4-Chloro­phenyl 4-chloro­benzoate

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

doi:10.1107/S1600536808022800

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1582

doi:10.1107/S1600536808022800

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4-Chlorophenyl 4-chlorobenzoate

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 18 July 2008; accepted 20 July 2008; online 23 July 2008)

The structure of the title compound (4CP4CBA), C₁₃H₈Cl₂O₂, resembles those of 4-methylphenyl 4-chlorobenzoate (4MP4CBA), 4-chlorophenyl 4-methylbenzoate (4CP4MBA) and 4-methylphenyl 4-methylbenzoate (4MP4MBA), with similar bond parameters. The dihedral angle between the two benzene rings in 4CP4CBA is 47.98 (7)°, compared with 51.86 (4)° in 4MP4CBA, 63.89 (8)° in 4CP4MBA and 63.57 (5)° in 4MP4MBA. In the crystal structure, molecules are linked into helical chains running along the b axis by 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

C₁₃H₈Cl₂O₂
M_r = 267.09
Monoclinic, P 2₁ /n
a = 15.370 (2) Å
b = 3.9528 (4) Å
c = 19.465 (2) Å
β = 91.804 (9)°
V = 1182.0 (2) Å³
Z = 4
Cu Kα radiation
μ = 4.83 mm⁻¹
T = 299 (2) K
0.45 × 0.23 × 0.18 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.194, T_max = 0.420
4211 measured reflections
2109 independent reflections
1724 reflections with I > 2σ(I)
R_int = 0.080
3 standard reflections frequency: 120 min intensity decay: 1.0%

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.139
S = 1.05
2109 reflections
178 parameters
Only H-atom coordinates refined
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O2ⁱ	0.92 (3)	2.58 (3)	3.168 (3)	123 (2)
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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/S1600536808022800/ci2640sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808022800/ci2640Isup2.hkl

checkCIF report

Comment top

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 crystal structure of 4-chlorophenyl 4-chlorobenzoate (4CP4CBA) has been determined. The structure (Fig. 1) is similar to those of 4-methylphenyl 4-chlorobenzoate (4MP4CBA) (Gowda, Svoboda et al., 2008), 4-chlorophenyl 4-methylbenzoate (4CP4MBA) (Gowda, Foro et al., 2008) and 4-methylphenyl 4-methylbenzoate (4MP4MBA) (Gowda et al., 2007). The bond parameters in 4CP4CBA are similar to those in afore mentioned 4MP4CBA, 4CP4MBA, 4MP4MBA and other aryl benzoates (Gowda et al., 2007; Gowda, Foro et al., 2008; Gowda, Svoboda et al., 2008). The dihedral angle between the benzene and benzoyl rings in 4CP4CBA is 47.98 (7)°, compared to the values of 51.86 (4)° in 4MP4CBA, 63.89 (8)° in 4CP4MBA and 63.57 (5)° in 4MP4MBA.

In the crystal structure, the molecules are linked into helical chains (Fig. 2) running along the b axis by C—H—O hydrogen bonds (Table 1).

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 labelling scheme. 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.

4-Chlorophenyl 4-chlorobenzoate top

Crystal data top

C₁₃H₈Cl₂O₂	F(000) = 544
M_r = 267.09	D_x = 1.501 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 15.370 (2) Å	θ = 11.5–24.3°
b = 3.9528 (4) Å	µ = 4.83 mm⁻¹
c = 19.465 (2) Å	T = 299 K
β = 91.804 (9)°	Rod, colourless
V = 1182.0 (2) Å³	0.45 × 0.23 × 0.18 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1724 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.080
Graphite monochromator	θ_max = 67.0°, θ_min = 3.6°
ω/2θ scans	h = −18→18
Absorption correction: ψ scan (North et al., 1968)	k = −4→0
T_min = 0.194, T_max = 0.420	l = −23→23
4211 measured reflections	3 standard reflections every 120 min
2109 independent reflections	intensity decay: 1.0%

