2-Chloro-N-(2,6-dimethyl­phen­yl)benzamide

Abstract

In the title compound, C₁₅H₁₄ClNO, the dihedral angle between the benzoyl and the aniline rings is 3.30 (18)°. In the crystal, N—H⋯O hydrogen bonds link the mol­ecules into chains running along the a axis.

Related literature  

For studies on the effects of substituents on the structures and other aspects of N-(ar­yl)-amides, see: Bowes et al. (2003 ▶); Gowda et al. (2000 ▶, 2007 ▶, 2008 ▶); Saeed et al. (2010 ▶), on N-chloro­aryl­sulfonamides, see: Jyothi & Gowda (2004 ▶) and on N-bromo­aryl­sulfonamides, see: Usha & Gowda (2006 ▶).

Experimental  

Crystal data  

• C₁₅H₁₄ClNO

• M _r = 259.72

• Monoclinic,

• a = 4.8322 (3) Å

• b = 12.7817 (10) Å

• c = 21.8544 (12) Å

• β = 90.778 (5)°

• V = 1349.69 (15) ų

• Z = 4

• Mo Kα radiation

• μ = 0.27 mm⁻¹

• T = 295 K

• 0.51 × 0.30 × 0.11 mm

Data collection  

• Oxford Diffraction Xcalibur Ruby Gemini diffractometer

• Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2009 ▶), based on expressions derived by Clark & Reid (1995 ▶)] T _min = 0.907, T _max = 0.971

• 18665 measured reflections

• 2469 independent reflections

• 1735 reflections with I > 2σ(I)

• R _int = 0.081

Refinement  

• R[F ² > 2σ(F ²)] = 0.092

• wR(F ²) = 0.248

• S = 1.12

• 2469 reflections

• 168 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.50 e Å⁻³

• Δρ_min = −0.27 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (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 ▶); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009 ▶) and WinGX (Farrugia, 1999 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812015607/bt5865Isup3.cml

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—H1⋯O1i	0.86 (2)	1.96 (2)	2.818 (4)	172 (4)

Symmetry code: (i) .

supplementary crystallographic information

Comment

The amide and sulfonamide moieties are the constituents of many biologically important compounds. As part of studies on the substituent effects on the structures and other aspects of N-(aryl)-amides (Bowes et al., 2003; Gowda et al., 2000, 2007, 2008; Saeed et al., 2010), N-chloroarylsulfonamides (Jyothi & Gowda, 2004) and N-bromoarylsulfonamides (Usha & Gowda, 2006), in the present work, the crystal structure of 2-chloro-N-(2,6-dimethylphenyl)benzamide has been determined (Fig. 1).

In the title compound, one of the ortho-methyl groups in the aniline ring is positioned syn to the N—H bond, while the other ortho- methyl group is positioned anti to the N—H bond, the latter and the C=O bond being anti to each other. Further, the amide oxygen is syn to the ortho-chloro group in the benzoyl ring, similar to that observed in 2-chloro-N-(2,6-dichlorophenyl)benzamide (Gowda et al., 2008). In the title compound, the amide group forms dihedral angles of 63.26 (22)° and 59.88 (23)°, respectively, with the 2-chlorobenzoyl and the 2,6-dimethyl- anilino rings, while the angle between the benzoyl and the anilino rings is 3.46 (17)°.

In the crystal structure, intermolecular N1—H1···O1 hydrogen bonds (Table 1) link the molecules into infinite chains running along the a-axis. Part of the crystal structure is shown in Fig. 2.

Experimental

The title compound was prepared by a method similar to the one described by Gowda et al. (2008). The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared and NMR spectra.

Rod like colourless single crystals of the title compound used in the X-ray diffraction studies were obtained by slow evaporation of the solvent from its ethanol solution of the compound (0.5 g in about 30 ml of ethanol) at room temperature.

