2,2-Dichloro-N-(3,4-dimethyl­phen­yl)acetamide

Gowda, B.T.; Foro, S.; Svoboda, I.; Fuess, H.

doi:10.1107/S1600536809022557

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1607

doi:10.1107/S1600536809022557

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2,2-Dichloro-N-(3,4-dimethylphenyl)acetamide

B. Thimme Gowda,^a ^* Sabine Foro,^b Ingrid Svoboda ^b and Hartmut Fuess ^b

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, and ^bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 4 June 2009; accepted 12 June 2009; online 17 June 2009)

In the title compound, C₁₀H₁₁Cl₂NO, the N—H bond is syn to the 3-methyl substituent in the aromatic ring, similar to that observed in N-(3,4-dimethylphenyl)acetamide and to the 3-chloro substituent in 2,2-dichloro-N-(3,4-dichlorophenyl)acetamide, and contrasting with the anti conformation observed for the 3-methyl substituent in 2,2,2-trichloro-N-(3,4-dimethylphenyl)acetamide. On the other hand, it is anti to the C=O bond. An intermolecular N—H⋯O hydrogen bond links molecules into infinite chains along the b axis.

Related literature

For the preparation of the compound, see: Shilpa & Gowda (2007 ). For related structures, see: Gowda et al. (2007 , 2008 , 2009 )

Experimental

Crystal data

C₁₀H₁₁Cl₂NO
M_r = 232.10
Monoclinic, P 2₁ /c
a = 11.951 (1) Å
b = 10.534 (1) Å
c = 9.303 (1) Å
β = 111.26 (1)°
V = 1091.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.56 mm⁻¹
T = 299 K
0.28 × 0.20 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis RED. Oxford Diffraction Ltd, Köln, Germany.]$ ) T_min = 0.859, T_max = 0.936
4567 measured reflections
2214 independent reflections
1495 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.187
S = 1.20
2214 reflections
144 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.37 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 (4)	2.07 (4)	2.894 (3)	166 (3)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2004 $[Oxford Diffraction (2004). CrysAlis CCD. Oxford Diffraction Ltd, Köln, Germany.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis RED. Oxford Diffraction Ltd, Köln, Germany.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809022557/bg2269sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809022557/bg2269Isup2.hkl

checkCIF report

Comment top

As part of a study of the effect of ring and side chain substitutions on the crystal structures of aromatic amides (Gowda et al., 2007; 2008; 2009), the structure of 2,2-dichloro-N-(3,4-dimethylphenyl)acetamide (I) has been determined. The conformation of the N—H bond in the title compound is syn to the 3-methyl substituent in the aromatic ring [ similar to that observed in N-(3,4-dimethylphenyl)acetamide (Gowda et al., 2008) and to the 3-chloro substituent in 2,2-dichloro-N- (3,4-dichlorophenyl)-acetamide (Gowda et al., 2007)], and contrasting the anti conformation observed for the 3-methyl substituent in 2,2,2-trichloro-N-(3,4-dimethylphenyl)acetamide (Gowda et al., 2009). On the other hand, it is anti to the C=O bond, as observed in other amides. A N—H···O intermolecular hydrogen bond links molecules into infinite chains along the b axis. (Table 1, Fig. 2).

Related literature top

For the preparation of the compound, see: Shilpa & Gowda (2007). For background literature, see: Gowda et al. (2007, 2008, 2009)

Experimental top

Compound (I) was prepared and characterized according to the literature method (Shilpa and Gowda, 2007). Single crystals were obtained from the slow evaporation of an ethanolic solution of (I).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I), showing the atom labelling scheme. The displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Molecular packing of (I) with hydrogen bonding shown as dashed lines.

2,2-Dichloro-N-(3,4-dimethylphenyl)acetamide top

Crystal data top

C₁₀H₁₁Cl₂NO	F(000) = 480
M_r = 232.10	D_x = 1.412 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1463 reflections
a = 11.951 (1) Å	θ = 2.6–27.9°
b = 10.534 (1) Å	µ = 0.56 mm⁻¹
c = 9.303 (1) Å	T = 299 K
β = 111.26 (1)°	Prism, colourless
V = 1091.5 (2) Å³	0.28 × 0.20 × 0.12 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2214 independent reflections
Radiation source: fine-focus sealed tube	1495 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Rotation method data acquisition using ω and ϕ scans	θ_max = 26.4°, θ_min = 2.7°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	h = −14→13
T_min = 0.859, T_max = 0.936	k = −13→6
4567 measured reflections	l = −11→11

