4-Chloro-2-hy­droxy-N-(4-methyl­phen­yl)benzamide

Raza, A.R.; Nisar, B.; Tahir, M.N.; Shamshad, S.

doi:10.1107/S1600536812000773

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o391

doi:10.1107/S1600536812000773

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4-Chloro-2-hydroxy-N-(4-methylphenyl)benzamide

Abdul Rauf Raza,^a Bushra Nisar,^a M. Nawaz Tahir ^b ^* and Sumaira Shamshad ^a

^aUniversity of Sargodha, Department of Chemistry, Sargodha, Pakistan, and ^bUniversity of Sargodha, Department of Physics, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 8 January 2012; accepted 8 January 2012; online 14 January 2012)

In the title compound, C₁₄H₁₂ClNO₂, the dihedral angle between the aromatic rings is 14.87 (11)° and an intramolecular N—H⋯O hydrogen bond generates an S(6) ring. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, generating C(6) chains propagating along the c-axis direction.

Related literature

For related structures, see: Raza et al. (2010 , 2011 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₄H₁₂ClNO₂
M_r = 261.70
Monoclinic, P 2₁ /c
a = 13.8553 (12) Å
b = 7.6197 (7) Å
c = 12.0114 (11) Å
β = 104.937 (5)°
V = 1225.23 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 296 K
0.34 × 0.14 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009) T_min = 0.979, T_max = 0.988
10366 measured reflections
2988 independent reflections
1832 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.163
S = 1.02
2988 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.39 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
N1—H1⋯O1	0.86	1.96	2.658 (3)	138
O1—H1A⋯O2ⁱ	0.82	1.85	2.664 (2)	173
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812000773/hb6597sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812000773/hb6597Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812000773/hb6597Isup3.cml

checkCIF report

Comment top

We have reported the crystal structures of (II) i.e., 2-hydroxy-N-(4-methylphenyl)benzamide (Raza et al., 2011) and (III) i.e., N-(4-chlorophenyl)-2-hydroxybenzamide (Raza et al., 2010) which are related to the title compound (I, Fig. 1). This compound has been prepared as a precursor for the synthesis of symmetric as well as asymmetric benzoxazepines.

In (I), the 3-chlorophenol group A (C1–C6/CL1/O1) and 4-methylanilinic group B (C8—C14) are roughly planar with r. m. s. deviations of 0.014 and 0.031 Å, respectively. The dihedral angle between A/B is 14.87 (11)°. The central formamide moiety C (O2/C7/N1) is of course planar. The dihedral angle between A/C and B/C is 7.59 (24)° and 18.74 (24)°, respectively. There exist intramolecular H-bondings of N—H···O and C—H···O types (Table 1, Fig. 1) completing S(6) ring motifs (Bernstein et al., 1995). There exists inter-molecular H-bondings of O—H···O type (Table 1, Fig. 2) due to which the molecules are linked in the form of one dimensional polymeric chains extending along the crystallographic c axis.

Related literature top

For related structures, see: Raza et al. (2010, 2011). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

The solution of 4-methylaniline (0.38 g, 4.0 mmol, 0.75 eq) in dry CHCl₃ and dry Et₃N (1 ml, 0.73 g, 7.0 mmol, 1.5 eq) was added slowly at room temperature to a mixture of 4-chloro-2-hydroxybenzoic acid (0.83 g, 5.0 mmol, 1 eq), SOCl₂ (3.24 ml, 5.28 g, 44.0 mmol, 1.2 eq) and catalytic amount of dimethylformamide (1 drop) followed by 4 h reflux. After completion of reaction, the reaction mixture was cooled to room temperature, neutralized with aqueous NaHCO₃ (10%), extracted with CHCl₃ (3×25 ml). The organic layer was combined, dried over anhydrous Na₂SO₄, filtered and concentrated under reduced pressure to afford crude product. The column chromatographic purification with 5% EtOAc in hexane (2 L) over a silica gel packed column (23 cm length) afforded the title compound I as a white crystalline solid in the 18–59^th fractions (50 ml each).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level. The dotted line indicate the intramolecular H-bond.
	Fig. 2. The partial packing showing polymeric chains extending along the c-axis.

