N-(2-Chloro­phen­yl)-3-methyl­benzamide

Rodrigues, V.Z.; Tokarčík, M.; Gowda, B.T.; Kožíšek, J.

doi:10.1107/S160053681000992X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o891

doi:10.1107/S160053681000992X

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N-(2-Chlorophenyl)-3-methylbenzamide

Vinola Zeena Rodrigues,^a Miroslav Tokarčík,^b B. Thimme Gowda ^a ^* and Jozef Kožíšek ^b

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, and ^bFaculty of Chemical and Food Technology, Slovak Technical University, Radlinského 9, SK-812 37 Bratislava, Slovak Republic
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 15 March 2010; accepted 17 March 2010; online 20 March 2010)

In the title compound, C₁₄H₁₂ClNO, the N—H bond is anti to the carbonyl bond and the two aromatic rings make a dihedral angle of 5.4 (2)°. In the crystal, intermolecular N—H⋯O hydrogen bonds connect the molecules into chains running along the b axis. The chains are interconnected through short Cl⋯Cl contacts [3.279 (1) Å].

Related literature

For the preparation of the compound, see: Gowda et al. (2003 ). For related structures, see: Bowes et al. (2003 ); Gowda et al. (2008a ,b ).

Experimental

Crystal data

C₁₄H₁₂ClNO
M_r = 245.7
Monoclinic, P 2₁ /c
a = 9.9972 (3) Å
b = 4.9124 (1) Å
c = 24.6662 (7) Å
β = 100.248 (3)°
V = 1192.04 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 295 K
0.55 × 0.35 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Ruby Gemini detector
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.897, T_max = 0.978
25420 measured reflections
2119 independent reflections
1884 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.108
S = 1.05
2119 reflections
157 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.86	2.16	2.936 (2)	151
Symmetry code: (i) x, y+1, z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2002 ); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009 ) and WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablock global. DOI: 10.1107/S160053681000992X/bt5219sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681000992X/bt5219Isup2.hkl

checkCIF report

Comment top

As part of a study of the substituent effects on the crystal structures of benzanilides (Gowda et al., 2008a,b), the structure of N-(2-chlorophenyl)3-methylbenzamide (I) has been determined. In the structure, the conformations of the N—H and C=O bonds are anti to each other (Fig. 1), similar to those observed in in N-(2-chlorophenyl)2-methylbenzamide (II), N-(2-chlorophenyl)benzamide (III)(Gowda et al., 2008b), 3-methyl-N-(phenyl)benzamide (IV) (Gowda et al., 2008a) and the parent benzanilide (Bowes et al., 2003). Further, the conformation of the C=O bond in (I) is also anti to the meta- methyl substituent in the benzoyl ring, while the conformation of the N—H bond is syn to the ortho-Cl group in the aniline ring..

The central amide group –NH—C(=O)– is twisted by 35.6 (2)° and 37.9 (2)° out of the planes of the 3-methylphenyl and 2-chlorophenyl rings, respectively.

The dihedral angle between the two benzene rings is 5.4 (2)°, compared to the values of 7.4 (3)° in (II) and 22.2 (2)°) & 75.9 (1), in the molecules 1 and 2 of (IV), respectively.

The packing diagram of molecules in (I) showing the intermolecular N–H···O hydrogen bonds (Table 1) involved in the formation of molecular chains running along the b-axis is shown in Fig. 2. The chains are interconnected through short Cl···Cl contacts of 3.279 (1) Å.

Related literature top

For the preparation of the compound, see: Gowda et al. (2003). For related structures, see: Bowes et al. (2003); Gowda et al. (2008a,b).

Experimental top

The title compound was prepared according to the literature method (Gowda et al., 2003). The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared and NMR spectra. Single crystals of the title compound used in X-ray diffraction studies were obtained from a slow evaporation of its ethanolic solution at room temperature.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Molecular structure of (I) showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Part of crystal structure of (I) showing molecular chains running along the b-axis and interconnected through the Cl—Cl contacts. Hydrogen bonds and short Cl—Cl contacts are shown as dashed lines. H atoms not involved in hydrogen bonding were omitted. Symmetry codes: (i) x, 1+y, z; (ii) -x, 1-y, 1-z.

