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

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

doi:10.1107/S1600536809013075

organic compounds

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Volume 65| Part 5| May 2009| Page o1041

doi:10.1107/S1600536809013075

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

B. Thimme Gowda,^a ^* Sabine Foro,^b 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 5 April 2009; accepted 6 April 2009; online 18 April 2009)

The conformation of the N—H bond in the title compound, C₁₀H₁₀Cl₃NO, is anti to the C=O bond. The amide H atom exhibits both intramolecular N—H⋯Cl and intermolecular N—H⋯O hydrogen bonding. The latter interactions link the molecules into infinite chains.

Related literature

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

Experimental

Crystal data

C₁₀H₁₀Cl₃NO
M_r = 266.54
Monoclinic, P 2₁ /c
a = 5.9003 (8) Å
b = 20.843 (2) Å
c = 9.996 (1) Å
β = 105.53 (1)°
V = 1184.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.75 mm⁻¹
T = 299 K
0.46 × 0.40 × 0.30 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 = 0.726, T_max = 0.807
9395 measured reflections
2407 independent reflections
1952 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.151
S = 1.08
2407 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.96 e Å⁻³
Δρ_min = −0.88 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.86	2.14	2.917 (3)	149
N1—H1N⋯Cl1	0.86	2.57	3.003 (3)	112
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/S1600536809013075/bt2926sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809013075/bt2926Isup2.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 2,2,2-trichloro-N-(3,4-dimethylphenyl)acetamide has been determined. The conformation of the N—H bond in the title compound is anti to the 3-methyl substituent in the aromatic ring similar to that observed with respect to the 3-chloro substituent in N- (3,4-dichlorophenyl)-2,2,2-trichloroacetamide (Gowda et al., 2007), but in contrast to the syn conformation observed with respect to the 3-methyl substituent in N-(3,4-dimethylphenyl)acetamide (Gowda et al., 2008). The conformation of the C=O bond in the structure is anti to the N—H bond similar to that observed in other amides. The amide H atom exhibits both N—H···Cl intramolecular and N—H···O intermolecular hydrogen bonding. The molecules in (I) are linked into infinite chains through intermolecular N—H···O hydrogen bonding (Table 1, Fig. 2).

Related literature top

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

Experimental top

The title compound was prepared according to the literature method (Shilpa & Gowda, 2007). Single crystals were obtained from the slow evaporation of an ethanolic solution.

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 the title compound, showing the atom labeling scheme and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Molecular packing of the title compound with hydrogen bonding shown as dashed lines.

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

Crystal data top

C₁₀H₁₀Cl₃NO	F(000) = 544
M_r = 266.54	D_x = 1.495 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3672 reflections
a = 5.9003 (8) Å	θ = 2.3–27.6°
b = 20.843 (2) Å	µ = 0.75 mm⁻¹
c = 9.996 (1) Å	T = 299 K
β = 105.53 (1)°	Prism, colourless
V = 1184.4 (2) Å³	0.46 × 0.40 × 0.30 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2407 independent reflections
Radiation source: fine-focus sealed tube	1952 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
Rotation method data acquisition using ω and ϕ scans	θ_max = 26.4°, θ_min = 2.3°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	h = −7→7
T_min = 0.726, T_max = 0.807	k = −25→26
9395 measured reflections	l = −12→12

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.151	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0592P)² + 1.4852P] where P = (F_o² + 2F_c²)/3
2407 reflections	(Δ/σ)_max < 0.001
138 parameters	Δρ_max = 0.96 e Å⁻³
0 restraints	Δρ_min = −0.88 e Å⁻³

Crystal data top

C₁₀H₁₀Cl₃NO	V = 1184.4 (2) Å³
M_r = 266.54	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.9003 (8) Å	µ = 0.75 mm⁻¹
b = 20.843 (2) Å	T = 299 K
c = 9.996 (1) Å	0.46 × 0.40 × 0.30 mm
β = 105.53 (1)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2407 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	1952 reflections with I > 2σ(I)
T_min = 0.726, T_max = 0.807	R_int = 0.015
9395 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.151	H-atom parameters constrained
S = 1.08	Δρ_max = 0.96 e Å⁻³
2407 reflections	Δρ_min = −0.88 e Å⁻³
138 parameters

