2-Chloro-N-(2,4-dimethyl­phen­yl)acetamide

Abstract

The conformation of the N—H bond in the structure of the title compound, C₁₀H₁₂ClNO, is syn to the ortho methyl group, similar to that observed with respect to the meta methyl group in 2-chloro-N-(3-methyl­phen­yl)acetamide and the ortho-chloro group in 2-chloro-N-(2-chloro­phen­yl)acetamide. The geometric parameters are similar to those of other acetanilides. The mol­ecules are linked into chains through inter­molecular N—H⋯O hydrogen bonds.

Related literature

For related literature, see: Gowda et al. (2007a ▶,b ▶,c ▶,d ▶,e ▶,f ▶, 2008 ▶); Shilpa & Gowda (2007 ▶).

Experimental

Crystal data

• C₁₀H₁₂ClNO

• M _r = 197.66

• Triclinic,

• a = 4.7235 (7) Å

• b = 10.407 (2) Å

• c = 11.451 (2) Å

• α = 67.07 (2)°

• β = 86.84 (1)°

• γ = 78.95 (2)°

• V = 508.69 (15) ų

• Z = 2

• Cu Kα radiation

• μ = 3.00 mm⁻¹

• T = 299 (2) K

• 0.60 × 0.06 × 0.04 mm

Data collection

• Enraf–Nonius CAD-4 diffractometer

• Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.803, T _max = 0.895

• 2059 measured reflections

• 1817 independent reflections

• 1394 reflections with I > 2σ(I)

• R _int = 0.015

• 3 standard reflections frequency: 120 min intensity decay: 1.0%

Refinement

• R[F ² > 2σ(F ²)] = 0.067

• wR(F ²) = 0.190

• S = 1.09

• 1817 reflections

• 123 parameters

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

• Δρ_max = 0.45 e Å⁻³

• Δρ_min = −0.47 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, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); 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	0.83 (4)	2.04 (4)	2.853 (3)	165 (3)

Symmetry code: (i) .

supplementary crystallographic information

Comment

In the present work, the structure of 2-chloro-N-(2,4-dimethylphenyl)- acetamide (24DMPCA) has been determined as part of a study of the effect of ring and side chain substitutions on the solid state geometry of aromatic amides (Gowda et al., 2007a, b, c, d, e). The conformation of the N—H bond in the structure of 24DMPCA is syn to the ortho methyl group (Fig. 1), similar to that observed with respect to the meta methyl group in the 2-chloro- N-(3-methylphenyl)acetamide (3MPCA)(Gowda et al., 2007e). and ortho chloro group in the 2-chloro-N-(2-chlorophenyl)- acetamide(2CPCA)(Gowda et al., 2007d). The geometric parameters in 24DMPCA are similar to those in 3MPCA (Gowda et al., 2007e), 2CPCA (Gowda et al., 2007d), 2-chloro-N-(4-methylphenyl)- acetamide (Gowda et al., 2007b), 2-chloro-N- (4-chlorophenyl)-acetamide (Gowda et al., 2007c) and other acetanilides (Gowda et al. , 2007a). The molecules in the structure are linked into chains through intermolecular N—H···O hydrogen bonding (Table 1 and Fig.2).

Experimental

The title compound was prepared according to the literature method (Shilpa and Gowda, 2007). The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared and NMR spectra (Shilpa and Gowda, 2007). Single crystals of the title compound were obtained from an ethanolic solution and used for X-ray diffraction studies at room temperature.

Refinement

The CH atoms were positioned with idealized geometry using a riding model with C—H = 0.93–0.97 Å. The NH atom was located in difference map and its coordinates were refined. U_iso(H) values were set equal to 1.2 U_eq(C,N) or 1.2 U_eq(C_methyl).

Figures

Fig. 1.

Molecular structure of the title compound showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. 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

C10H12ClNO	Z = 2
Mr = 197.66	F000 = 208
Triclinic, P1	Dx = 1.290 Mg m−3
Hall symbol: -P 1	Cu Kα radiation λ = 1.54180 Å
a = 4.7235 (7) Å	Cell parameters from 25 reflections
b = 10.407 (2) Å	θ = 4.2–26.4º
c = 11.451 (2) Å	µ = 3.00 mm−1
α = 67.07 (2)º	T = 299 (2) K
β = 86.84 (1)º	Needle, colourless
γ = 78.95 (2)º	0.60 × 0.06 × 0.04 mm
V = 508.69 (15) Å3

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.015
Radiation source: fine-focus sealed tube	θmax = 66.9º
Monochromator: graphite	θmin = 4.2º
T = 299(2) K	h = 0→5
ω/2θ scans	k = −12→12
Absorption correction: ψ scanNorth et al. (1968)	l = −13→13
Tmin = 0.803, Tmax = 0.895	3 standard reflections
2059 measured reflections	every 120 min
1817 independent reflections	intensity decay: 1.0%
1394 reflections with I > 2σ(I)

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)] = 0.067	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.190	w = 1/[σ2(Fo2) + (0.1035P)2 + 0.2646P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.044
1817 reflections	Δρmax = 0.45 e Å−3
123 parameters	Δρmin = −0.47 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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
Cl1	0.5208 (2)	−0.02640 (14)	0.75189 (11)	0.1062 (6)
O1	0.2611 (4)	0.1946 (3)	0.5165 (2)	0.0695 (8)
N1	0.6642 (5)	0.2847 (3)	0.4451 (2)	0.0411 (6)
H1N	0.842 (8)	0.271 (3)	0.453 (3)	0.049*
C1	0.5306 (5)	0.4140 (3)	0.3481 (3)	0.0380 (6)
C2	0.6351 (5)	0.4545 (3)	0.2256 (3)	0.0426 (7)
C3	0.5019 (7)	0.5837 (3)	0.1357 (3)	0.0520 (8)
H3	0.5711	0.6130	0.0536	0.062*
C4	0.2697 (7)	0.6709 (3)	0.1634 (3)	0.0539 (8)
C5	0.1706 (7)	0.6261 (3)	0.2857 (3)	0.0536 (8)
H5	0.0142	0.6822	0.3062	0.064*
C6	0.2985 (6)	0.5003 (3)	0.3774 (3)	0.0461 (7)
H6	0.2300	0.4724	0.4597	0.055*
C7	0.5218 (5)	0.1865 (3)	0.5227 (3)	0.0449 (7)
C8	0.7104 (6)	0.0592 (4)	0.6200 (3)	0.0590 (9)
H8A	0.8681	0.0901	0.6462	0.071*
H8B	0.7927	−0.0072	0.5812	0.071*
C9	0.8830 (7)	0.3623 (4)	0.1907 (3)	0.0569 (8)
H9A	1.0565	0.3590	0.2325	0.085*
H9B	0.9069	0.4011	0.1006	0.085*
H9C	0.8435	0.2681	0.2168	0.085*
C10	0.1310 (10)	0.8109 (4)	0.0632 (4)	0.0815 (12)
H10A	0.2775	0.8560	0.0104	0.122*
H10B	0.0287	0.8712	0.1032	0.122*
H10C	−0.0013	0.7944	0.0121	0.122*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0551 (6)	0.1112 (9)	0.0893 (8)	−0.0082 (5)	0.0147 (5)	0.0236 (6)
O1	0.0134 (9)	0.0749 (15)	0.0926 (17)	−0.0115 (9)	−0.0051 (10)	−0.0006 (13)
N1	0.0138 (9)	0.0512 (13)	0.0519 (13)	−0.0051 (9)	−0.0010 (9)	−0.0132 (11)
C1	0.0211 (12)	0.0446 (15)	0.0476 (15)	−0.0062 (10)	−0.0031 (10)	−0.0166 (12)
C2	0.0263 (13)	0.0534 (17)	0.0504 (15)	−0.0104 (11)	0.0017 (11)	−0.0213 (13)
C3	0.0456 (17)	0.0573 (18)	0.0484 (16)	−0.0122 (14)	−0.0006 (13)	−0.0141 (14)
C4	0.0493 (18)	0.0474 (17)	0.0599 (18)	−0.0044 (13)	−0.0087 (14)	−0.0160 (14)
C5	0.0394 (16)	0.0548 (18)	0.0628 (19)	0.0047 (13)	−0.0037 (13)	−0.0242 (15)
C6	0.0278 (13)	0.0567 (17)	0.0503 (16)	−0.0021 (12)	0.0016 (11)	−0.0195 (13)
C7	0.0174 (12)	0.0522 (16)	0.0586 (17)	−0.0060 (11)	−0.0004 (11)	−0.0147 (13)
C8	0.0233 (13)	0.0593 (19)	0.073 (2)	−0.0076 (12)	−0.0009 (13)	−0.0021 (16)
C9	0.0369 (16)	0.072 (2)	0.0603 (18)	−0.0050 (14)	0.0090 (14)	−0.0270 (16)
C10	0.087 (3)	0.059 (2)	0.075 (2)	0.006 (2)	−0.009 (2)	−0.0087 (19)