N-(2-Chlorophenyl)-3-methylbenzamide top

Crystal data top

C₁₄H₁₂ClNO	F(000) = 512
M_r = 245.7	D_x = 1.369 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 16100 reflections
a = 9.9972 (3) Å	θ = 2.1–29.5°
b = 4.9124 (1) Å	µ = 0.30 mm⁻¹
c = 24.6662 (7) Å	T = 295 K
β = 100.248 (3)°	Block, colourless
V = 1192.04 (5) Å³	0.55 × 0.35 × 0.08 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Ruby Gemini detector	2119 independent reflections
Graphite monochromator	1884 reflections with I > 2σ(I)
Detector resolution: 10.434 pixels mm^-1	R_int = 0.050
ω scans	θ_max = 25.1°, θ_min = 2.1°
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2009)	h = −11→11
T_min = 0.897, T_max = 0.978	k = −5→5
25420 measured reflections	l = −29→29

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0534P)² + 0.5999P] where P = (F_o² + 2F_c²)/3
2119 reflections	(Δ/σ)_max < 0.001
157 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₄H₁₂ClNO	V = 1192.04 (5) Å³
M_r = 245.7	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.9972 (3) Å	µ = 0.30 mm⁻¹
b = 4.9124 (1) Å	T = 295 K
c = 24.6662 (7) Å	0.55 × 0.35 × 0.08 mm
β = 100.248 (3)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Ruby Gemini detector	2119 independent reflections
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2009)	1884 reflections with I > 2σ(I)
T_min = 0.897, T_max = 0.978	R_int = 0.050
25420 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.05	Δρ_max = 0.22 e Å⁻³
2119 reflections	Δρ_min = −0.22 e Å⁻³
157 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	Occ. (<1)
C1	0.29838 (18)	−0.1699 (3)	0.57259 (7)	0.0361 (4)
C2	0.28794 (18)	−0.0729 (3)	0.62913 (7)	0.0351 (4)
C3	0.19358 (19)	0.1212 (4)	0.63886 (8)	0.0379 (4)
H3	0.1363	0.1997	0.6091	0.045*
C4	0.18309 (19)	0.2001 (4)	0.69191 (8)	0.0396 (4)
C5	0.2713 (2)	0.0838 (4)	0.73564 (8)	0.0459 (5)
H5	0.2666	0.1359	0.7715	0.055*
C6	0.3659 (2)	−0.1087 (4)	0.72660 (8)	0.0479 (5)
H6	0.4246	−0.1841	0.7563	0.057*
C7	0.3737 (2)	−0.1891 (4)	0.67377 (8)	0.0425 (5)
H7	0.4362	−0.3211	0.6679	0.051*
C8	0.27931 (18)	−0.0271 (3)	0.47628 (7)	0.0349 (4)
C9	0.18735 (19)	0.1059 (4)	0.43608 (8)	0.0385 (4)
