3-Chloro­phenyl 4-methyl­benzoate

Abstract

The crystal structure of the title compound 3CP4MBA, C₁₄H₁₁ClO₂, resembles those of 3-methyl­phenyl 4-methyl­benzoate (3MP4MBA), 4-methyl­phenyl 4-methyl­benzoate (4MP4MBA), 4-methyl­phenyl 4-chloro­benzoate (4CP4MBA) and other aryl benzoates with similar bond parameters. The dihedral angle between the benzene rings in 3CP4MBA is 71.75 (7)°, compared with 56.82 (7)° in 3MP4MBA and 63.57 (5)° in 4MP4MBA. In the crystal structure, the mol­ecules are aligned with their long axis approximately along the [101] direction and stacked along the c axis.

Related literature

For related literature, see: Gowda et al. (2007 ▶, 2008 ▶); Nayak & Gowda (2008 ▶).

Experimental

Crystal data

• C₁₄H₁₁ClO₂

• M _r = 246.68

• Monoclinic,

• a = 13.706 (2) Å

• b = 12.142 (2) Å

• c = 7.3807 (5) Å

• β = 100.625 (9)°

• V = 1207.2 (3) ų

• Z = 4

• Cu Kα radiation

• μ = 2.69 mm⁻¹

• T = 299 (2) K

• 0.50 × 0.27 × 0.10 mm

Data collection

• Enraf–Nonius CAD-4 diffractometer

• Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.344, T _max = 0.767

• 4283 measured reflections

• 2146 independent reflections

• 1801 reflections with I > 2σ(I)

• R _int = 0.033

• 3 standard reflections frequency: 120 min intensity decay: 1.0%

Refinement

• R[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 0.111

• S = 1.04

• 2146 reflections

• 179 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.19 e Å⁻³

• Δρ_min = −0.28 e Å⁻³

Data collection: CAD-4-PC (Enraf–Nonius, 1996 ▶); cell refinement: CAD-4-PC; data reduction: REDU4 (Stoe & Cie, 1987 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

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

supplementary crystallographic information

Comment

In the present work, as part of a study of the substituent effects on the solid state geometries of aryl benzoates (Gowda et al., 2007, 2008), the structure of 3-chlorophenyl 4-methylbenzoate (3CP4MBA) has been determined. The structure of 3CP4MBA (Fig. 1) is similar to those of 3-methylphenyl 4-methyl- benzoate (3MP4MBA), 4-methylphenyl 4-methylbenzoate (4MP4MBA), 4-methylphenyl 4-chlorobenzoate (4MP4CBA) and other aryl benzoates (Gowda et al., 2007, 2008). The bond parameters in 3CP4MBA are similar to those in 3MP4MBA, 4MP4MBA, 4CP4MBA and other aryl benzoates. The dihedral angle between the benzene and phenyl rings in 3CP4MBA is 71.75 (7)°, compared to the values of 56.82 (7)° in 3MP4MBA and 63.57 (5)° in 4MP4MBA. In the crystal structure, the molecules are elongated approximatelly along the [101] direction and stacked along the c axis (Fig. 2).

Experimental

The title compound was prepared according to a literature method (Nayak & Gowda, 2008). The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared and NMR spectra (Nayak & Gowda, 2008). Single crystals of the title compound were obtained by slow evaporation of its ethanolic solution.

Refinement

H atoms (for CH) were located in difference map and refined [ C-H = 0.89 (2) -0.98 (2) Å; U_iso(H) = 0.067-0.079 Ų]. The methyl H atoms were positioned geometrically, with C-H= 0.96 Å, and constrained to ride on the parent atom, with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

Molecular structure of the title compound, showing the atom labeling. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radius.

Fig. 2.

Molecular packing of the title compound.

Crystal data

C14H11ClO2	F000 = 512
Mr = 246.68	Dx = 1.357 Mg m−3
Monoclinic, P21/c	Cu Kα radiation λ = 1.54180 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 13.706 (2) Å	θ = 4.9–22.0º
b = 12.142 (2) Å	µ = 2.69 mm−1
c = 7.3807 (5) Å	T = 299 (2) K
β = 100.625 (9)º	Plate, colorless
V = 1207.2 (3) Å3	0.50 × 0.27 × 0.10 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.033
Radiation source: fine-focus sealed tube	θmax = 67.0º
Monochromator: graphite	θmin = 3.3º
T = 299(2) K	h = −16→16
ω/2θ scans	k = −14→0
Absorption correction: ψ scan(North et al., 1968)	l = −8→8
Tmin = 0.344, Tmax = 0.767	3 standard reflections
4283 measured reflections	every 120 min
2146 independent reflections	intensity decay: 1.0%
1801 reflections with I > 2σ(I)

