N-(4-Chloro­phen­yl)-2-methyl­benzamide

Gowda, B.T.; Foro, S.; Sowmya, B.P.; Terao, H.; Fuess, H.

doi:10.1107/S1600536809002633

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o389

doi:10.1107/S1600536809002633

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N-(4-Chlorophenyl)-2-methylbenzamide

B. Thimme Gowda,^a ^* Sabine Foro,^b B. P. Sowmya,^a Hiromitsu Terao ^c and Hartmut Fuess ^b

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, ^bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany, and ^cFaculty of Integrated Arts and Sciences, Tokushima University, Minamijosanjima-cho, Tokushima 770-8502, Japan
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 20 January 2009; accepted 21 January 2009; online 28 January 2009)

In the structure of the title compound, C₁₄H₁₂ClNO, the N—H and C=O bonds are trans to each other. Furthermore, the C=O bond is syn to the ortho-methyl group in the benzoyl ring, similar to what is observed in 2-methyl-N-(4-methylphenyl)benzamide and 2-methyl-N-phenylbenzamide. The amide linkage (–NHCO–) makes dihedral angles of 36.9 (7) and 46.4 (5)° with the aniline and benzoyl rings, respectively, while the dihedral angle between the benzoyl and aniline rings is 83.1 (1)°. In the crystal structure, molecules form chains running along the b axis through N—H⋯O hydrogen bonds.

Related literature

For related structures, see: Gowda et al. (2003 , 2008a ,b ); Gowda, Tokarčík et al. (2008 ).

Experimental

Crystal data

C₁₄H₁₂ClNO
M_r = 245.70
Monoclinic, C 2/c
a = 22.345 (2) Å
b = 5.1092 (4) Å
c = 22.222 (1) Å
β = 109.593 (6)°
V = 2390.1 (3) Å³
Z = 8
Cu Kα radiation
μ = 2.67 mm⁻¹
T = 299 (2) K
0.50 × 0.13 × 0.13 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
2213 measured reflections
2085 independent reflections
1741 reflections with I > 2σ(I)
R_int = 0.074
3 standard reflections frequency: 120 min intensity decay: 1.0%

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.159
S = 1.08
2085 reflections
182 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.84 (3)	2.14 (3)	2.937 (3)	159 (2)
Symmetry code: (i) x, y-1, 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/S1600536809002633/bt2857sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809002633/bt2857Isup2.hkl

checkCIF report

Comment top

In the present work, as part of a study of the substituent effects on the solid state structures of benzanilides (Gowda et al., 2003; 2008a, b, c), the structure of 2-methyl-N-(4-chlorophenyl)- benzamide has been determined. In the structure of the title compound (Fig. 1), the N—H and C=O bonds are trans to each other. Further, the C=O bond is syn to the ortho-methyl substituent in the benzoyl ring. These observations are similar to those observed in 2-methyl-N-(phenyl)-benzamide (Gowda et al., 2008a), 2-methyl-N-(4-methylphenyl)- benzamide (Gowda, Tokarčík et al., 2008), 2-methyl-N- (2-chlorophenyl)-benzamide and 2-methyl-N-(3-chlorophenyl)- benzamide (Gowda et al., 2008b). The amide linkage, –NHCO– makes dihedral angles of 36.9 (7)° and 46.4 (5)° with the aniline and benzoyl rings, respectively, while the dihedral angle between the benzoyl and aniline rings is 83.1 (1)°, in comparison with the central amide group –NHCO– being tilted to the benzoyl ring at an angle of 60.0 (1)° and the two rings (benzoyl & aniline) making a dihedral angle of 81.4 (1)° in N4MP2MBA. The other bond parameters in the title compound are similar to those in the previously mentioned structures. The packing diagram shows N—H···O (Table 1) hydrogen bonds connnecting the molecules into chains running along the b-axis (Fig. 2).

Related literature top

For related structures, see: Gowda et al. (2003, 2008a,b); Gowda, Tokarčík et al. (2008).

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: 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 scheme. The displacement ellipsoids are drawn at the 50% probability level. The H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Molecular packing of the title compound with hydrogen bonding shown as dashed lines..

