Crystal structure of 4-acetyl­phenyl 3-methyl­benzoate

Abstract

The planes of the aromatic rings of the title compound, C₁₆H₁₄O₃, make a dihedral angle of 82.52 (8)°. The acetyl group and the phenyl ring make a dihedral angle of 1.65 (1)°. In the crystal, the molecules are linked by C—H⋯O interactions, generating C(7) chains along the a-axis direction.

Related literature  

For the biological activity of aceto­phenone derivatives, see: Chung et al. (2003 ▶).

Experimental  

Crystal data  

• C₁₆H₁₄O₃

• M _r = 254.27

• Monoclinic,

• a = 8.7167 (3) Å

• b = 9.8521 (3) Å

• c = 15.4938 (4) Å

• β = 95.149 (2)°

• V = 1325.20 (7) ų

• Z = 4

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 293 K

• 0.30 × 0.25 × 0.20 mm

Data collection  

• Bruker SMART APEXII area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.974, T _max = 0.983

• 12798 measured reflections

• 3303 independent reflections

• 2130 reflections with I > 2σ(I)

• R _int = 0.033

Refinement  

• R[F ² > 2σ(F ²)] = 0.048

• wR(F ²) = 0.162

• S = 1.00

• 3303 reflections

• 174 parameters

• H-atom parameters constrained

• Δρ_max = 0.14 e Å⁻³

• Δρ_min = −0.19 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

CCDC reference: 1020285

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16B⋯O1i	0.96	2.57	3.509 (3)	167
C3—H3⋯O3ii	0.93	2.52	3.265 (2)	137

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

S1. Comment

Acetophenone derivatives are popular in organic synthesis for their applications in biology and pharmacological activities. They are known to exhibit antioxidant and antityrosinase activities (Chung et al., 2003).

The ORTEP plot of the molecule is shown in Fig. 1. The carbonyl groups are coplanar with the rings to which they are attached, which is evident from torsion angles [C5-C6-C8-O3 2.1 (2)° and C11-C12-C15-O1 0.9 (2)]. The dihedral angle between the two aromatic rings is 82.52 (8)°.

The molecular structure is stabilized by an intramolecular and the crystal packing by intermolecular C—H···O hydrogen bonds (Table 1 & Fig. 2).

S2. Experimental

A clean and dry 250ml two neck RB flask was fitted with a condenser and an addition funnel. 0.5 mol of 4- hydroxy acetophenone was taken and 200ml of chloroform was added to it with stirring. The reaction mixture was cooled at 5-10°c. 0.5 mol of meta-tolouyl chloride was added dropwise to the reaction mixture. Stirring was continued for another 15 mins and 0.5 mol of potassium carbonate was slowly added. The reaction was continued for 2 hours and monitored using TLC. The reaction mixture was transferred into a 1 l beaker and washed twice with water (2 x 250 ml). The chloroform layer was separated and washed with 10% NaOH solution (2x250ml). The chloroform layer was separated and dried with anhydrous sodium sulphate. The chloroform layer was then filtered and concentrated under reduced pressure using rotary vacuum. It was cooled and hexane was added to it. The solid which precipitated was filtered and the product was air dried. After purification the compound was recrystallised in CHCl₃ by slow evaporation method.

S3. Refinement

The hydrogen atoms were placed in calculated positions with C—H = 0.93Å to 0.96 Å, refined in the riding model with fixed isotropic displacement parameters: U_iso(H) = 1.5U_eq(C) for methyl groups and U_iso(H) = 1.2U_eq(C) for C_aromatic. The methyl groups were allowed to rotate but not to tip.

Figures

Fig. 1.

The molecular structure of the title compound, showing the atomic numbering and displacement ellipsoids drawn at 30% probability level.

Fig. 2.

The crystal packing of the title compound viewed down the a axis. Intermolecular hydrogen bonds are shown as dashed lines. H-atoms not involved in H-bonds have been excluded for clarity.

Crystal data

C16H14O3	F(000) = 536
Mr = 254.27	Dx = 1.274 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3303 reflections
a = 8.7167 (3) Å	θ = 2.4–28.3°
b = 9.8521 (3) Å	µ = 0.09 mm−1
c = 15.4938 (4) Å	T = 293 K
β = 95.149 (2)°	Block, colourless
V = 1325.20 (7) Å3	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection

Bruker SMART APEXII area-detector diffractometer	3303 independent reflections
Radiation source: fine-focus sealed tube	2130 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω and φ scans	θmax = 28.3°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→9
Tmin = 0.974, Tmax = 0.983	k = −10→13
12798 measured reflections	l = −20→20