4-Chloro-2-hydroxy-N-(4-methylphenyl)benzamide top

Crystal data top

C₁₄H₁₂ClNO₂	F(000) = 544
M_r = 261.70	D_x = 1.419 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1243 reflections
a = 13.8553 (12) Å	θ = 1.1–27.9°
b = 7.6197 (7) Å	µ = 0.30 mm⁻¹
c = 12.0114 (11) Å	T = 296 K
β = 104.937 (5)°	Block, colorless
V = 1225.23 (19) Å³	0.34 × 0.14 × 0.12 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	2988 independent reflections
Radiation source: fine-focus sealed tube	1832 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 7.6 pixels mm^-1	θ_max = 28.3°, θ_min = 3.0°
ω scans	h = −18→17
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −10→10
T_min = 0.979, T_max = 0.988	l = −15→15
10366 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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.163	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0803P)² + 0.1504P] where P = (F_o² + 2F_c²)/3
2988 reflections	(Δ/σ)_max < 0.001
165 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₄H₁₂ClNO₂	V = 1225.23 (19) Å³
M_r = 261.70	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.8553 (12) Å	µ = 0.30 mm⁻¹
b = 7.6197 (7) Å	T = 296 K
c = 12.0114 (11) Å	0.34 × 0.14 × 0.12 mm
β = 104.937 (5)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2988 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1832 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.988	R_int = 0.048
10366 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.163	H-atom parameters constrained
S = 1.02	Δρ_max = 0.39 e Å⁻³
2988 reflections	Δρ_min = −0.21 e Å⁻³
165 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 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	−0.34725 (5)	0.76527 (10)	−0.20816 (6)	0.0577 (3)
O1	0.02457 (12)	0.6924 (3)	−0.03254 (14)	0.0433 (6)
O2	0.00477 (12)	0.9612 (3)	0.26357 (13)	0.0429 (6)
N1	0.11035 (14)	0.8338 (3)	0.17119 (16)	0.0362 (7)
C1	−0.06586 (16)	0.8587 (3)	0.07420 (18)	0.0307 (7)
C2	−0.06343 (17)	0.7590 (3)	−0.02354 (19)	0.0309 (7)
C3	−0.15057 (17)	0.7321 (3)	−0.1100 (2)	0.0369 (8)
C4	−0.23926 (18)	0.8024 (3)	−0.1004 (2)	0.0395 (8)
C5	−0.24347 (18)	0.9064 (4)	−0.0066 (2)	0.0433 (9)
C6	−0.15738 (17)	0.9312 (3)	0.0788 (2)	0.0378 (8)
