4-Chloro­phenyl 4-methyl­benzoate

Gowda, B.T.; Foro, S.; Babitha, K.S.; Fuess, H.

doi:10.1107/S1600536808021697

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1518

doi:10.1107/S1600536808021697

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4-Chlorophenyl 4-methylbenzoate

B. Thimme Gowda,^a ^* Sabine Foro,^b K. S. Babitha ^a and Hartmut Fuess ^b

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, and ^bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 10 July 2008; accepted 12 July 2008; online 16 July 2008)

The crystal structure of the title compound (4CP4MBA), C₁₄H₁₁ClO₂, resembles those of 3-chlorophenyl 4-methylbenzoate (3CP4MBA), 4-methylphenyl 4-methylbenzoate (4MP4MBA), 4-methylphenyl 4-chlorobenzoate (4MP4CBA) and other aryl benzoates with similar bond parameters. The dihedral angle between the benzene rings in 4CP4MBA is 63.89 (8)°, compared with 71.75 (7)° in 3CP4MBA, 63.57 (5)° in 4MP4MBA and 51.86 (4)° in 4MP4CBA. In the crystal structure of the title compound, the molecules are linked into an infinite chain along the a axis via C—H—O hydrogen bonds.

Related literature

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

Experimental

Crystal data

C₁₄H₁₁ClO₂
M_r = 246.68
Monoclinic, P 2₁ /n
a = 6.048 (2) Å
b = 7.559 (2) Å
c = 26.487 (5) Å
β = 95.68 (4)°
V = 1205.0 (6) Å³
Z = 4
Cu Kα radiation
μ = 2.69 mm⁻¹
T = 299 (2) K
0.65 × 0.60 × 0.45 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.216, T_max = 0.298
2872 measured reflections
2141 independent reflections
1968 reflections with I > 2σ(I)
R_int = 0.053
3 standard reflections frequency: 120 min intensity decay: 1.5%

Refinement

R[F² > 2σ(F²)] = 0.092
wR(F²) = 0.313
S = 1.51
2141 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.94 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2ⁱ	0.93	2.51	3.212 (3)	132
Symmetry code: (i) x+1, y, z.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808021697/is2314sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808021697/is2314Isup2.hkl

checkCIF report

Comment top

In the present work, as part of a study of the substituent effects on the solid state structures of aryl benzoates (Gowda et al. 2007; Gowda, Foro, et al., 2008; Gowda, Svoboda et al., 2008), the structure of 4-chlorophenyl 4-methylbenzoate (4CP4MBA) has been determined. The structure of 4CP4MBA (Fig. 1) is similar to those of 3-chlorophenyl 4-methylbenzoate (3CP4MBA)(Gowda, Foro et al., 2008), 4-methylphenyl 4-methylbenzoate (4MP4MBA)(Gowda et al., 2007), 4-methylphenyl 4-chlorobenzoate (4MP4CBA) (Gowda, Svoboda et al., 2008) The bond parameters in 4CP4MBA are similar to those in 3CP4MBA, 4MP4MBA, 4MP4CBA and other aryl benzoates. The dihedral angle between the benzene and benzoyl rings in 4CP4MBA is 63.89 (8)°, compared to the values of 71.75 (7)° in 3CP4MeBA, 63.57 (5)° in 4MP4MBA and 51.86 (4)° in 4MP4CBA. The molecules in the crystal structure of 4CP4MBA are packed into chains via C—H—O hydrogen bonds (Table 1 and Fig. 2).

Related literature top

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

Experimental top

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 used in X-ray diffraction studies were obtained by slow evaporation of its ethanol solution.

Computing details top

Data collection: CAD-4-PC (Enraf–Nonius, 1996); cell refinement: CAD-4-PC (Enraf–Nonius, 1996); 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 (Sheldrick, 2008).

Figures top

	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, viewed along the b axis.