Refinement top

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: difference Fourier map
wR(F²) = 0.139	Only H-atom coordinates refined
S = 1.05	w = 1/[σ²(F_o²) + (0.0736P)² + 0.2805P] where P = (F_o² + 2F_c²)/3
2109 reflections	(Δ/σ)_max = 0.021
178 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₃H₈Cl₂O₂	V = 1182.0 (2) Å³
M_r = 267.09	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 15.370 (2) Å	µ = 4.83 mm⁻¹
b = 3.9528 (4) Å	T = 299 K
c = 19.465 (2) Å	0.45 × 0.23 × 0.18 mm
β = 91.804 (9)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1724 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.080
T_min = 0.194, T_max = 0.420	3 standard reflections every 120 min
4211 measured reflections	intensity decay: 1.0%
2109 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.139	Only H-atom coordinates refined
S = 1.05	Δρ_max = 0.39 e Å⁻³
2109 reflections	Δρ_min = −0.33 e Å⁻³
178 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	0.49228 (5)	0.7640 (2)	0.08027 (4)	0.0690 (3)
Cl2	0.72347 (5)	−0.0839 (2)	0.67678 (3)	0.0704 (3)
O1	0.59363 (10)	0.3353 (5)	0.36024 (9)	0.0529 (5)
O2	0.72448 (12)	0.5904 (7)	0.36130 (10)	0.0737 (7)
C1	0.57335 (13)	0.4453 (6)	0.29332 (12)	0.0444 (5)
C2	0.49523 (15)	0.6088 (7)	0.28247 (14)	0.0518 (6)
H2	0.4603 (19)	0.657 (8)	0.3193 (16)	0.062*
C3	0.46945 (15)	0.7062 (7)	0.21667 (15)	0.0546 (6)
H3	0.4132 (19)	0.820 (9)	0.2133 (15)	0.066*
C4	0.52292 (14)	0.6377 (6)	0.16294 (13)	0.0469 (5)
C5	0.60108 (15)	0.4709 (7)	0.17399 (13)	0.0492 (6)
H5	0.6337 (18)	0.438 (8)	0.1358 (16)	0.059*
C6	0.62658 (14)	0.3724 (7)	0.23892 (13)	0.0488 (6)
H6	0.6762 (19)	0.246 (8)	0.2482 (15)	0.059*
C7	0.67225 (14)	0.4158 (7)	0.38938 (12)	0.0482 (6)
C8	0.68345 (13)	0.2812 (6)	0.45961 (12)	0.0452 (5)
C9	0.61746 (15)	0.1152 (8)	0.49299 (14)	0.0530 (6)
H9	0.5619 (19)	0.089 (8)	0.4691 (16)	0.064*
C10	0.62957 (16)	0.0048 (8)	0.55961 (13)	0.0538 (6)
H10	0.584 (2)	−0.108 (8)	0.5807 (16)	0.065*
C11	0.70901 (15)	0.0570 (7)	0.59276 (13)	0.0494 (6)
C12	0.77573 (16)	0.2151 (8)	0.56050 (15)	0.0579 (7)
H12	0.826 (2)	0.225 (9)	0.5856 (17)	0.069*
C13	0.76306 (14)	0.3276 (8)	0.49402 (14)	0.0534 (6)
H13	0.8067 (19)	0.428 (9)	0.4718 (16)	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0694 (4)	0.0793 (5)	0.0574 (4)	0.0037 (3)	−0.0138 (3)	0.0097 (4)
Cl2	0.0777 (5)	0.0819 (6)	0.0507 (4)	0.0114 (4)	−0.0142 (3)	0.0012 (3)
O1	0.0419 (8)	0.0685 (12)	0.0480 (9)	−0.0142 (8)	−0.0015 (6)	0.0071 (9)
O2	0.0623 (11)	0.0998 (18)	0.0589 (11)	−0.0387 (11)	0.0032 (9)	0.0064 (11)
C1	0.0394 (10)	0.0469 (13)	0.0469 (12)	−0.0087 (9)	0.0002 (9)	−0.0007 (11)
C2	0.0404 (11)	0.0604 (16)	0.0553 (14)	−0.0009 (10)	0.0094 (10)	−0.0063 (12)
C3	0.0395 (11)	0.0581 (15)	0.0659 (16)	0.0061 (11)	−0.0023 (10)	−0.0024 (13)
C4	0.0447 (11)	0.0462 (13)	0.0492 (12)	−0.0044 (10)	−0.0046 (9)	0.0006 (11)
C5	0.0451 (11)	0.0537 (14)	0.0491 (13)	0.0034 (10)	0.0054 (10)	−0.0044 (12)
C6	0.0393 (11)	0.0553 (14)	0.0518 (13)	0.0056 (10)	0.0007 (9)	−0.0009 (12)
C7	0.0378 (10)	0.0605 (15)	0.0463 (12)	−0.0070 (10)	0.0038 (9)	−0.0042 (11)
C8	0.0367 (10)	0.0513 (13)	0.0477 (13)	−0.0032 (9)	0.0027 (9)	−0.0065 (11)
C9	0.0368 (10)	0.0715 (17)	0.0504 (13)	−0.0101 (11)	−0.0043 (9)	0.0033 (12)
C10	0.0428 (11)	0.0678 (16)	0.0507 (13)	−0.0070 (12)	0.0003 (10)	0.0049 (13)
C11	0.0514 (12)	0.0502 (14)	0.0460 (12)	0.0065 (10)	−0.0064 (10)	−0.0059 (11)
C12	0.0413 (11)	0.0657 (17)	0.0659 (16)	0.0002 (11)	−0.0123 (11)	−0.0106 (14)
C13	0.0356 (10)	0.0625 (16)	0.0622 (15)	−0.0079 (11)	0.0026 (10)	−0.0057 (13)

