C4—C5—O4	179.48 (11)	C11—C12—C13—C14	0.3 (2)
C3—C4—C5—C6	−0.47 (19)	C12—C13—C14—C15	0.3 (2)
O4—C5—C6—C7	−179.23 (11)	C13—C14—C15—C10	−0.8 (2)
C4—C5—C6—C7	0.72 (18)	C11—C10—C15—C14	0.68 (19)
C5—C6—C7—C2	−0.22 (19)	C9—C10—C15—C14	179.86 (12)
C3—C2—C7—C6	−0.52 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O1^i	0.97	2.28	3.2447 (17)	172
C12—H12···O3^ii	0.93	2.55	3.2973 (16)	137
C11—H11···Cg1^ii	0.93	2.86	3.6552 (15)	144

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1, y, z.