N-(4-Chlorophenyl)-2-methylbenzamide top

Crystal data top

C₁₄H₁₂ClNO	F(000) = 1024
M_r = 245.70	D_x = 1.366 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 22.345 (2) Å	θ = 8.1–22.2°
b = 5.1092 (4) Å	µ = 2.67 mm⁻¹
c = 22.222 (1) Å	T = 299 K
β = 109.593 (6)°	Rod, colourless
V = 2390.1 (3) Å³	0.50 × 0.13 × 0.13 mm
Z = 8

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.074
Radiation source: fine-focus sealed tube	θ_max = 66.9°, θ_min = 4.2°
Graphite monochromator	h = −25→26
ω/2θ scans	k = −6→0
2213 measured reflections	l = −26→1
2085 independent reflections	3 standard reflections every 120 min
1741 reflections with I > 2σ(I)	intensity decay: 1.0%

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)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.159	w = 1/[σ²(F_o²) + (0.1089P)² + 0.7738P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.002
2085 reflections	Δρ_max = 0.27 e Å⁻³
182 parameters	Δρ_min = −0.39 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: 0.0012 (3)

Crystal data top

C₁₄H₁₂ClNO	V = 2390.1 (3) Å³
M_r = 245.70	Z = 8
Monoclinic, C2/c	Cu Kα radiation
a = 22.345 (2) Å	µ = 2.67 mm⁻¹
b = 5.1092 (4) Å	T = 299 K
c = 22.222 (1) Å	0.50 × 0.13 × 0.13 mm
β = 109.593 (6)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.074
2213 measured reflections	3 standard reflections every 120 min
2085 independent reflections	intensity decay: 1.0%
1741 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.159	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.27 e Å⁻³
2085 reflections	Δρ_min = −0.39 e Å⁻³
182 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
C1	0.38579 (10)	−0.0174 (4)	0.97284 (10)	0.0427 (5)
C2	0.43053 (12)	−0.1978 (5)	0.96925 (11)	0.0531 (6)
H2	0.4467 (13)	−0.343 (6)	1.0021 (12)	0.064*
C3	0.45905 (12)	−0.1751 (6)	0.92298 (12)	0.0582 (6)
H3	0.4906 (14)	−0.296 (6)	0.9225 (13)	0.070*
C4	0.44190 (11)	0.0270 (5)	0.88024 (10)	0.0501 (6)
C5	0.39547 (13)	0.2001 (5)	0.88127 (11)	0.0556 (6)
H5	0.3833 (13)	0.344 (7)	0.8502 (13)	0.067*
C6	0.36711 (12)	0.1774 (5)	0.92743 (10)	0.0541 (6)
H6	0.3328 (14)	0.277 (6)	0.9283 (12)	0.065*
C7	0.34840 (11)	0.1669 (4)	1.05601 (10)	0.0464 (5)