C7	0.01973 (17)	0.8882 (3)	0.17747 (19)	0.0330 (7)
C8	0.20016 (17)	0.8321 (3)	0.25990 (19)	0.0336 (7)
C9	0.21756 (18)	0.9335 (3)	0.3585 (2)	0.0398 (8)
C10	0.30691 (19)	0.9134 (4)	0.4426 (2)	0.0442 (9)
C11	0.38017 (19)	0.7971 (4)	0.4309 (2)	0.0447 (9)
C12	0.36287 (19)	0.7055 (4)	0.3288 (2)	0.0498 (9)
C13	0.27424 (19)	0.7211 (3)	0.2442 (2)	0.0440 (8)
C14	0.4741 (2)	0.7698 (4)	0.5263 (3)	0.0643 (11)
H1	0.11427	0.79538	0.10518	0.0435*
H1A	0.01808	0.65337	−0.09769	0.0649*
H3	−0.14878	0.66625	−0.17466	0.0443*
H5	−0.30317	0.95784	−0.00191	0.0519*
H6	−0.16000	0.99904	0.14229	0.0454*
H9	0.17007	1.01407	0.36852	0.0478*
H10	0.31781	0.98082	0.50924	0.0531*
H12	0.41224	0.63092	0.31648	0.0598*
H13	0.26452	0.65658	0.17647	0.0528*
H14A	0.52971	0.75280	0.49345	0.0964*
H14B	0.46641	0.66814	0.57041	0.0964*
H14C	0.48596	0.87099	0.57550	0.0964*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0388 (4)	0.0747 (6)	0.0499 (4)	−0.0043 (3)	−0.0061 (3)	−0.0010 (4)
O1	0.0351 (9)	0.0606 (12)	0.0338 (10)	0.0033 (8)	0.0084 (7)	−0.0120 (9)
O2	0.0414 (10)	0.0602 (12)	0.0272 (9)	0.0023 (9)	0.0092 (7)	−0.0060 (8)
N1	0.0368 (11)	0.0452 (13)	0.0260 (10)	−0.0010 (9)	0.0068 (8)	−0.0022 (9)
C1	0.0343 (12)	0.0321 (13)	0.0252 (12)	−0.0021 (10)	0.0070 (9)	0.0041 (10)
C2	0.0314 (12)	0.0324 (13)	0.0294 (12)	−0.0004 (9)	0.0089 (9)	0.0042 (10)
C3	0.0388 (13)	0.0418 (15)	0.0294 (13)	−0.0043 (11)	0.0078 (10)	−0.0026 (10)
C4	0.0348 (13)	0.0446 (15)	0.0358 (14)	−0.0041 (11)	0.0034 (10)	0.0053 (11)
C5	0.0346 (14)	0.0503 (17)	0.0444 (15)	0.0045 (11)	0.0093 (11)	0.0018 (12)
C6	0.0395 (13)	0.0400 (14)	0.0341 (13)	0.0025 (11)	0.0098 (10)	−0.0020 (11)
C7	0.0386 (13)	0.0331 (13)	0.0284 (12)	−0.0039 (10)	0.0108 (10)	0.0054 (10)
C8	0.0352 (12)	0.0374 (14)	0.0276 (12)	−0.0045 (10)	0.0071 (10)	0.0026 (10)
C9	0.0386 (14)	0.0428 (15)	0.0374 (14)	−0.0022 (11)	0.0088 (11)	−0.0047 (11)
C10	0.0453 (15)	0.0510 (17)	0.0338 (14)	−0.0094 (12)	0.0056 (11)	−0.0053 (12)
C11	0.0385 (14)	0.0516 (16)	0.0394 (15)	−0.0056 (12)	0.0017 (11)	0.0051 (12)
C12	0.0364 (14)	0.0592 (18)	0.0513 (17)	0.0051 (12)	0.0066 (12)	−0.0047 (14)
C13	0.0418 (14)	0.0518 (16)	0.0381 (14)	−0.0005 (12)	0.0098 (11)	−0.0089 (12)
C14	0.0489 (18)	0.074 (2)	0.057 (2)	−0.0018 (15)	−0.0098 (14)	0.0058 (16)