4-Chlorophenyl 4-methylbenzoate top

Crystal data top

C₁₄H₁₁ClO₂	F(000) = 512
M_r = 246.68	D_x = 1.360 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 6.048 (2) Å	θ = 3.4–16.9°
b = 7.559 (2) Å	µ = 2.69 mm⁻¹
c = 26.487 (5) Å	T = 299 K
β = 95.68 (4)°	Prism, colourless
V = 1205.0 (6) Å³	0.65 × 0.60 × 0.45 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1968 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.053
Graphite monochromator	θ_max = 67.0°, θ_min = 3.4°
ω/2θ scans	h = −7→2
Absorption correction: ψ scan (North et al., 1968)	k = −9→0
T_min = 0.216, T_max = 0.298	l = −31→31
2872 measured reflections	3 standard reflections every 120 min
2141 independent reflections	intensity decay: 1.5%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.092	H-atom parameters constrained
wR(F²) = 0.313	w = 1/[σ²(F_o²) + (0.2P)²] where P = (F_o² + 2F_c²)/3
S = 1.51	(Δ/σ)_max = 0.001
2141 reflections	Δρ_max = 0.53 e Å⁻³
156 parameters	Δρ_min = −0.94 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.048 (9)

Crystal data top

C₁₄H₁₁ClO₂	V = 1205.0 (6) Å³
M_r = 246.68	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 6.048 (2) Å	µ = 2.69 mm⁻¹
b = 7.559 (2) Å	T = 299 K
c = 26.487 (5) Å	0.65 × 0.60 × 0.45 mm
β = 95.68 (4)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1968 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.053
T_min = 0.216, T_max = 0.298	3 standard reflections every 120 min
2872 measured reflections	intensity decay: 1.5%
2141 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.092	0 restraints
wR(F²) = 0.313	H-atom parameters constrained
S = 1.51	Δρ_max = 0.53 e Å⁻³
2141 reflections	Δρ_min = −0.94 e Å⁻³
156 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.75384 (13)	0.28660 (13)	0.53235 (3)	0.0895 (6)
O1	0.2922 (3)	0.3273 (3)	0.32780 (7)	0.0708 (7)
O2	0.0565 (3)	0.5372 (3)	0.34855 (6)	0.0655 (7)
C1	0.3932 (4)	0.3235 (3)	0.37781 (9)	0.0577 (7)
C2	0.5981 (4)	0.4028 (4)	0.38707 (10)	0.0627 (8)
H2	0.6612	0.4629	0.3614	0.075*
C3	0.7081 (4)	0.3910 (3)	0.43527 (11)	0.0643 (8)
H3	0.8467	0.4436	0.4425	0.077*
C4	0.6124 (5)	0.3022 (3)	0.47205 (10)	0.0618 (8)
C5	0.4096 (5)	0.2231 (4)	0.46293 (11)	0.0697 (8)
H5	0.3473	0.1627	0.4886	0.084*
C6	0.2981 (4)	0.2344 (4)	0.41478 (11)	0.0693 (8)
H6	0.1596	0.1815	0.4078	0.083*
C7	0.1213 (3)	0.4406 (3)	0.31755 (8)	0.0522 (7)
C8	0.0302 (3)	0.4314 (3)	0.26348 (8)	0.0492 (7)