C10	0.1894 (2)	0.0693 (5)	0.38088 (8)	0.0523 (5)
H10	0.1269	0.1598	0.3546	0.063*
C11	0.2843 (3)	−0.1017 (5)	0.36470 (9)	0.0583 (6)
H11	0.2861	−0.1271	0.3275	0.07*
C12	0.3762 (2)	−0.2344 (5)	0.40389 (9)	0.0539 (5)
H12	0.4401	−0.3504	0.393	0.065*
C13	0.3748 (2)	−0.1975 (4)	0.45914 (8)	0.0437 (5)
H13	0.4382	−0.2873	0.4852	0.052*
C14	0.0792 (2)	0.4081 (4)	0.70160 (9)	0.0534 (5)
H14A	0.0666	0.3986	0.7392	0.08*	0.66 (3)
H14B	−0.0056	0.3716	0.6776	0.08*	0.66 (3)
H14C	0.1103	0.5868	0.6941	0.08*	0.66 (3)
H14D	0.0476	0.506	0.6681	0.08*	0.34 (3)
H14E	0.1198	0.5331	0.7297	0.08*	0.34 (3)
H14F	0.0039	0.3179	0.7132	0.08*	0.34 (3)
N1	0.27660 (16)	0.0202 (3)	0.53244 (6)	0.0373 (4)
H1N	0.2597	0.1834	0.5419	0.045*
O1	0.32539 (16)	−0.4076 (3)	0.56431 (6)	0.0511 (4)
Cl1	0.06537 (6)	0.31991 (12)	0.45519 (2)	0.0569 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0421 (10)	0.0259 (9)	0.0396 (10)	0.0012 (7)	0.0058 (8)	0.0004 (7)
C2	0.0404 (10)	0.0263 (9)	0.0390 (10)	−0.0015 (7)	0.0081 (8)	0.0021 (7)
C3	0.0458 (10)	0.0287 (9)	0.0389 (10)	0.0016 (8)	0.0067 (8)	0.0041 (7)
C4	0.0465 (11)	0.0300 (9)	0.0447 (10)	−0.0042 (8)	0.0149 (8)	−0.0015 (8)
C5	0.0594 (13)	0.0444 (11)	0.0355 (10)	−0.0052 (9)	0.0129 (9)	−0.0041 (8)
C6	0.0527 (12)	0.0505 (12)	0.0384 (10)	0.0024 (10)	0.0025 (9)	0.0049 (9)
C7	0.0457 (11)	0.0378 (10)	0.0441 (11)	0.0067 (8)	0.0079 (8)	0.0029 (8)
C8	0.0412 (10)	0.0264 (9)	0.0381 (9)	−0.0006 (7)	0.0096 (7)	−0.0024 (7)
C9	0.0423 (10)	0.0330 (9)	0.0410 (10)	0.0054 (8)	0.0097 (8)	−0.0023 (8)
C10	0.0593 (13)	0.0581 (13)	0.0383 (10)	0.0138 (11)	0.0052 (9)	0.0003 (9)
C11	0.0753 (15)	0.0626 (14)	0.0405 (11)	0.0123 (12)	0.0195 (10)	−0.0065 (10)
C12	0.0595 (13)	0.0512 (12)	0.0556 (13)	0.0149 (10)	0.0227 (10)	−0.0088 (10)
C13	0.0469 (11)	0.0386 (10)	0.0464 (11)	0.0100 (9)	0.0099 (9)	−0.0013 (9)
C14	0.0628 (14)	0.0444 (11)	0.0571 (13)	0.0064 (10)	0.0222 (10)	−0.0039 (10)
N1	0.0514 (9)	0.0248 (7)	0.0361 (8)	0.0072 (7)	0.0091 (7)	−0.0016 (6)
O1	0.0801 (10)	0.0252 (7)	0.0494 (8)	0.0073 (6)	0.0152 (7)	−0.0007 (6)
Cl1	0.0570 (3)	0.0622 (4)	0.0510 (3)	0.0279 (3)	0.0085 (2)	−0.0044 (2)

