4-Chloro-2-(2-chloro­benzoyl)phenol

Bushra Begum, A.; Madan Kumar, S.; Manjunath, B.C.; Khanum, S.A.; Lokanath, N.K.

doi:10.1107/S1600536813025609

organic compounds

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ISSN: 2056-9890

Volume 69| Part 10| October 2013| Page o1568

doi:10.1107/S1600536813025609

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4-Chloro-2-(2-chlorobenzoyl)phenol

A. Bushra Begum,^a S. Madan Kumar,^b B. C. Manjunath,^b Shaukath Ara Khanum ^a ^* and N. K. Lokanath ^b

^aDepartment of Chemistry, Yuvaraja's College (Autonomous), University of Mysore, Mysore, 570 005, India, and ^bDepartment of Studies in Physics, Manasagangotri, University of Mysore, Mysore, 570 006, India
^*Correspondence e-mail: shaukathara@yahoo.co.in

(Received 4 September 2013; accepted 16 September 2013; online 21 September 2013)

In the title molecule, C₁₃H₈Cl₂O₂, the dihedral angle between the benzene rings is 74.53 (9)°. An intramolecular O—H⋯O hydrogen bond leading to a S(6) ring is observed. In the crystal, the molecules are connected into a three-dimensional network by C—H⋯O and π–π [inter-centroid distance = 3.6254 (10) Å] interactions.

CCDC reference: 960967

Related literature

For the biological activity of benzophenone derivatives, see: Khanum et al. (2005 , 2010 ). For a related structure, see: Devaiah et al. (2006 ).

Experimental

Crystal data

C₁₃H₈Cl₂O₂
M_r = 267.09
Orthorhombic, P b c a
a = 16.0231 (4) Å
b = 7.4216 (2) Å
c = 19.6843 (5) Å
V = 2340.80 (10) Å³
Z = 8
Cu Kα radiation
μ = 4.87 mm⁻¹
T = 295 K
0.20 × 0.19 × 0.18 mm

Data collection

Bruker X8 Proteum diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ) T_min = 0.442, T_max = 0.474
15868 measured reflections
1972 independent reflections
1712 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.105
S = 1.06
1972 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O16—H16⋯O9	0.82	1.88	2.598 (2)	146
C13—H13⋯O9ⁱ	0.93	2.50	3.413 (3)	168
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008 ); software used to prepare material for publication: Mercury.

Supporting information

CCDC reference: 960967

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813025609/tk5253sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813025609/tk5253Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813025609/tk5253Isup3.cml

checkCIF report

Comment top

The on-going research in synthesizing benzophenone derivatives in our laboratory resulted in the title molecule. These derivatives used in the preparation of anti-inflammatory (Khanum et al., 2010) and anti-fungal (Khanum et al., 2005) compounds.

In the title molecule (Fig. 1), the dihedral angle between chlorobenzene (C1–C6) and chlorohydroxybenzene (C10–C15) rings is 74.53 (9)°. The molecule features an intramolecular O—H..O hydrogen bond forming a S(6) ring (Table 1). The bond lengths and bond angles are similar to those in the 5-chloro-2-hydroxyphenyl-4-chlorophenyl-methanone structure (Devaiah et al., 2006)

The molecules are connected by C13–H13···O9 hydrogen bonds forming chains along the a axis (Fig. 2 and Table 1). Additional C6—Cl7···π(Cg1), Table 1, and π(Cg2···π(Cg2) interactions, with inter-centroid distance 3.6254 (10) Å [x-1, -y, z-1], lead to a three-dimensional architecture, Fig. 2; where Cg1: C1–C6 and Cg2: C10–C15.

Related literature top

For the biological activity of benzophenone derivatives, see: Khanum et al. (2005, 2010). For a related structure, see: Devaiah et al. (2006).