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.038	w = 1/[σ2(Fo2) + (0.0556P)2 + 0.2388P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.111	(Δ/σ)max = 0.004
S = 1.04	Δρmax = 0.19 e Å−3
2146 reflections	Δρmin = −0.28 e Å−3
179 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0200 (13)
Secondary atom site location: difference Fourier map

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 > 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
Cl1	0.09746 (4)	0.45783 (6)	0.18459 (7)	0.0902 (3)
O1	0.38017 (9)	0.38035 (10)	0.71453 (19)	0.0659 (4)
O2	0.38682 (9)	0.19643 (10)	0.6950 (2)	0.0690 (4)
C1	0.27767 (12)	0.37826 (14)	0.6477 (3)	0.0550 (4)
C2	0.24434 (13)	0.41200 (15)	0.4698 (3)	0.0557 (4)
H2	0.2874 (15)	0.4294 (17)	0.388 (3)	0.067*
C3	0.14290 (13)	0.41514 (15)	0.4089 (2)	0.0566 (4)
C4	0.07707 (14)	0.38530 (16)	0.5193 (3)	0.0612 (5)
H4	0.0062 (16)	0.3899 (17)	0.472 (3)	0.073*
C5	0.11328 (15)	0.35196 (18)	0.6970 (3)	0.0655 (5)
H5	0.0675 (17)	0.3304 (19)	0.779 (3)	0.079*
C6	0.21440 (15)	0.34873 (16)	0.7635 (3)	0.0627 (5)
H6	0.2394 (16)	0.3273 (18)	0.878 (3)	0.075*
C7	0.42774 (12)	0.28135 (14)	0.7426 (2)	0.0518 (4)
C8	0.53187 (12)	0.29444 (13)	0.8356 (2)	0.0492 (4)
C9	0.58762 (14)	0.20077 (15)	0.8849 (3)	0.0581 (5)
H9	0.5605 (15)	0.1327 (19)	0.856 (3)	0.070*
C10	0.68465 (14)	0.20926 (17)	0.9760 (3)	0.0631 (5)
H10	0.7217 (16)	0.1486 (19)	1.014 (3)	0.076*
C11	0.72884 (13)	0.31058 (17)	1.0174 (3)	0.0602 (5)
C12	0.67287 (14)	0.40421 (17)	0.9643 (3)	0.0614 (5)
H12	0.7006 (16)	0.4749 (19)	0.989 (3)	0.074*
C13	0.57564 (13)	0.39698 (15)	0.8758 (3)	0.0561 (4)
H13	0.5378 (15)	0.4611 (17)	0.839 (3)	0.067*
C14	0.83424 (15)	0.3191 (2)	1.1193 (3)	0.0819 (7)
H14A	0.8782	0.3245	1.0322	0.098*
H14B	0.8506	0.2549	1.1944	0.098*
H14C	0.8412	0.3835	1.1961	0.098*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0729 (4)	0.1236 (6)	0.0670 (4)	0.0106 (3)	−0.0054 (2)	0.0248 (3)
O1	0.0505 (7)	0.0512 (7)	0.0862 (9)	−0.0002 (5)	−0.0126 (6)	0.0011 (6)
O2	0.0537 (7)	0.0552 (8)	0.0950 (10)	−0.0058 (6)	0.0059 (7)	−0.0148 (7)
C1	0.0483 (9)	0.0433 (9)	0.0673 (10)	0.0012 (7)	−0.0055 (8)	−0.0030 (8)
C2	0.0517 (9)	0.0516 (9)	0.0619 (10)	0.0013 (8)	0.0050 (8)	0.0000 (8)
C3	0.0541 (9)	0.0547 (10)	0.0566 (10)	0.0075 (8)	−0.0011 (8)	0.0029 (8)
C4	0.0496 (9)	0.0574 (11)	0.0735 (12)	0.0050 (8)	0.0031 (9)	0.0024 (9)
C5	0.0618 (11)	0.0634 (11)	0.0720 (12)	0.0015 (9)	0.0139 (9)	0.0075 (10)
C6	0.0679 (11)	0.0571 (11)	0.0583 (10)	0.0017 (9)	−0.0006 (9)	0.0054 (9)
C7	0.0502 (9)	0.0519 (9)	0.0525 (9)	−0.0013 (8)	0.0071 (7)	−0.0023 (7)
C8	0.0482 (9)	0.0513 (9)	0.0477 (8)	0.0003 (7)	0.0074 (7)	−0.0004 (7)
C9	0.0559 (10)	0.0495 (10)	0.0688 (11)	−0.0001 (8)	0.0111 (8)	0.0004 (9)
C10	0.0533 (10)	0.0620 (11)	0.0733 (12)	0.0108 (9)	0.0096 (9)	0.0114 (9)
C11	0.0487 (9)	0.0764 (12)	0.0543 (10)	0.0012 (8)	0.0062 (7)	0.0041 (8)
C12	0.0553 (10)	0.0593 (11)	0.0659 (11)	−0.0069 (9)	0.0016 (8)	−0.0070 (9)
C13	0.0530 (9)	0.0496 (10)	0.0622 (10)	0.0020 (8)	0.0016 (8)	−0.0026 (8)
C14	0.0545 (11)	0.1051 (18)	0.0804 (14)	−0.0022 (11)	−0.0028 (10)	0.0104 (13)