C9	0.1415 (4)	0.3453 (3)	0.22735 (9)	0.0571 (7)
H9	0.2781	0.2919	0.2366	0.068*
C10	0.0495 (4)	0.3389 (3)	0.17768 (10)	0.0591 (7)
H10	0.1266	0.2834	0.1535	0.071*
C11	−0.1566 (4)	0.4140 (3)	0.16318 (9)	0.0549 (7)
C12	−0.2636 (4)	0.5008 (3)	0.19962 (10)	0.0605 (7)
H12	−0.4012	0.5527	0.1905	0.073*
C13	−0.1715 (4)	0.5122 (3)	0.24905 (9)	0.0579 (7)
H13	−0.2446	0.5741	0.2728	0.069*
C14	−0.2612 (5)	0.4005 (4)	0.10953 (11)	0.0718 (8)
H14A	−0.1757	0.3214	0.0908	0.086*
H14B	−0.2651	0.5154	0.0940	0.086*
H14C	−0.4099	0.3559	0.1094	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0931 (9)	0.1079 (9)	0.0595 (8)	−0.0047 (4)	−0.0318 (5)	0.0080 (3)
O1	0.0735 (12)	0.0844 (13)	0.0496 (12)	0.0203 (9)	−0.0187 (8)	−0.0115 (9)
O2	0.0671 (12)	0.0793 (12)	0.0480 (11)	0.0089 (8)	−0.0050 (7)	−0.0095 (8)
C1	0.0570 (13)	0.0664 (13)	0.0460 (14)	0.0066 (9)	−0.0130 (9)	−0.0050 (10)
C2	0.0586 (14)	0.0753 (15)	0.0522 (15)	−0.0014 (10)	−0.0054 (10)	0.0072 (12)
C3	0.0543 (13)	0.0703 (15)	0.0644 (16)	−0.0030 (10)	−0.0135 (10)	0.0029 (12)
C4	0.0653 (15)	0.0640 (14)	0.0518 (15)	0.0026 (9)	−0.0152 (10)	0.0020 (10)
C5	0.0730 (16)	0.0801 (17)	0.0532 (16)	−0.0130 (12)	−0.0069 (12)	0.0089 (12)
C6	0.0609 (15)	0.0791 (16)	0.0637 (17)	−0.0128 (11)	−0.0148 (11)	−0.0027 (13)
C7	0.0480 (12)	0.0595 (13)	0.0471 (13)	−0.0029 (8)	−0.0061 (9)	−0.0003 (9)
C8	0.0506 (11)	0.0511 (11)	0.0439 (13)	−0.0028 (7)	−0.0058 (8)	0.0004 (8)
C9	0.0525 (13)	0.0604 (12)	0.0557 (14)	0.0063 (9)	−0.0076 (9)	−0.0049 (10)
C10	0.0635 (15)	0.0665 (14)	0.0458 (13)	0.0082 (10)	−0.0025 (10)	−0.0061 (10)
C11	0.0635 (13)	0.0499 (11)	0.0481 (14)	−0.0014 (8)	−0.0103 (10)	0.0022 (9)
C12	0.0555 (13)	0.0675 (14)	0.0556 (14)	0.0098 (9)	−0.0085 (10)	0.0043 (11)
C13	0.0607 (14)	0.0665 (14)	0.0452 (13)	0.0081 (9)	−0.0012 (9)	−0.0032 (10)
C14	0.0862 (19)	0.0737 (16)	0.0512 (16)	0.0040 (12)	−0.0150 (12)	−0.0004 (12)

Geometric parameters (Å, º) top

Cl1—C4	1.740 (3)	C8—C13	1.384 (3)
O1—C7	1.350 (3)	C8—C9	1.386 (3)
O1—C1	1.403 (3)	C9—C10	1.378 (3)
O2—C7	1.193 (3)	C9—H9	0.9300
C1—C6	1.362 (4)	C10—C11	1.389 (3)
C1—C2	1.376 (4)	C10—H10	0.9300
C2—C3	1.383 (4)	C11—C12	1.380 (4)
C2—H2	0.9300	C11—C14	1.501 (3)
C3—C4	1.359 (4)	C12—C13	1.374 (4)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.364 (4)	C13—H13	0.9300
C5—C6	1.385 (4)	C14—H14A	0.9600
C5—H5	0.9300	C14—H14B	0.9600
C6—H6	0.9300	C14—H14C	0.9600
C7—C8	1.484 (3)