Experimental top

A mixture of anhydrous aluminium chloride (1.74 g, 12.94 mmol) and include the name of the compound here (2.0 g, 8.62 mmol), was protected from moisture by a calcium chloride guard tube and heated over an oil bath at 80–90 °C for 45 min. At the end of this period the contents were cooled and decomposed by acidulated ice-cold water. The residual solid was crushed into a powder, dissolved in ether (40 ml) and extracted with 10% sodium hydroxide (3 x 30 ml). The basic aqueous solution was neutralized with 10% hydrochloric acid. The filtered solid was washed with distilled water (3 x 30 ml) and recrystallized from ethanol to afford yellow needles of the title compound. Yield 1.6 g (80%). M.Pt: 357–359 K. IR (Nujol): 1615 ν(C═O), 3525–3655 cm^-1 ν(OH). ¹H NMR (CDCl₃): δ 6.9–7.5 (m, 7H, Ar—H), 9.2 (bs, 1H, OH). EI–MS: m/z 267 (M+, 81), 266 (100), 154.5 (57), 111.5 (50). Anal. Calcd. for C₁₃H₈Cl₂O₂ (267): C, 58.46; H, 3.02; Cl, 26.55. Found: C, 58.54; H, 3.25; Cl, 26.32%.

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: Mercury (Macrae et al., 2008).

Figures top

	Fig. 1. Molecular structure of the title compound along b-axis with 50% probability ellipsoids.
	Fig. 2. Packing diagram, viewed along the crystallographic b axis. Dotted lines represents C—H···O interactions.

4-Chloro-2-(2-chlorobenzoyl)phenol top

Crystal data top

C₁₃H₈Cl₂O₂	F(000) = 1088
M_r = 267.09	D_x = 1.516 Mg m⁻³
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1972 reflections
a = 16.0231 (4) Å	θ = 4.5–64.9°
b = 7.4216 (2) Å	µ = 4.87 mm⁻¹
c = 19.6843 (5) Å	T = 295 K
V = 2340.80 (10) Å³	Needle, yellow
Z = 8	0.20 × 0.19 × 0.18 mm

Data collection top

Bruker X8 Proteum diffractometer	1972 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	1712 reflections with I > 2σ(I)
Helios multilayer optics monochromator	R_int = 0.062
Detector resolution: 10.7 pixels mm^-1	θ_max = 64.9°, θ_min = 4.5°
\ϕ and \ω scans	h = −18→18
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −8→4
T_min = 0.442, T_max = 0.474	l = −23→22
15868 measured reflections

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0717P)² + 0.4839P] where P = (F_o² + 2F_c²)/3
1972 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₃H₈Cl₂O₂	V = 2340.80 (10) Å³
M_r = 267.09	Z = 8
Orthorhombic, Pbca	Cu Kα radiation
a = 16.0231 (4) Å	µ = 4.87 mm⁻¹
b = 7.4216 (2) Å	T = 295 K
c = 19.6843 (5) Å	0.20 × 0.19 × 0.18 mm