Geometric parameters (Å, º) top

Cl1—C4	1.731 (3)	C9—C10	1.390 (4)
O1—C2	1.351 (3)	C10—C11	1.382 (4)
O2—C7	1.238 (3)	C11—C12	1.377 (4)
O1—H1A	0.8200	C11—C14	1.510 (4)
N1—C7	1.343 (3)	C12—C13	1.383 (4)
N1—C8	1.414 (3)	C3—H3	0.9300
N1—H1	0.8600	C5—H5	0.9300
C1—C7	1.496 (3)	C6—H6	0.9300
C1—C6	1.397 (3)	C9—H9	0.9300
C1—C2	1.406 (3)	C10—H10	0.9300
C2—C3	1.390 (3)	C12—H12	0.9300
C3—C4	1.372 (3)	C13—H13	0.9300
C4—C5	1.391 (3)	C14—H14A	0.9600
C5—C6	1.371 (3)	C14—H14B	0.9600
C8—C13	1.380 (3)	C14—H14C	0.9600
C8—C9	1.382 (3)

C2—O1—H1A	109.00	C10—C11—C12	116.9 (2)
C7—N1—C8	127.9 (2)	C12—C11—C14	121.6 (3)
C7—N1—H1	116.00	C11—C12—C13	121.9 (3)
C8—N1—H1	116.00	C8—C13—C12	120.2 (2)
C2—C1—C6	117.6 (2)	C2—C3—H3	120.00
C2—C1—C7	126.1 (2)	C4—C3—H3	120.00
C6—C1—C7	116.2 (2)	C4—C5—H5	121.00
C1—C2—C3	120.0 (2)	C6—C5—H5	121.00
O1—C2—C1	119.1 (2)	C1—C6—H6	119.00
O1—C2—C3	120.9 (2)	C5—C6—H6	119.00
C2—C3—C4	120.3 (2)	C8—C9—H9	120.00
Cl1—C4—C3	119.57 (18)	C10—C9—H9	120.00
Cl1—C4—C5	119.4 (2)	C9—C10—H10	119.00
C3—C4—C5	121.1 (2)	C11—C10—H10	119.00
C4—C5—C6	118.3 (2)	C11—C12—H12	119.00
C1—C6—C5	122.6 (2)	C13—C12—H12	119.00
N1—C7—C1	117.4 (2)	C8—C13—H13	120.00
O2—C7—C1	119.5 (2)	C12—C13—H13	120.00
O2—C7—N1	123.1 (2)	C11—C14—H14A	109.00
N1—C8—C9	124.5 (2)	C11—C14—H14B	109.00
N1—C8—C13	116.3 (2)	C11—C14—H14C	110.00
C9—C8—C13	119.2 (2)	H14A—C14—H14B	109.00
C8—C9—C10	119.2 (2)	H14A—C14—H14C	109.00
C9—C10—C11	122.5 (2)	H14B—C14—H14C	110.00
C10—C11—C14	121.5 (2)

C8—N1—C7—O2	6.7 (4)	C2—C3—C4—Cl1	−179.23 (18)
C8—N1—C7—C1	−173.7 (2)	C2—C3—C4—C5	2.2 (4)
C7—N1—C8—C9	−20.6 (4)	Cl1—C4—C5—C6	178.8 (2)
C7—N1—C8—C13	159.8 (2)	C3—C4—C5—C6	−2.7 (4)
C6—C1—C2—O1	177.7 (2)	C4—C5—C6—C1	1.1 (4)
C6—C1—C2—C3	−1.5 (3)	N1—C8—C9—C10	176.5 (2)
C7—C1—C2—O1	−5.5 (4)	C13—C8—C9—C10	−3.9 (4)
C7—C1—C2—C3	175.4 (2)	N1—C8—C13—C12	−177.2 (2)
C2—C1—C6—C5	1.0 (4)	C9—C8—C13—C12	3.1 (4)
C7—C1—C6—C5	−176.2 (2)	C8—C9—C10—C11	0.9 (4)
C2—C1—C7—O2	−171.4 (2)	C9—C10—C11—C12	2.7 (4)
C2—C1—C7—N1	8.9 (3)	C9—C10—C11—C14	−176.4 (3)
C6—C1—C7—O2	5.5 (3)	C10—C11—C12—C13	−3.5 (4)
C6—C1—C7—N1	−174.1 (2)	C14—C11—C12—C13	175.6 (3)
O1—C2—C3—C4	−179.2 (2)	C11—C12—C13—C8	0.7 (4)
C1—C2—C3—C4	−0.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.96	2.658 (3)	138
O1—H1A···O2ⁱ	0.82	1.85	2.664 (2)	173

Symmetry code: (i) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂ClNO₂
M_r	261.70
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	13.8553 (12), 7.6197 (7), 12.0114 (11)
β (°)	104.937 (5)
V (Å³)	1225.23 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.34 × 0.14 × 0.12

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.979, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	10366, 2988, 1832
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.163, 1.02
No. of reflections	2988
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.21

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.96	2.658 (3)	138
O1—H1A···O2ⁱ	0.82	1.85	2.664 (2)	173

Symmetry code: (i) x, −y+3/2, z−1/2.

Acknowledgements

The authors acknowledge the provision of funds for the purchase of diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. The authors also acknowledge the technical support provided by Syed Muhammad Hussain Rizvi of Bana International, Karachi, Pakistan. ARR also acknowledges the Higher Education Commission, Government of Pakistan, for generous support of a research project (20–819).

References

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