Refinement

Hydrogen atoms were placed in calculated positions with C–H distances of 0.93 Å (C-aromatic), 0.96 Å (C-methyl) and constrained to ride on their parent atoms. The amide H atom was visible in a difference map and refined with the N—H distance restrained to 0.86 (1) Å. The U_iso(H) values were set at 1.2U_eq (C-aromatic, N) or 1.5U_eq (C-methyl).

Figures

Fig. 1.

Molecular structure of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.

Fig. 2.

Packing view of the title compound. Molecular links along a-axis are generated by N–H···O hydrogen bonds which are shown by dashed lines. H atoms have been omitted for clarity.

Crystal data

C15H14ClNO	F(000) = 544
Mr = 259.72	Dx = 1.278 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3462 reflections
a = 4.8322 (3) Å	θ = 3.7–29.5°
b = 12.7817 (10) Å	µ = 0.27 mm−1
c = 21.8544 (12) Å	T = 295 K
β = 90.778 (5)°	Rod, colourless
V = 1349.69 (15) Å3	0.51 × 0.30 × 0.11 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	2469 independent reflections
Graphite monochromator	1735 reflections with I > 2σ(I)
Detector resolution: 10.434 pixels mm-1	Rint = 0.081
ω scans	θmax = 25.3°, θmin = 4.2°
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)]	h = −5→5
Tmin = 0.907, Tmax = 0.971	k = −15→15
18665 measured reflections	l = −26→26