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.162	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0803P)2 + 0.1756P] where P = (Fo2 + 2Fc2)/3
3303 reflections	(Δ/σ)max = 0.043
174 parameters	Δρmax = 0.14 e Å−3
0 restraints	Δρmin = −0.19 e Å−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.2306 (3)	1.0754 (3)	−0.43251 (12)	0.0957 (7)
H1A	0.3009	1.1250	−0.4649	0.144*
H1B	0.1793	1.1370	−0.3966	0.144*
H1C	0.1557	1.0305	−0.4718	0.144*
C2	0.31775 (19)	0.97205 (18)	−0.37669 (9)	0.0637 (4)
C3	0.4192 (2)	0.88402 (19)	−0.41068 (11)	0.0747 (5)
H3	0.4342	0.8893	−0.4693	0.090*
C4	0.4986 (2)	0.7889 (2)	−0.36009 (13)	0.0826 (6)
H4	0.5666	0.7306	−0.3845	0.099*
C5	0.4783 (2)	0.77929 (17)	−0.27263 (11)	0.0711 (5)
H5	0.5326	0.7151	−0.2381	0.085*
C6	0.37624 (16)	0.86609 (15)	−0.23730 (9)	0.0538 (4)
C7	0.29747 (17)	0.96191 (16)	−0.28903 (9)	0.0562 (4)
H7	0.2297	1.0207	−0.2648	0.067*
C8	0.35490 (18)	0.85016 (16)	−0.14433 (9)	0.0576 (4)
C9	0.21558 (18)	0.92477 (16)	−0.03042 (9)	0.0581 (4)
C10	0.10870 (19)	0.83096 (17)	−0.01086 (10)	0.0669 (4)
H10	0.0630	0.7740	−0.0536	0.080*
C11	0.06933 (19)	0.82189 (17)	0.07360 (11)	0.0655 (4)
H11	−0.0027	0.7578	0.0876	0.079*
C12	0.13591 (17)	0.90698 (15)	0.13718 (9)	0.0553 (4)
C13	0.24248 (19)	1.00229 (17)	0.11470 (10)	0.0621 (4)
H13	0.2874	1.0609	0.1567	0.075*
C14	0.28287 (19)	1.01129 (17)	0.03027 (10)	0.0642 (4)
H14	0.3545	1.0752	0.0154	0.077*
C15	0.0930 (2)	0.89341 (17)	0.22797 (11)	0.0662 (4)
C16	0.1621 (3)	0.9862 (2)	0.29564 (11)	0.0912 (6)
H16A	0.1261	0.9627	0.3505	0.137*
H16B	0.1329	1.0779	0.2811	0.137*
H16C	0.2723	0.9783	0.2993	0.137*
O1	0.00206 (19)	0.80739 (15)	0.24608 (9)	0.0967 (5)
O2	0.25094 (14)	0.93822 (12)	−0.11686 (6)	0.0694 (3)
O3	0.42165 (16)	0.77076 (15)	−0.09685 (7)	0.0882 (4)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0939 (14)	0.1320 (18)	0.0614 (10)	0.0018 (13)	0.0082 (9)	0.0211 (11)
C2	0.0628 (9)	0.0782 (11)	0.0507 (8)	−0.0189 (8)	0.0079 (7)	−0.0029 (7)
C3	0.0875 (12)	0.0843 (12)	0.0551 (8)	−0.0229 (10)	0.0220 (8)	−0.0151 (8)
C4	0.0967 (14)	0.0730 (12)	0.0838 (12)	−0.0033 (10)	0.0388 (10)	−0.0202 (10)
C5	0.0796 (11)	0.0615 (10)	0.0747 (10)	0.0042 (8)	0.0199 (9)	−0.0054 (8)
C6	0.0544 (8)	0.0544 (8)	0.0533 (7)	−0.0079 (6)	0.0089 (6)	−0.0067 (6)
C7	0.0549 (8)	0.0630 (9)	0.0513 (7)	−0.0068 (7)	0.0082 (6)	−0.0048 (6)
C8	0.0596 (9)	0.0581 (8)	0.0555 (8)	0.0002 (7)	0.0080 (6)	0.0000 (7)
C9	0.0636 (9)	0.0639 (9)	0.0473 (7)	0.0127 (7)	0.0090 (6)	0.0038 (6)
C10	0.0697 (10)	0.0673 (10)	0.0635 (9)	−0.0004 (8)	0.0047 (8)	−0.0113 (7)
C11	0.0629 (9)	0.0638 (9)	0.0716 (9)	−0.0035 (7)	0.0164 (7)	−0.0027 (8)
C12	0.0558 (8)	0.0564 (8)	0.0550 (8)	0.0108 (6)	0.0115 (6)	0.0026 (6)
C13	0.0682 (9)	0.0672 (9)	0.0511 (7)	−0.0030 (8)	0.0066 (7)	−0.0032 (7)
C14	0.0692 (10)	0.0687 (10)	0.0556 (8)	−0.0057 (8)	0.0107 (7)	0.0051 (7)
C15	0.0742 (10)	0.0623 (9)	0.0652 (9)	0.0159 (8)	0.0240 (8)	0.0063 (7)
C16	0.1263 (17)	0.0948 (14)	0.0551 (9)	0.0026 (13)	0.0238 (10)	−0.0015 (9)
O1	0.1189 (11)	0.0866 (9)	0.0923 (9)	−0.0109 (8)	0.0523 (8)	0.0021 (7)
O2	0.0850 (8)	0.0765 (7)	0.0481 (5)	0.0207 (6)	0.0143 (5)	0.0048 (5)
O3	0.0999 (10)	0.0972 (9)	0.0702 (7)	0.0355 (8)	0.0226 (7)	0.0232 (7)