C7—O1—C1	117.12 (18)	C13—C8—C7	118.57 (19)
C6—C1—C2	121.6 (3)	C9—C8—C7	122.0 (2)
C6—C1—O1	120.9 (2)	C10—C9—C8	119.8 (2)
C2—C1—O1	117.4 (2)	C10—C9—H9	120.1
C1—C2—C3	118.6 (2)	C8—C9—H9	120.1
C1—C2—H2	120.7	C9—C10—C11	121.1 (2)
C3—C2—H2	120.7	C9—C10—H10	119.4
C4—C3—C2	119.6 (2)	C11—C10—H10	119.4
C4—C3—H3	120.2	C12—C11—C10	118.1 (2)
C2—C3—H3	120.2	C12—C11—C14	120.8 (2)
C3—C4—C5	121.9 (3)	C10—C11—C14	121.1 (2)
C3—C4—Cl1	119.1 (2)	C13—C12—C11	121.5 (2)
C5—C4—Cl1	119.0 (2)	C13—C12—H12	119.2
C4—C5—C6	118.9 (3)	C11—C12—H12	119.2
C4—C5—H5	120.5	C12—C13—C8	119.9 (2)
C6—C5—H5	120.5	C12—C13—H13	120.0
C1—C6—C5	119.4 (2)	C8—C13—H13	120.0
C1—C6—H6	120.3	C11—C14—H14A	109.5
C5—C6—H6	120.3	C11—C14—H14B	109.5
O2—C7—O1	123.2 (2)	H14A—C14—H14B	109.5
O2—C7—C8	125.2 (2)	C11—C14—H14C	109.5
O1—C7—C8	111.57 (19)	H14A—C14—H14C	109.5
C13—C8—C9	119.5 (2)	H14B—C14—H14C	109.5

C7—O1—C1—C6	79.0 (3)	O2—C7—C8—C13	−13.8 (3)
C7—O1—C1—C2	−105.3 (3)	O1—C7—C8—C13	167.3 (2)
C6—C1—C2—C3	−0.2 (4)	O2—C7—C8—C9	165.9 (2)
O1—C1—C2—C3	−175.8 (2)	O1—C7—C8—C9	−12.9 (3)
C1—C2—C3—C4	0.1 (4)	C13—C8—C9—C10	−0.8 (3)
C2—C3—C4—C5	0.1 (4)	C7—C8—C9—C10	179.5 (2)
C2—C3—C4—Cl1	179.36 (19)	C8—C9—C10—C11	−1.5 (4)
C3—C4—C5—C6	−0.2 (5)	C9—C10—C11—C12	2.2 (4)
Cl1—C4—C5—C6	−179.4 (2)	C9—C10—C11—C14	−177.4 (2)
C2—C1—C6—C5	0.1 (4)	C10—C11—C12—C13	−0.5 (4)
O1—C1—C6—C5	175.6 (2)	C14—C11—C12—C13	179.1 (2)
C4—C5—C6—C1	0.1 (5)	C11—C12—C13—C8	−1.8 (4)
C1—O1—C7—O2	1.1 (3)	C9—C8—C13—C12	2.5 (4)
C1—O1—C7—C8	179.94 (19)	C7—C8—C13—C12	−177.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱ	0.93	2.51	3.212 (3)	132

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁ClO₂
M_r	246.68
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	299
a, b, c (Å)	6.048 (2), 7.559 (2), 26.487 (5)
β (°)	95.68 (4)
V (Å³)	1205.0 (6)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	2.69
Crystal size (mm)	0.65 × 0.60 × 0.45

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.216, 0.298
No. of measured, independent and observed [I > 2σ(I)] reflections	2872, 2141, 1968
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.092, 0.313, 1.51
No. of reflections	2141
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.94

Computer programs: CAD-4-PC (Enraf–Nonius, 1996), REDU4 (Stoe & Cie, 1987), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱ	0.93	2.51	3.212 (3)	132.4

Symmetry code: (i) x+1, y, z.

Acknowledgements

BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany, for extensions of his research fellowship.

References

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