Geometric parameters (Å, °)

C1—C2	1.371 (3)	C8—C9	1.381 (2)
C1—C6	1.373 (3)	C8—C13	1.390 (2)
C1—O1	1.401 (2)	C9—C10	1.379 (3)
C2—C3	1.381 (2)	C9—H9	0.91 (2)
C2—H2	0.94 (2)	C10—C11	1.380 (3)
C3—C4	1.371 (3)	C10—H10	0.91 (2)
C3—Cl1	1.7372 (18)	C11—C12	1.387 (3)
C4—C5	1.375 (3)	C11—C14	1.504 (3)
C4—H4	0.97 (2)	C12—C13	1.374 (3)
C5—C6	1.383 (3)	C12—H12	0.94 (2)
C5—H5	0.98 (2)	C13—H13	0.95 (2)
C6—H6	0.89 (2)	C14—H14A	0.9600
C7—O2	1.195 (2)	C14—H14B	0.9600
C7—O1	1.365 (2)	C14—H14C	0.9600
C7—C8	1.474 (2)
C2—C1—C6	122.49 (17)	C13—C8—C7	122.60 (15)
C2—C1—O1	117.87 (17)	C10—C9—C8	120.27 (17)
C6—C1—O1	119.54 (17)	C10—C9—H9	119.7 (13)
C1—C2—C3	117.26 (18)	C8—C9—H9	120.1 (13)
C1—C2—H2	122.8 (13)	C9—C10—C11	121.26 (18)
C3—C2—H2	119.9 (13)	C9—C10—H10	121.6 (14)
C4—C3—C2	122.20 (17)	C11—C10—H10	117.1 (14)
C4—C3—Cl1	119.04 (14)	C10—C11—C12	118.08 (17)
C2—C3—Cl1	118.76 (15)	C10—C11—C14	120.93 (18)
C3—C4—C5	118.89 (17)	C12—C11—C14	120.98 (19)
C3—C4—H4	119.9 (12)	C13—C12—C11	121.28 (18)
C5—C4—H4	121.2 (13)	C13—C12—H12	118.1 (13)
C4—C5—C6	120.6 (2)	C11—C12—H12	120.6 (14)
C4—C5—H5	120.3 (13)	C12—C13—C8	120.07 (17)
C6—C5—H5	119.1 (13)	C12—C13—H13	121.0 (13)
C1—C6—C5	118.57 (18)	C8—C13—H13	118.9 (13)
C1—C6—H6	119.4 (14)	C11—C14—H14A	109.5
C5—C6—H6	122.0 (14)	C11—C14—H14B	109.5
O2—C7—O1	122.00 (15)	H14A—C14—H14B	109.5
O2—C7—C8	126.27 (16)	C11—C14—H14C	109.5
O1—C7—C8	111.73 (14)	H14A—C14—H14C	109.5
C9—C8—C13	119.03 (16)	H14B—C14—H14C	109.5
C9—C8—C7	118.37 (15)	C7—O1—C1	117.23 (13)
C6—C1—C2—C3	−0.2 (3)	C13—C8—C9—C10	1.3 (3)
O1—C1—C2—C3	−176.61 (15)	C7—C8—C9—C10	−178.50 (17)
C1—C2—C3—C4	−0.5 (3)	C8—C9—C10—C11	−1.0 (3)
C1—C2—C3—Cl1	179.81 (14)	C9—C10—C11—C12	−0.2 (3)
C2—C3—C4—C5	0.5 (3)	C9—C10—C11—C14	179.1 (2)
Cl1—C3—C4—C5	−179.75 (15)	C10—C11—C12—C13	1.1 (3)
C3—C4—C5—C6	0.1 (3)	C14—C11—C12—C13	−178.1 (2)
C2—C1—C6—C5	0.8 (3)	C11—C12—C13—C8	−0.8 (3)
O1—C1—C6—C5	177.16 (17)	C9—C8—C13—C12	−0.4 (3)
C4—C5—C6—C1	−0.8 (3)	C7—C8—C13—C12	179.41 (17)
O2—C7—C8—C9	−4.5 (3)	O2—C7—O1—C1	7.6 (3)
O1—C7—C8—C9	175.56 (16)	C8—C7—O1—C1	−172.44 (15)
O2—C7—C8—C13	175.72 (19)	C2—C1—O1—C7	−109.35 (18)
O1—C7—C8—C13	−4.2 (2)	C6—C1—O1—C7	74.1 (2)