Data collection top

Bruker X8 Proteum diffractometer	1972 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	1712 reflections with I > 2σ(I)
T_min = 0.442, T_max = 0.474	R_int = 0.062
15868 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.06	Δρ_max = 0.30 e Å⁻³
1972 reflections	Δρ_min = −0.21 e Å⁻³
154 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
Cl7	0.41862 (4)	0.46830 (6)	0.29403 (2)	0.0481 (2)
Cl17	0.68664 (3)	0.11456 (7)	0.40130 (3)	0.0439 (2)
O9	0.29828 (9)	0.2266 (2)	0.43513 (7)	0.0486 (5)
O16	0.38062 (10)	0.3221 (2)	0.54298 (7)	0.0428 (5)
C1	0.37955 (13)	0.1912 (2)	0.21207 (9)	0.0330 (5)
C2	0.35120 (13)	0.0191 (2)	0.19888 (9)	0.0341 (5)
C3	0.32654 (14)	−0.0927 (2)	0.25143 (10)	0.0376 (6)
C4	0.33080 (13)	−0.0318 (2)	0.31807 (9)	0.0356 (6)
C5	0.36117 (12)	0.1391 (2)	0.33254 (9)	0.0289 (5)
C6	0.38485 (12)	0.2493 (2)	0.27869 (9)	0.0296 (5)
C8	0.36471 (13)	0.1988 (2)	0.40532 (9)	0.0317 (5)
C10	0.44516 (12)	0.2149 (2)	0.43988 (9)	0.0288 (5)
C11	0.44873 (12)	0.2764 (2)	0.50758 (9)	0.0310 (5)
C12	0.52597 (14)	0.2929 (2)	0.53977 (9)	0.0390 (6)
C13	0.59771 (13)	0.2463 (3)	0.50739 (10)	0.0373 (5)
C14	0.59454 (12)	0.1799 (2)	0.44109 (10)	0.0324 (5)
C15	0.52003 (12)	0.1657 (2)	0.40762 (9)	0.0289 (5)
H1	0.39490	0.26710	0.17660	0.0400*
H2	0.34870	−0.02210	0.15430	0.0410*
H3	0.30720	−0.20820	0.24220	0.0450*
H4	0.31320	−0.10620	0.35330	0.0430*
H12	0.52840	0.33640	0.58400	0.0470*
H13	0.64880	0.25860	0.52940	0.0450*
H15	0.51890	0.12320	0.36320	0.0350*
H16	0.33910	0.30760	0.51930	0.0640*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl7	0.0670 (4)	0.0413 (3)	0.0359 (3)	−0.0138 (2)	−0.0087 (2)	0.0009 (2)
Cl17	0.0269 (3)	0.0563 (3)	0.0484 (3)	0.0061 (2)	−0.0024 (2)	0.0039 (2)
O9	0.0283 (8)	0.0882 (10)	0.0294 (7)	0.0028 (7)	0.0032 (7)	−0.0086 (7)
O16	0.0401 (9)	0.0647 (8)	0.0237 (7)	−0.0061 (7)	0.0043 (6)	−0.0069 (6)
C1	0.0312 (10)	0.0440 (9)	0.0239 (9)	0.0027 (8)	−0.0001 (8)	0.0026 (7)
C2	0.0311 (10)	0.0465 (9)	0.0247 (9)	0.0068 (8)	−0.0053 (8)	−0.0055 (7)
C3	0.0368 (11)	0.0413 (9)	0.0347 (10)	−0.0027 (8)	−0.0084 (10)	−0.0037 (7)
C4	0.0332 (10)	0.0454 (10)	0.0281 (9)	−0.0050 (8)	−0.0019 (9)	0.0052 (7)
C5	0.0208 (9)	0.0437 (8)	0.0222 (8)	0.0011 (7)	−0.0026 (8)	0.0000 (6)
C6	0.0264 (9)	0.0381 (8)	0.0244 (8)	0.0004 (7)	−0.0020 (8)	−0.0006 (7)
C8	0.0262 (10)	0.0449 (9)	0.0241 (9)	0.0002 (7)	0.0020 (8)	0.0012 (7)
C10	0.0295 (10)	0.0349 (8)	0.0220 (8)	−0.0020 (7)	−0.0023 (8)	0.0030 (6)
C11	0.0331 (11)	0.0382 (8)	0.0216 (8)	−0.0044 (7)	0.0024 (8)	0.0022 (6)
C12	0.0465 (13)	0.0476 (9)	0.0228 (9)	−0.0109 (9)	−0.0073 (9)	0.0013 (7)
C13	0.0336 (10)	0.0475 (9)	0.0307 (9)	−0.0070 (8)	−0.0104 (9)	0.0074 (7)
C14	0.0291 (10)	0.0359 (8)	0.0322 (9)	−0.0006 (7)	−0.0036 (9)	0.0066 (7)
C15	0.0291 (10)	0.0353 (8)	0.0224 (8)	0.0005 (7)	−0.0009 (8)	0.0013 (6)

Geometric parameters (Å, º) top

Cl7—C6	1.7394 (16)	C10—C15	1.406 (3)
Cl17—C14	1.740 (2)	C10—C11	1.410 (2)
O9—C8	1.233 (2)	C11—C12	1.396 (3)
O16—C11	1.339 (2)	C12—C13	1.359 (3)
O16—H16	0.8200	C13—C14	1.396 (3)
C1—C6	1.383 (2)	C14—C15	1.368 (3)
C1—C2	1.380 (2)	C1—H1	0.9300
C2—C3	1.384 (3)	C2—H2	0.9300
C3—C4	1.389 (3)	C3—H3	0.9300
C4—C5	1.388 (2)	C4—H4	0.9300
C5—C6	1.392 (2)	C12—H12	0.9300
C5—C8	1.501 (2)	C13—H13	0.9300
C8—C10	1.462 (3)	C15—H15	0.9300