Refinement

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)] = 0.092	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.248	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ2(Fo2) + (0.080P)2 + 2.4052P] where P = (Fo2 + 2Fc2)/3
2469 reflections	(Δ/σ)max < 0.001
168 parameters	Δρmax = 0.50 e Å−3
1 restraint	Δρmin = −0.27 e Å−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	0.5223 (8)	0.2456 (4)	0.47475 (19)	0.0494 (10)
C2	0.3612 (11)	0.3360 (4)	0.4743 (2)	0.0660 (13)
C3	0.3033 (14)	0.3824 (5)	0.5300 (3)	0.0892 (19)
H3	0.1927	0.4419	0.5307	0.107*
C4	0.4038 (14)	0.3431 (5)	0.5834 (3)	0.094 (2)
H4	0.3632	0.3761	0.6202	0.113*
C5	0.5672 (11)	0.2539 (5)	0.5836 (2)	0.0720 (15)
H5	0.6349	0.2271	0.6204	0.086*
C6	0.6293 (9)	0.2050 (4)	0.5296 (2)	0.0528 (11)
C7	0.8109 (11)	0.1086 (4)	0.5297 (2)	0.0720 (15)
H7A	0.8096	0.0771	0.5696	0.108*
H7B	0.9967	0.1281	0.5197	0.108*
H7C	0.7417	0.0596	0.5	0.108*
C8	0.2532 (14)	0.3832 (4)	0.4152 (3)	0.0830 (17)
H8A	0.2349	0.4575	0.42	0.124*
H8B	0.0759	0.3534	0.4052	0.124*
H8C	0.3803	0.3685	0.3829	0.124*
C9	0.3874 (8)	0.1464 (3)	0.38474 (18)	0.0438 (10)
C10	0.4897 (8)	0.0847 (4)	0.3306 (2)	0.0533 (11)
C11	0.6640 (10)	0.0015 (4)	0.3394 (2)	0.0661 (13)
H11	0.7286	−0.0141	0.3786	0.079*
C12	0.7455 (13)	−0.0601 (5)	0.2903 (3)	0.0911 (19)
H12	0.8633	−0.1166	0.2968	0.109*
C13	0.6524 (15)	−0.0373 (6)	0.2326 (3)	0.097 (2)
H13	0.7055	−0.0789	0.1998	0.116*
C14	0.4789 (14)	0.0476 (6)	0.2226 (3)	0.0887 (19)
H14	0.4174	0.0643	0.1833	0.106*
C15	0.3997 (10)	0.1063 (4)	0.2718 (2)	0.0649 (13)
N1	0.5818 (7)	0.1927 (3)	0.41875 (15)	0.0460 (9)
H1	0.756 (4)	0.180 (4)	0.415 (2)	0.055*
O1	0.1424 (6)	0.1494 (3)	0.39531 (15)	0.0656 (10)
Cl1	0.1880 (4)	0.21406 (14)	0.25687 (7)	0.0994 (7)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.050 (2)	0.053 (3)	0.045 (2)	0.0038 (19)	0.0043 (18)	−0.0021 (19)
C2	0.079 (3)	0.063 (3)	0.057 (3)	0.019 (3)	0.001 (2)	0.000 (2)
C3	0.119 (5)	0.076 (4)	0.073 (4)	0.039 (4)	0.007 (3)	−0.022 (3)
C4	0.127 (5)	0.096 (5)	0.061 (4)	0.029 (4)	0.013 (3)	−0.028 (3)
C5	0.086 (3)	0.089 (4)	0.041 (3)	0.002 (3)	−0.001 (2)	−0.006 (3)
C6	0.056 (2)	0.056 (3)	0.046 (2)	0.004 (2)	0.0018 (19)	−0.002 (2)
C7	0.079 (3)	0.082 (4)	0.055 (3)	0.018 (3)	−0.009 (2)	0.007 (3)
C8	0.118 (5)	0.065 (3)	0.066 (3)	0.033 (3)	−0.004 (3)	0.006 (3)
C9	0.041 (2)	0.052 (3)	0.039 (2)	0.0011 (18)	−0.0020 (16)	0.0078 (18)
C10	0.042 (2)	0.070 (3)	0.048 (2)	−0.005 (2)	0.0017 (18)	−0.005 (2)
C11	0.061 (3)	0.070 (3)	0.067 (3)	0.001 (3)	0.002 (2)	−0.016 (3)
C12	0.087 (4)	0.079 (4)	0.107 (5)	0.007 (3)	0.012 (4)	−0.036 (4)
C13	0.110 (5)	0.108 (5)	0.073 (4)	−0.019 (4)	0.020 (4)	−0.046 (4)
C14	0.101 (4)	0.112 (5)	0.053 (3)	−0.019 (4)	0.000 (3)	−0.019 (3)
C15	0.068 (3)	0.074 (3)	0.052 (3)	−0.012 (3)	0.004 (2)	−0.003 (2)
N1	0.0393 (17)	0.056 (2)	0.0428 (19)	0.0052 (16)	0.0047 (15)	−0.0015 (16)
O1	0.0413 (17)	0.093 (3)	0.062 (2)	0.0015 (16)	0.0020 (14)	−0.0100 (18)
Cl1	0.1313 (14)	0.1054 (13)	0.0612 (9)	0.0210 (10)	−0.0121 (8)	0.0189 (8)

Geometric parameters (Å, º)