C8	0.32646 (10)	0.0953 (4)	1.11029 (10)	0.0422 (5)
C9	0.35181 (9)	0.2246 (4)	1.16938 (9)	0.0437 (5)
C10	0.32915 (11)	0.1468 (5)	1.21792 (11)	0.0529 (6)
H10	0.3491 (12)	0.242 (6)	1.2606 (13)	0.063*
C11	0.28353 (12)	−0.0416 (5)	1.20908 (12)	0.0573 (6)
H11	0.2695 (14)	−0.099 (6)	1.2430 (14)	0.069*
C12	0.25847 (11)	−0.1652 (5)	1.15110 (12)	0.0567 (6)
H12	0.2257 (13)	−0.308 (6)	1.1438 (12)	0.068*
C13	0.28029 (11)	−0.0955 (5)	1.10188 (11)	0.0497 (5)
H13	0.2621 (12)	−0.182 (6)	1.0597 (12)	0.060*
C14	0.40270 (12)	0.4269 (5)	1.18350 (12)	0.0570 (6)
H14A	0.4283	0.4180	1.2278	0.068*
H14B	0.3837	0.5973	1.1741	0.068*
H14C	0.4288	0.3958	1.1576	0.068*
N1	0.36006 (10)	−0.0392 (4)	1.02268 (8)	0.0461 (5)
H1N	0.3609 (12)	−0.189 (6)	1.0382 (12)	0.055*
O1	0.35554 (12)	0.3935 (3)	1.04201 (9)	0.0740 (6)
Cl1	0.48134 (3)	0.07146 (16)	0.82524 (3)	0.0760 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0526 (11)	0.0351 (10)	0.0411 (10)	−0.0047 (9)	0.0164 (9)	−0.0033 (8)
C2	0.0640 (13)	0.0443 (13)	0.0541 (12)	0.0073 (10)	0.0240 (10)	0.0077 (10)
C3	0.0597 (13)	0.0582 (15)	0.0617 (14)	0.0086 (11)	0.0270 (11)	0.0013 (12)
C4	0.0588 (12)	0.0507 (13)	0.0445 (11)	−0.0110 (10)	0.0220 (10)	−0.0055 (9)
C5	0.0773 (15)	0.0458 (14)	0.0448 (11)	0.0035 (11)	0.0220 (10)	0.0053 (10)
C6	0.0688 (14)	0.0485 (14)	0.0479 (12)	0.0123 (11)	0.0233 (10)	0.0040 (10)
C7	0.0638 (12)	0.0334 (11)	0.0459 (11)	0.0005 (9)	0.0234 (9)	0.0011 (8)
C8	0.0485 (10)	0.0354 (11)	0.0447 (10)	0.0052 (8)	0.0185 (8)	0.0017 (8)
C9	0.0458 (10)	0.0394 (11)	0.0479 (11)	0.0053 (8)	0.0184 (8)	0.0003 (8)
C10	0.0592 (13)	0.0557 (14)	0.0485 (11)	0.0053 (11)	0.0245 (10)	−0.0031 (10)
C11	0.0628 (14)	0.0616 (15)	0.0590 (13)	0.0013 (11)	0.0358 (12)	0.0055 (11)
C12	0.0522 (12)	0.0537 (14)	0.0695 (15)	−0.0074 (11)	0.0274 (11)	0.0023 (12)
C13	0.0513 (11)	0.0461 (13)	0.0505 (11)	−0.0004 (10)	0.0155 (9)	0.0001 (10)
C14	0.0600 (13)	0.0505 (15)	0.0621 (13)	−0.0057 (10)	0.0226 (11)	−0.0080 (10)
N1	0.0669 (11)	0.0315 (9)	0.0455 (10)	0.0002 (8)	0.0262 (8)	0.0018 (7)
O1	0.1407 (18)	0.0319 (9)	0.0708 (11)	−0.0004 (10)	0.0636 (12)	0.0022 (7)
Cl1	0.0838 (5)	0.0892 (6)	0.0706 (5)	−0.0083 (4)	0.0465 (4)	0.0039 (4)