Geometric parameters (Å, º) top

C1—O1	1.224 (2)	C9—C10	1.377 (3)
C1—N1	1.350 (2)	C9—Cl1	1.7375 (18)
C1—C2	1.495 (3)	C10—C11	1.378 (3)
C2—C7	1.392 (3)	C10—H10	0.93
C2—C3	1.392 (3)	C11—C12	1.374 (3)
C3—C4	1.386 (3)	C11—H11	0.93
C3—H3	0.93	C12—C13	1.377 (3)
C4—C5	1.389 (3)	C12—H12	0.93
C4—C14	1.507 (3)	C13—H13	0.93
C5—C6	1.384 (3)	C14—H14A	0.96
C5—H5	0.93	C14—H14B	0.96
C6—C7	1.377 (3)	C14—H14C	0.96
C6—H6	0.93	C14—H14D	0.96
C7—H7	0.93	C14—H14E	0.96
C8—C9	1.390 (3)	C14—H14F	0.96
C8—C13	1.391 (3)	N1—H1N	0.86
C8—N1	1.410 (2)

O1—C1—N1	123.31 (17)	C8—C9—Cl1	119.86 (14)
O1—C1—C2	120.91 (16)	C9—C10—C11	119.87 (19)
N1—C1—C2	115.78 (15)	C9—C10—H10	120.1
C7—C2—C3	119.03 (17)	C11—C10—H10	120.1
C7—C2—C1	118.18 (16)	C12—C11—C10	119.63 (19)
C3—C2—C1	122.76 (16)	C12—C11—H11	120.2
C4—C3—C2	121.43 (17)	C10—C11—H11	120.2
C4—C3—H3	119.3	C11—C12—C13	120.66 (19)
C2—C3—H3	119.3	C11—C12—H12	119.7
C3—C4—C5	118.30 (17)	C13—C12—H12	119.7
C3—C4—C14	120.62 (18)	C12—C13—C8	120.58 (19)
C5—C4—C14	121.08 (18)	C12—C13—H13	119.7
C6—C5—C4	120.91 (18)	C8—C13—H13	119.7
C6—C5—H5	119.5	C4—C14—H14A	109.5
C4—C5—H5	119.5	C4—C14—H14B	109.5
C7—C6—C5	120.24 (18)	C4—C14—H14C	109.5
C7—C6—H6	119.9	C4—C14—H14D	109.5
C5—C6—H6	119.9	C4—C14—H14E	109.5
C6—C7—C2	120.07 (18)	H14D—C14—H14E	109.5
C6—C7—H7	120	C4—C14—H14F	109.5
C2—C7—H7	120	H14D—C14—H14F	109.5
C9—C8—C13	117.94 (17)	H14E—C14—H14F	109.5
C9—C8—N1	119.86 (16)	C1—N1—C8	125.30 (15)
C13—C8—N1	122.16 (17)	C1—N1—H1N	117.3
C10—C9—C8	121.32 (17)	C8—N1—H1N	117.3
C10—C9—Cl1	118.82 (15)

O1—C1—C2—C7	34.3 (3)	N1—C8—C9—C10	178.40 (18)
N1—C1—C2—C7	−145.58 (18)	C13—C8—C9—Cl1	179.69 (14)
O1—C1—C2—C3	−143.6 (2)	N1—C8—C9—Cl1	−2.4 (2)
N1—C1—C2—C3	36.5 (2)	C8—C9—C10—C11	−0.1 (3)
C7—C2—C3—C4	−0.2 (3)	Cl1—C9—C10—C11	−179.31 (18)
C1—C2—C3—C4	177.67 (17)	C9—C10—C11—C12	0.0 (4)
C2—C3—C4—C5	1.1 (3)	C10—C11—C12—C13	−0.2 (4)
C2—C3—C4—C14	−179.28 (17)	C11—C12—C13—C8	0.6 (3)
C3—C4—C5—C6	−0.9 (3)	C9—C8—C13—C12	−0.8 (3)
C14—C4—C5—C6	179.54 (19)	N1—C8—C13—C12	−178.60 (18)
C4—C5—C6—C7	−0.3 (3)	O1—C1—N1—C8	1.2 (3)
C5—C6—C7—C2	1.3 (3)	C2—C1—N1—C8	−178.98 (16)
C3—C2—C7—C6	−1.0 (3)	C9—C8—N1—C1	142.39 (19)
C1—C2—C7—C6	−178.99 (18)	C13—C8—N1—C1	−39.8 (3)
C13—C8—C9—C10	0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.86	2.16	2.936 (2)	151

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂ClNO
M_r	245.7
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	9.9972 (3), 4.9124 (1), 24.6662 (7)
β (°)	100.248 (3)
V (Å³)	1192.04 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.55 × 0.35 × 0.08

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with a Ruby Gemini detector
Absorption correction	Analytical (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.897, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	25420, 2119, 1884
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.108, 1.05
No. of reflections	2119
No. of parameters	157
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.22

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2002), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.86	2.16	2.936 (2)	151

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

Acknowledgements

MT and JK thank the Grant Agency of the Slovak Republic (VEGA 1/0817/08) and the Structural Funds, Interreg IIIA, for financial support in purchasing the diffractometer. VZR thanks the University Grants Commission, Government of India, New Delhi, for the award of a research fellowship.

References

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