C1—C2	1.394 (6)	C8—H8C	0.96
C1—C6	1.398 (6)	C9—O1	1.210 (5)
C1—N1	1.431 (5)	C9—N1	1.329 (5)
C2—C3	1.386 (7)	C9—C10	1.511 (6)
C2—C8	1.511 (7)	C10—C11	1.369 (7)
C3—C4	1.355 (9)	C10—C15	1.379 (7)
C3—H3	0.93	C11—C12	1.392 (8)
C4—C5	1.387 (8)	C11—H11	0.93
C4—H4	0.93	C12—C13	1.365 (10)
C5—C6	1.373 (7)	C12—H12	0.93
C5—H5	0.93	C13—C14	1.387 (9)
C6—C7	1.512 (7)	C13—H13	0.93
C7—H7A	0.96	C14—C15	1.370 (8)
C7—H7B	0.96	C14—H14	0.93
C7—H7C	0.96	C15—Cl1	1.744 (6)
C8—H8A	0.96	N1—H1	0.860 (19)
C8—H8B	0.96
C2—C1—C6	120.9 (4)	C2—C8—H8C	109.5
C2—C1—N1	120.3 (4)	H8A—C8—H8C	109.5
C6—C1—N1	118.8 (4)	H8B—C8—H8C	109.5
C3—C2—C1	117.9 (5)	O1—C9—N1	124.4 (4)
C3—C2—C8	120.6 (5)	O1—C9—C10	119.8 (4)
C1—C2—C8	121.5 (4)	N1—C9—C10	115.7 (3)
C4—C3—C2	121.6 (5)	C11—C10—C15	118.2 (5)
C4—C3—H3	119.2	C11—C10—C9	120.2 (4)
C2—C3—H3	119.2	C15—C10—C9	121.6 (4)
C3—C4—C5	120.2 (5)	C10—C11—C12	120.7 (6)
C3—C4—H4	119.9	C10—C11—H11	119.6
C5—C4—H4	119.9	C12—C11—H11	119.6
C6—C5—C4	120.3 (5)	C13—C12—C11	119.9 (6)
C6—C5—H5	119.9	C13—C12—H12	120
C4—C5—H5	119.9	C11—C12—H12	120
C5—C6—C1	119.0 (4)	C12—C13—C14	120.2 (6)
C5—C6—C7	120.2 (4)	C12—C13—H13	119.9
C1—C6—C7	120.8 (4)	C14—C13—H13	119.9
C6—C7—H7A	109.5	C15—C14—C13	118.7 (6)
C6—C7—H7B	109.5	C15—C14—H14	120.7
H7A—C7—H7B	109.5	C13—C14—H14	120.7
C6—C7—H7C	109.5	C14—C15—C10	122.3 (6)
H7A—C7—H7C	109.5	C14—C15—Cl1	117.1 (5)
H7B—C7—H7C	109.5	C10—C15—Cl1	120.6 (4)
C2—C8—H8A	109.5	C9—N1—C1	122.7 (3)
C2—C8—H8B	109.5	C9—N1—H1	124 (3)
H8A—C8—H8B	109.5	C1—N1—H1	112 (3)
C6—C1—C2—C3	−2.0 (8)	N1—C9—C10—C15	−122.9 (5)
N1—C1—C2—C3	178.2 (5)	C15—C10—C11—C12	−0.6 (7)
C6—C1—C2—C8	177.6 (5)	C9—C10—C11—C12	175.8 (5)
N1—C1—C2—C8	−2.2 (8)	C10—C11—C12—C13	0.3 (9)
C1—C2—C3—C4	1.4 (10)	C11—C12—C13—C14	0.6 (10)
C8—C2—C3—C4	−178.2 (7)	C12—C13—C14—C15	−1.2 (10)
C2—C3—C4—C5	−0.6 (11)	C13—C14—C15—C10	0.9 (9)
C3—C4—C5—C6	0.3 (10)	C13—C14—C15—Cl1	178.6 (5)
C4—C5—C6—C1	−0.9 (8)	C11—C10—C15—C14	0.0 (7)
C4—C5—C6—C7	179.1 (5)	C9—C10—C15—C14	−176.4 (5)
C2—C1—C6—C5	1.8 (7)	C11—C10—C15—Cl1	−177.6 (4)
N1—C1—C6—C5	−178.4 (4)	C9—C10—C15—Cl1	6.0 (6)
C2—C1—C6—C7	−178.2 (5)	O1—C9—N1—C1	4.6 (7)
N1—C1—C6—C7	1.6 (7)	C10—C9—N1—C1	−173.9 (4)
O1—C9—C10—C11	−117.8 (5)	C2—C1—N1—C9	−65.8 (6)
N1—C9—C10—C11	60.8 (6)	C6—C1—N1—C9	114.4 (5)
O1—C9—C10—C15	58.5 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.86 (2)	1.96 (2)	2.818 (4)	172 (4)

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