Geometric parameters (Å, º) top

C1—C6	1.378 (3)	C8—C13	1.386 (3)
C1—C2	1.382 (3)	C8—C9	1.408 (3)
C1—N1	1.413 (3)	C9—C10	1.394 (3)
C2—C3	1.384 (3)	C9—C14	1.490 (3)
C2—H2	1.02 (3)	C10—C11	1.368 (4)
C3—C4	1.368 (4)	C10—H10	1.03 (3)
C3—H3	0.94 (3)	C11—C12	1.374 (4)
C4—C5	1.369 (4)	C11—H11	0.95 (3)
C4—Cl1	1.745 (2)	C12—C13	1.385 (3)
C5—C6	1.380 (3)	C12—H12	1.01 (3)
C5—H5	0.98 (3)	C13—H13	0.99 (3)
C6—H6	0.93 (3)	C14—H14A	0.9600
C7—O1	1.223 (3)	C14—H14B	0.9600
C7—N1	1.362 (3)	C14—H14C	0.9600
C7—C8	1.492 (3)	N1—H1N	0.84 (3)

C6—C1—C2	119.1 (2)	C10—C9—C8	116.8 (2)
C6—C1—N1	121.9 (2)	C10—C9—C14	119.0 (2)
C2—C1—N1	119.03 (19)	C8—C9—C14	124.18 (19)
C1—C2—C3	120.6 (2)	C11—C10—C9	122.4 (2)
C1—C2—H2	122.3 (15)	C11—C10—H10	122.6 (16)
C3—C2—H2	116.9 (15)	C9—C10—H10	115.0 (16)
C4—C3—C2	119.2 (2)	C10—C11—C12	120.5 (2)
C4—C3—H3	121.7 (17)	C10—C11—H11	122.0 (18)
C2—C3—H3	119.1 (17)	C12—C11—H11	117.4 (19)
C3—C4—C5	120.9 (2)	C11—C12—C13	118.8 (2)
C3—C4—Cl1	119.67 (19)	C11—C12—H12	122.0 (15)
C5—C4—Cl1	119.40 (19)	C13—C12—H12	119.2 (15)
C4—C5—C6	119.8 (2)	C12—C13—C8	121.2 (2)
C4—C5—H5	120.3 (17)	C12—C13—H13	119.4 (16)
C6—C5—H5	119.8 (17)	C8—C13—H13	119.4 (16)
C1—C6—C5	120.2 (2)	C9—C14—H14A	109.5
C1—C6—H6	115.6 (17)	C9—C14—H14B	109.5
C5—C6—H6	124.0 (17)	H14A—C14—H14B	109.5
O1—C7—N1	121.9 (2)	C9—C14—H14C	109.5
O1—C7—C8	122.95 (19)	H14A—C14—H14C	109.5
N1—C7—C8	115.14 (19)	H14B—C14—H14C	109.5
C13—C8—C9	120.3 (2)	C7—N1—C1	124.59 (19)
C13—C8—C7	119.68 (19)	C7—N1—H1N	117.7 (18)
C9—C8—C7	120.03 (19)	C1—N1—H1N	115.8 (18)

C6—C1—C2—C3	3.7 (4)	C7—C8—C9—C10	−179.84 (19)
N1—C1—C2—C3	−176.8 (2)	C13—C8—C9—C14	178.3 (2)
C1—C2—C3—C4	−0.7 (4)	C7—C8—C9—C14	−2.8 (3)
C2—C3—C4—C5	−2.4 (4)	C8—C9—C10—C11	−1.4 (3)
C2—C3—C4—Cl1	175.54 (19)	C14—C9—C10—C11	−178.6 (2)
C3—C4—C5—C6	2.5 (4)	C9—C10—C11—C12	0.7 (4)
Cl1—C4—C5—C6	−175.48 (19)	C10—C11—C12—C13	0.0 (4)
C2—C1—C6—C5	−3.7 (4)	C11—C12—C13—C8	−0.1 (4)
N1—C1—C6—C5	176.9 (2)	C9—C8—C13—C12	−0.6 (3)
C4—C5—C6—C1	0.6 (4)	C7—C8—C13—C12	−179.5 (2)
O1—C7—C8—C13	135.1 (3)	O1—C7—N1—C1	5.2 (4)
N1—C7—C8—C13	−44.8 (3)	C8—C7—N1—C1	−174.86 (18)
O1—C7—C8—C9	−43.7 (3)	C6—C1—N1—C7	−41.2 (3)
N1—C7—C8—C9	136.3 (2)	C2—C1—N1—C7	139.3 (2)
C13—C8—C9—C10	1.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.84 (3)	2.14 (3)	2.937 (3)	159 (2)

Symmetry code: (i) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂ClNO
M_r	245.70
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	299
a, b, c (Å)	22.345 (2), 5.1092 (4), 22.222 (1)
β (°)	109.593 (6)
V (Å³)	2390.1 (3)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	2.67
Crystal size (mm)	0.50 × 0.13 × 0.13

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2213, 2085, 1741
R_int	0.074
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.159, 1.08
No. of reflections	2085
No. of parameters	182
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.39

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
N1—H1N···O1ⁱ	0.84 (3)	2.14 (3)	2.937 (3)	159 (2)

Symmetry code: (i) x, y−1, z.

Acknowledgements

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

References

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