Geometric parameters (Å, º)

C1—C2	1.498 (3)	C9—C14	1.362 (2)
C1—H1A	0.9600	C9—C10	1.366 (2)
C1—H1B	0.9600	C9—O2	1.4071 (17)
C1—H1C	0.9600	C10—C11	1.385 (2)
C2—C3	1.377 (2)	C10—H10	0.9300
C2—C7	1.389 (2)	C11—C12	1.381 (2)
C3—C4	1.369 (3)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.387 (2)
C4—C5	1.386 (2)	C12—C15	1.494 (2)
C4—H4	0.9300	C13—C14	1.388 (2)
C5—C6	1.382 (2)	C13—H13	0.9300
C5—H5	0.9300	C14—H14	0.9300
C6—C7	1.381 (2)	C15—O1	1.210 (2)
C6—C8	1.477 (2)	C15—C16	1.478 (3)
C7—H7	0.9300	C16—H16A	0.9600
C8—O3	1.1895 (18)	C16—H16B	0.9600
C8—O2	1.3506 (18)	C16—H16C	0.9600
C2—C1—H1A	109.5	C14—C9—O2	118.72 (15)
C2—C1—H1B	109.5	C10—C9—O2	119.14 (14)
H1A—C1—H1B	109.5	C9—C10—C11	119.01 (15)
C2—C1—H1C	109.5	C9—C10—H10	120.5
H1A—C1—H1C	109.5	C11—C10—H10	120.5
H1B—C1—H1C	109.5	C12—C11—C10	120.72 (15)
C3—C2—C7	118.12 (16)	C12—C11—H11	119.6
C3—C2—C1	121.15 (15)	C10—C11—H11	119.6
C7—C2—C1	120.73 (16)	C11—C12—C13	118.68 (14)
C4—C3—C2	121.42 (15)	C11—C12—C15	119.52 (14)
C4—C3—H3	119.3	C13—C12—C15	121.80 (14)
C2—C3—H3	119.3	C12—C13—C14	120.81 (14)
C3—C4—C5	120.28 (17)	C12—C13—H13	119.6
C3—C4—H4	119.9	C14—C13—H13	119.6
C5—C4—H4	119.9	C9—C14—C13	118.74 (15)
C6—C5—C4	119.25 (17)	C9—C14—H14	120.6
C6—C5—H5	120.4	C13—C14—H14	120.6
C4—C5—H5	120.4	O1—C15—C16	120.15 (16)
C7—C6—C5	119.82 (14)	O1—C15—C12	120.37 (16)
C7—C6—C8	122.62 (13)	C16—C15—C12	119.48 (15)
C5—C6—C8	117.55 (14)	C15—C16—H16A	109.5
C6—C7—C2	121.10 (14)	C15—C16—H16B	109.5
C6—C7—H7	119.4	H16A—C16—H16B	109.5
C2—C7—H7	119.4	C15—C16—H16C	109.5
O3—C8—O2	122.16 (14)	H16A—C16—H16C	109.5
O3—C8—C6	125.13 (14)	H16B—C16—H16C	109.5
O2—C8—C6	112.70 (13)	C8—O2—C9	116.74 (11)
C14—C9—C10	122.03 (14)
C7—C2—C3—C4	−0.1 (2)	C9—C10—C11—C12	0.5 (2)
C1—C2—C3—C4	−179.69 (18)	C10—C11—C12—C13	0.3 (2)
C2—C3—C4—C5	0.0 (3)	C10—C11—C12—C15	−179.06 (14)
C3—C4—C5—C6	0.4 (3)	C11—C12—C13—C14	−0.7 (2)
C4—C5—C6—C7	−0.7 (2)	C15—C12—C13—C14	178.71 (14)
C4—C5—C6—C8	178.48 (15)	C10—C9—C14—C13	0.8 (2)
C5—C6—C7—C2	0.6 (2)	O2—C9—C14—C13	176.97 (13)
C8—C6—C7—C2	−178.52 (13)	C12—C13—C14—C9	0.1 (2)
C3—C2—C7—C6	−0.2 (2)	C11—C12—C15—O1	0.9 (2)
C1—C2—C7—C6	179.38 (16)	C13—C12—C15—O1	−178.43 (16)
C7—C6—C8—O3	−178.76 (16)	C11—C12—C15—C16	−178.87 (16)
C5—C6—C8—O3	2.1 (2)	C13—C12—C15—C16	1.8 (2)
C7—C6—C8—O2	0.3 (2)	O3—C8—O2—C9	−4.9 (2)
C5—C6—C8—O2	−178.88 (14)	C6—C8—O2—C9	176.01 (13)
C14—C9—C10—C11	−1.1 (2)	C14—C9—O2—C8	100.57 (17)
O2—C9—C10—C11	−177.29 (13)	C10—C9—O2—C8	−83.11 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O2	0.93	2.42	2.7439 (17)	100
C16—H16B···O1i	0.96	2.57	3.509 (3)	167
C3—H3···O3ii	0.93	2.52	3.265 (2)	137

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, −y+3/2, z−1/2.