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.187	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
2214 reflections	(Δ/σ)_max = 0.023
144 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₁₀H₁₁Cl₂NO	V = 1091.5 (2) Å³
M_r = 232.10	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.951 (1) Å	µ = 0.56 mm⁻¹
b = 10.534 (1) Å	T = 299 K
c = 9.303 (1) Å	0.28 × 0.20 × 0.12 mm
β = 111.26 (1)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2214 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	1495 reflections with I > 2σ(I)
T_min = 0.859, T_max = 0.936	R_int = 0.020
4567 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.187	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	Δρ_max = 0.32 e Å⁻³
2214 reflections	Δρ_min = −0.37 e Å⁻³
144 parameters

Special details top

Experimental. CrysAlis RED (Oxford Diffraction, 2007) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
Cl1	−0.02466 (12)	0.39913 (11)	0.15433 (13)	0.0798 (4)
Cl2	−0.11319 (10)	0.15743 (13)	0.00649 (16)	0.0885 (5)
O1	0.1417 (2)	0.1762 (2)	0.2797 (2)	0.0521 (7)
N1	0.1947 (2)	0.1901 (3)	0.0686 (3)	0.0389 (6)
H1N	0.173 (3)	0.217 (3)	−0.023 (4)	0.047*
C1	0.3132 (3)	0.1393 (3)	0.1286 (3)	0.0360 (7)
C2	0.3945 (3)	0.1829 (3)	0.0644 (3)	0.0383 (7)
H2	0.370 (3)	0.240 (3)	−0.020 (4)	0.046*
C3	0.5126 (3)	0.1407 (3)	0.1172 (4)	0.0400 (7)
C4	0.5503 (3)	0.0526 (3)	0.2372 (4)	0.0442 (8)
C5	0.4666 (3)	0.0078 (3)	0.2959 (4)	0.0493 (9)
H5	0.487 (3)	−0.050 (4)	0.367 (4)	0.059*
C6	0.3489 (3)	0.0492 (3)	0.2448 (4)	0.0439 (8)
H6	0.295 (3)	0.013 (3)	0.284 (4)	0.053*
C7	0.1210 (3)	0.2076 (3)	0.1455 (3)	0.0384 (7)
C8	0.0029 (3)	0.2709 (4)	0.0500 (4)	0.0481 (8)
H8	−0.003 (3)	0.302 (4)	−0.051 (4)	0.058*
C9	0.5985 (3)	0.1928 (4)	0.0464 (5)	0.0580 (10)
H9A	0.6372	0.1238	0.0153	0.070*
H9B	0.6580	0.2442	0.1209	0.070*
H9C	0.5550	0.2435	−0.0420	0.070*
C10	0.6786 (3)	0.0066 (4)	0.3023 (5)	0.0664 (11)
H10A	0.7313	0.0774	0.3425	0.080*
H10B	0.6986	−0.0336	0.2221	0.080*
H10C	0.6876	−0.0532	0.3835	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0971 (9)	0.0780 (8)	0.0699 (7)	0.0313 (6)	0.0370 (6)	−0.0031 (5)
Cl2	0.0435 (6)	0.1112 (10)	0.1088 (10)	−0.0225 (6)	0.0251 (6)	−0.0137 (8)
O1	0.0568 (15)	0.0711 (16)	0.0349 (12)	0.0059 (12)	0.0246 (11)	0.0034 (11)
N1	0.0367 (14)	0.0520 (16)	0.0303 (13)	−0.0016 (12)	0.0147 (11)	0.0027 (12)
C1	0.0375 (16)	0.0395 (16)	0.0341 (15)	−0.0027 (13)	0.0167 (13)	−0.0061 (13)
C2	0.0411 (18)	0.0404 (17)	0.0348 (15)	0.0007 (13)	0.0154 (14)	0.0031 (13)
C3	0.0377 (17)	0.0404 (17)	0.0442 (17)	0.0008 (13)	0.0174 (15)	−0.0070 (14)
C4	0.0420 (18)	0.0405 (17)	0.0447 (17)	0.0050 (14)	0.0092 (15)	−0.0068 (15)
C5	0.061 (2)	0.0444 (19)	0.0425 (18)	0.0087 (17)	0.0188 (17)	0.0064 (16)
C6	0.051 (2)	0.0427 (18)	0.0412 (17)	−0.0029 (15)	0.0208 (15)	0.0018 (15)
C7	0.0385 (17)	0.0451 (17)	0.0352 (16)	−0.0079 (14)	0.0176 (13)	−0.0056 (14)
C8	0.0407 (18)	0.065 (2)	0.0426 (18)	−0.0003 (16)	0.0199 (15)	−0.0017 (17)
C9	0.044 (2)	0.059 (2)	0.082 (3)	0.0034 (16)	0.036 (2)	0.0025 (19)
C10	0.052 (2)	0.068 (3)	0.069 (2)	0.0146 (19)	0.011 (2)	0.001 (2)