Geometric parameters (Å, °)

Cl1—C8	1.728 (3)	C5—C6	1.371 (4)
O1—C7	1.223 (3)	C5—H5	0.9300
N1—C7	1.333 (4)	C6—H6	0.9300
N1—C1	1.425 (3)	C7—C8	1.516 (4)
N1—H1N	0.83 (4)	C8—H8A	0.9700
C1—C2	1.389 (4)	C8—H8B	0.9700
C1—C6	1.392 (4)	C9—H9A	0.9600
C2—C3	1.390 (4)	C9—H9B	0.9600
C2—C9	1.506 (4)	C9—H9C	0.9600
C3—C4	1.390 (5)	C10—H10A	0.9600
C3—H3	0.9300	C10—H10B	0.9600
C4—C5	1.378 (5)	C10—H10C	0.9600
C4—C10	1.511 (5)
C7—N1—C1	124.3 (2)	O1—C7—N1	123.9 (3)
C7—N1—H1N	119 (2)	O1—C7—C8	121.4 (3)
C1—N1—H1N	117 (2)	N1—C7—C8	114.6 (2)
C2—C1—C6	120.4 (3)	C7—C8—Cl1	112.3 (2)
C2—C1—N1	120.0 (2)	C7—C8—H8A	109.1
C6—C1—N1	119.6 (2)	Cl1—C8—H8A	109.1
C1—C2—C3	117.6 (3)	C7—C8—H8B	109.1
C1—C2—C9	121.6 (3)	Cl1—C8—H8B	109.1
C3—C2—C9	120.9 (3)	H8A—C8—H8B	107.9
C4—C3—C2	122.8 (3)	C2—C9—H9A	109.5
C4—C3—H3	118.6	C2—C9—H9B	109.5
C2—C3—H3	118.6	H9A—C9—H9B	109.5
C5—C4—C3	117.8 (3)	C2—C9—H9C	109.5
C5—C4—C10	120.9 (3)	H9A—C9—H9C	109.5
C3—C4—C10	121.2 (3)	H9B—C9—H9C	109.5
C6—C5—C4	121.2 (3)	C4—C10—H10A	109.5
C6—C5—H5	119.4	C4—C10—H10B	109.5
C4—C5—H5	119.4	H10A—C10—H10B	109.5
C5—C6—C1	120.3 (3)	C4—C10—H10C	109.5
C5—C6—H6	119.9	H10A—C10—H10C	109.5
C1—C6—H6	119.9	H10B—C10—H10C	109.5
C7—N1—C1—C2	−130.4 (3)	C3—C4—C5—C6	0.7 (5)
C7—N1—C1—C6	50.8 (4)	C10—C4—C5—C6	−179.0 (3)
C6—C1—C2—C3	0.7 (4)	C4—C5—C6—C1	−0.8 (5)
N1—C1—C2—C3	−178.1 (2)	C2—C1—C6—C5	0.1 (4)
C6—C1—C2—C9	−179.1 (3)	N1—C1—C6—C5	178.9 (3)
N1—C1—C2—C9	2.1 (4)	C1—N1—C7—O1	2.5 (5)
C1—C2—C3—C4	−0.9 (4)	C1—N1—C7—C8	−178.9 (3)
C9—C2—C3—C4	178.9 (3)	O1—C7—C8—Cl1	−25.2 (4)
C2—C3—C4—C5	0.2 (5)	N1—C7—C8—Cl1	156.2 (3)
C2—C3—C4—C10	179.9 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1i	0.83 (4)	2.04 (4)	2.853 (3)	165 (3)

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