Geometric parameters (Å, º) top

Cl1—C4	1.736 (3)	C5—H5	0.92 (3)
Cl2—C11	1.735 (3)	C6—H6	0.93 (3)
O1—C7	1.356 (3)	C7—C8	1.472 (3)
O1—C1	1.399 (3)	C8—C9	1.387 (3)
O2—C7	1.203 (3)	C8—C13	1.389 (3)
C1—C2	1.374 (3)	C9—C10	1.375 (4)
C1—C6	1.389 (3)	C9—H9	0.96 (3)
C2—C3	1.383 (4)	C10—C11	1.379 (3)
C2—H2	0.93 (3)	C10—H10	0.93 (3)
C3—C4	1.377 (4)	C11—C12	1.370 (4)
C3—H3	0.97 (3)	C12—C13	1.376 (4)
C4—C5	1.381 (3)	C12—H12	0.90 (3)
C5—C6	1.368 (4)	C13—H13	0.90 (3)

C7—O1—C1	119.07 (17)	O2—C7—C8	124.7 (2)
C2—C1—C6	120.9 (2)	O1—C7—C8	112.34 (19)
C2—C1—O1	117.2 (2)	C9—C8—C13	118.9 (2)
C6—C1—O1	121.7 (2)	C9—C8—C7	122.7 (2)
C1—C2—C3	119.8 (2)	C13—C8—C7	118.4 (2)
C1—C2—H2	120.1 (19)	C10—C9—C8	120.8 (2)
C3—C2—H2	120.1 (19)	C10—C9—H9	120.8 (18)
C4—C3—C2	119.2 (2)	C8—C9—H9	118.3 (18)
C4—C3—H3	126.1 (17)	C11—C10—C9	119.0 (2)
C2—C3—H3	114.7 (17)	C11—C10—H10	122 (2)
C3—C4—C5	120.8 (2)	C9—C10—H10	119 (2)
C3—C4—Cl1	119.77 (19)	C12—C11—C10	121.2 (2)
C5—C4—Cl1	119.41 (19)	C12—C11—Cl2	120.19 (19)
C6—C5—C4	120.1 (2)	C10—C11—Cl2	118.6 (2)
C6—C5—H5	124.0 (19)	C11—C12—C13	119.5 (2)
C4—C5—H5	115.8 (19)	C11—C12—H12	114 (2)
C5—C6—C1	119.1 (2)	C13—C12—H12	126 (2)
C5—C6—H6	123.0 (18)	C12—C13—C8	120.5 (2)
C1—C6—H6	117.8 (18)	C12—C13—H13	121 (2)
O2—C7—O1	122.9 (2)	C8—C13—H13	119 (2)

C7—O1—C1—C2	−129.5 (3)	O2—C7—C8—C9	172.1 (3)
C7—O1—C1—C6	55.0 (3)	O1—C7—C8—C9	−4.8 (4)
C6—C1—C2—C3	−0.8 (4)	O2—C7—C8—C13	−6.9 (4)
O1—C1—C2—C3	−176.3 (2)	O1—C7—C8—C13	176.2 (2)
C1—C2—C3—C4	−0.1 (4)	C13—C8—C9—C10	1.5 (4)
C2—C3—C4—C5	0.7 (4)	C7—C8—C9—C10	−177.5 (3)
C2—C3—C4—Cl1	−179.0 (2)	C8—C9—C10—C11	−0.9 (4)
C3—C4—C5—C6	−0.3 (4)	C9—C10—C11—C12	−0.2 (4)
Cl1—C4—C5—C6	179.4 (2)	C9—C10—C11—Cl2	−179.9 (2)
C4—C5—C6—C1	−0.6 (4)	C10—C11—C12—C13	0.7 (4)
C2—C1—C6—C5	1.1 (4)	Cl2—C11—C12—C13	−179.5 (2)
O1—C1—C6—C5	176.5 (2)	C11—C12—C13—C8	−0.1 (4)
C1—O1—C7—O2	3.2 (4)	C9—C8—C13—C12	−1.0 (4)
C1—O1—C7—C8	−179.9 (2)	C7—C8—C13—C12	178.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2ⁱ	0.92 (3)	2.58 (3)	3.168 (3)	123 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₃H₈Cl₂O₂
M_r	267.09
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	299
a, b, c (Å)	15.370 (2), 3.9528 (4), 19.465 (2)
β (°)	91.804 (9)
V (Å³)	1182.0 (2)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	4.83
Crystal size (mm)	0.45 × 0.23 × 0.18

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.194, 0.420
No. of measured, independent and observed [I > 2σ(I)] reflections	4211, 2109, 1724
R_int	0.080
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.139, 1.05
No. of reflections	2109
No. of parameters	178
H-atom treatment	Only H-atom coordinates refined
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.33

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
C5—H5···O2ⁱ	0.92 (3)	2.58 (3)	3.168 (3)	123 (2)

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

Acknowledgements

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

References

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