Geometric parameters (Å, º) top

Cl1—C8	1.763 (4)	C4—C10	1.510 (5)
Cl2—C8	1.763 (4)	C5—C6	1.382 (5)
O1—C7	1.227 (4)	C5—H5	0.87 (4)
N1—C7	1.334 (4)	C6—H6	0.93 (4)
N1—C1	1.425 (4)	C7—C8	1.522 (5)
N1—H1N	0.84 (4)	C8—H8	0.97 (4)
C1—C6	1.384 (4)	C9—H9A	0.9600
C1—C2	1.390 (4)	C9—H9B	0.9600
C2—C3	1.389 (4)	C9—H9C	0.9600
C2—H2	0.95 (3)	C10—H10A	0.9600
C3—C4	1.395 (5)	C10—H10B	0.9600
C3—C9	1.510 (5)	C10—H10C	0.9600
C4—C5	1.385 (5)

C7—N1—C1	126.7 (3)	O1—C7—N1	125.4 (3)
C7—N1—H1N	118 (2)	O1—C7—C8	121.0 (3)
C1—N1—H1N	115 (2)	N1—C7—C8	113.6 (3)
C6—C1—C2	119.8 (3)	C7—C8—Cl1	109.5 (2)
C6—C1—N1	123.0 (3)	C7—C8—Cl2	108.9 (3)
C2—C1—N1	117.2 (3)	Cl1—C8—Cl2	110.92 (18)
C3—C2—C1	121.4 (3)	C7—C8—H8	116 (2)
C3—C2—H2	118 (2)	Cl1—C8—H8	108 (2)
C1—C2—H2	121 (2)	Cl2—C8—H8	103 (2)
C2—C3—C4	119.2 (3)	C3—C9—H9A	109.5
C2—C3—C9	119.6 (3)	C3—C9—H9B	109.5
C4—C3—C9	121.2 (3)	H9A—C9—H9B	109.5
C5—C4—C3	118.2 (3)	C3—C9—H9C	109.5
C5—C4—C10	120.4 (3)	H9A—C9—H9C	109.5
C3—C4—C10	121.4 (3)	H9B—C9—H9C	109.5
C6—C5—C4	123.2 (3)	C4—C10—H10A	109.5
C6—C5—H5	117 (3)	C4—C10—H10B	109.5
C4—C5—H5	119 (3)	H10A—C10—H10B	109.5
C5—C6—C1	118.2 (3)	C4—C10—H10C	109.5
C5—C6—H6	120 (2)	H10A—C10—H10C	109.5
C1—C6—H6	122 (2)	H10B—C10—H10C	109.5

C7—N1—C1—C6	31.6 (5)	C10—C4—C5—C6	177.8 (3)
C7—N1—C1—C2	−149.1 (3)	C4—C5—C6—C1	0.4 (5)
C6—C1—C2—C3	−1.8 (5)	C2—C1—C6—C5	1.6 (5)
N1—C1—C2—C3	178.8 (3)	N1—C1—C6—C5	−179.1 (3)
C1—C2—C3—C4	0.0 (5)	C1—N1—C7—O1	−4.0 (5)
C1—C2—C3—C9	−178.6 (3)	C1—N1—C7—C8	176.7 (3)
C2—C3—C4—C5	2.0 (5)	O1—C7—C8—Cl1	50.4 (4)
C9—C3—C4—C5	−179.4 (3)	N1—C7—C8—Cl1	−130.4 (3)
C2—C3—C4—C10	−178.1 (3)	O1—C7—C8—Cl2	−71.0 (3)
C9—C3—C4—C10	0.5 (5)	N1—C7—C8—Cl2	108.2 (3)
C3—C4—C5—C6	−2.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.84 (4)	2.07 (4)	2.894 (3)	166 (3)

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁Cl₂NO
M_r	232.10
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	299
a, b, c (Å)	11.951 (1), 10.534 (1), 9.303 (1)
β (°)	111.26 (1)
V (Å³)	1091.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.56
Crystal size (mm)	0.28 × 0.20 × 0.12

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.859, 0.936
No. of measured, independent and observed [I > 2σ(I)] reflections	4567, 2214, 1495
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.187, 1.20
No. of reflections	2214
No. of parameters	144
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.37

Computer programs: CrysAlis CCD (Oxford Diffraction, 2004), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.84 (4)	2.07 (4)	2.894 (3)	166 (3)

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

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

References

Gowda, B. T., Foro, S. & Fuess, H. (2007). Acta Cryst. E63, o3875. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gowda, B. T., Foro, S. & Fuess, H. (2008). Acta Cryst. E64, o11. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gowda, B. T., Foro, S., Terao, H. & Fuess, H. (2009). Acta Cryst. E65, o1041. Web of Science CSD CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2004). CrysAlis CCD. Oxford Diffraction Ltd, Köln, Germany. Google Scholar
Oxford Diffraction (2007). CrysAlis RED. Oxford Diffraction Ltd, Köln, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shilpa and Gowda, B. T. (2007). Z. Naturforsch. Teil A, 62, 84–90. Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar