N-(4-Chloro­phen­yl)-2-methyl­benzamide

Abstract

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,

• a = 22.345 (2) Å

• b = 5.1092 (4) Å

• c = 22.222 (1) Å

• β = 109.593 (6)°

• V = 2390.1 (3) ų

• 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[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The H atoms of the methyl group were positioned with idealized geometry using a riding model with C—H = 0.96 Å. The other H atoms were located in difference map, and their positional parameters were refined freely. The isotropic displacement parameters of all H atoms were set to 1.2 U_eq(C-aromatic, N) or 1.5 U_eq(C-methyl).

Figures

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..

Crystal data

C14H12ClNO	F(000) = 1024
Mr = 245.70	Dx = 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

Enraf–Nonius CAD-4 diffractometer	Rint = 0.074
Radiation source: fine-focus sealed tube	θmax = 66.9°, θmin = 4.2°
graphite	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

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(Fo2) + (0.1089P)2 + 0.7738P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max = 0.002
2085 reflections	Δρmax = 0.27 e Å−3
182 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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 codes: (i) x, y−1, z.