C11—O16—H16	109.00	C11—C12—C13	120.98 (17)
C2—C1—C6	119.15 (16)	C12—C13—C14	119.83 (19)
C1—C2—C3	120.55 (16)	Cl17—C14—C13	119.24 (15)
C2—C3—C4	119.79 (15)	C13—C14—C15	120.62 (18)
C3—C4—C5	120.55 (16)	Cl17—C14—C15	120.14 (15)
C4—C5—C8	118.62 (15)	C10—C15—C14	120.49 (17)
C6—C5—C8	122.91 (14)	C2—C1—H1	120.00
C4—C5—C6	118.45 (16)	C6—C1—H1	120.00
Cl7—C6—C5	120.12 (13)	C1—C2—H2	120.00
C1—C6—C5	121.49 (15)	C3—C2—H2	120.00
Cl7—C6—C1	118.36 (13)	C2—C3—H3	120.00
O9—C8—C10	121.73 (16)	C4—C3—H3	120.00
C5—C8—C10	120.10 (17)	C3—C4—H4	120.00
O9—C8—C5	118.11 (18)	C5—C4—H4	120.00
C8—C10—C11	120.13 (17)	C11—C12—H12	120.00
C8—C10—C15	121.39 (16)	C13—C12—H12	119.00
C11—C10—C15	118.46 (17)	C12—C13—H13	120.00
O16—C11—C10	122.76 (17)	C14—C13—H13	120.00
O16—C11—C12	117.67 (16)	C10—C15—H15	120.00
C10—C11—C12	119.57 (17)	C14—C15—H15	120.00

C6—C1—C2—C3	1.5 (3)	O9—C8—C10—C15	173.55 (16)
C2—C1—C6—Cl7	−178.65 (16)	C5—C8—C10—C11	178.00 (14)
C2—C1—C6—C5	−0.9 (3)	C5—C8—C10—C15	−3.7 (2)
C1—C2—C3—C4	−0.4 (3)	C8—C10—C11—O16	0.0 (2)
C2—C3—C4—C5	−1.3 (3)	C8—C10—C11—C12	−179.36 (14)
C3—C4—C5—C6	1.8 (3)	C15—C10—C11—O16	−178.36 (15)
C3—C4—C5—C8	−179.90 (19)	C15—C10—C11—C12	2.3 (2)
C4—C5—C6—Cl7	176.96 (15)	C8—C10—C15—C14	−179.27 (15)
C4—C5—C6—C1	−0.7 (3)	C11—C10—C15—C14	−0.9 (2)
C8—C5—C6—Cl7	−1.2 (3)	O16—C11—C12—C13	178.94 (17)
C8—C5—C6—C1	−178.93 (18)	C10—C11—C12—C13	−1.7 (2)
C4—C5—C8—O9	−69.0 (2)	C11—C12—C13—C14	−0.4 (3)
C4—C5—C8—C10	108.3 (2)	C12—C13—C14—Cl17	−178.09 (14)
C6—C5—C8—O9	109.2 (2)	C12—C13—C14—C15	1.8 (3)
C6—C5—C8—C10	−73.5 (2)	Cl17—C14—C15—C10	178.75 (12)
O9—C8—C10—C11	−4.8 (2)	C13—C14—C15—C10	−1.1 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O16—H16···O9	0.82	1.88	2.598 (2)	146
C13—H13···O9ⁱ	0.93	2.50	3.413 (3)	168
C6—Cl7···Cg1ⁱⁱ	1.74 (1)	3.89 (1)	4.901 (2)	116 (1)

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O16—H16···O9	0.82	1.88	2.598 (2)	146
C13—H13···O9ⁱ	0.93	2.50	3.413 (3)	168
C6—Cl7···Cg1ⁱⁱ	1.7394 (16)	3.8879 (10)	4.901 (2)	115.77 (7)

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

Acknowledgements

The authors thank the IOE and the University of Mysore for providing the single crystal X-ray diffractometer facility.

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