Special details top

Experimental. Absorption correction: 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	1.2122 (2)	0.19521 (5)	0.59191 (11)	0.0833 (4)
Cl2	1.1512 (2)	0.15721 (6)	0.31037 (12)	0.0939 (5)
Cl3	0.8043 (2)	0.12567 (5)	0.45005 (16)	0.0919 (4)
O1	0.8060 (5)	0.25550 (12)	0.2520 (2)	0.0643 (7)
N1	0.8025 (4)	0.28196 (11)	0.4703 (2)	0.0403 (5)
H1N	0.8600	0.2723	0.5563	0.048*
C1	0.6475 (5)	0.33590 (13)	0.4375 (3)	0.0377 (6)
C2	0.6550 (5)	0.37830 (13)	0.3319 (3)	0.0399 (6)
H2	0.7657	0.3724	0.2819	0.048*
C3	0.4996 (5)	0.42941 (13)	0.2998 (3)	0.0413 (6)
C4	0.3341 (5)	0.43886 (14)	0.3749 (3)	0.0459 (7)
C5	0.3325 (6)	0.39622 (17)	0.4814 (4)	0.0552 (8)
H5	0.2243	0.4024	0.5329	0.066*
C6	0.4852 (6)	0.34532 (15)	0.5131 (3)	0.0500 (7)
H6	0.4796	0.3174	0.5848	0.060*
C7	0.8629 (5)	0.24601 (13)	0.3758 (3)	0.0391 (6)
C8	1.0067 (5)	0.18464 (14)	0.4322 (3)	0.0440 (7)
C9	0.5074 (7)	0.47305 (17)	0.1813 (4)	0.0618 (9)
H9A	0.6361	0.4609	0.1449	0.074*
H9B	0.5285	0.5166	0.2138	0.074*
H9C	0.3625	0.4695	0.1096	0.074*
C10	0.1610 (7)	0.49358 (19)	0.3417 (4)	0.0662 (10)
H10A	0.2428	0.5334	0.3672	0.079*
H10B	0.0457	0.4884	0.3929	0.079*
H10C	0.0843	0.4937	0.2441	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0948 (8)	0.0602 (6)	0.0657 (6)	0.0180 (5)	−0.0288 (5)	−0.0006 (4)
Cl2	0.1151 (9)	0.1008 (9)	0.0806 (7)	0.0593 (7)	0.0517 (7)	0.0208 (6)
Cl3	0.0866 (8)	0.0481 (5)	0.1423 (11)	−0.0182 (5)	0.0329 (7)	0.0060 (6)
O1	0.0981 (18)	0.0639 (14)	0.0272 (10)	0.0322 (13)	0.0104 (11)	−0.0009 (10)
N1	0.0564 (14)	0.0378 (12)	0.0244 (10)	0.0055 (10)	0.0067 (10)	0.0019 (9)
C1	0.0476 (15)	0.0331 (13)	0.0305 (13)	−0.0007 (11)	0.0074 (11)	−0.0030 (10)
C2	0.0472 (15)	0.0398 (14)	0.0344 (14)	0.0002 (12)	0.0141 (12)	0.0006 (11)
C3	0.0482 (16)	0.0346 (14)	0.0389 (14)	−0.0022 (12)	0.0078 (12)	0.0003 (11)
C4	0.0460 (16)	0.0386 (15)	0.0520 (17)	−0.0001 (12)	0.0113 (13)	−0.0036 (13)
C5	0.0551 (19)	0.0589 (19)	0.060 (2)	0.0054 (15)	0.0295 (16)	−0.0003 (16)
C6	0.0630 (19)	0.0491 (17)	0.0430 (16)	0.0002 (15)	0.0230 (14)	0.0058 (13)
C7	0.0475 (15)	0.0370 (14)	0.0305 (13)	0.0016 (12)	0.0064 (11)	−0.0009 (11)
C8	0.0501 (17)	0.0389 (15)	0.0418 (15)	0.0020 (12)	0.0100 (13)	0.0007 (12)
C9	0.073 (2)	0.0528 (19)	0.063 (2)	0.0143 (17)	0.0238 (18)	0.0199 (16)
C10	0.059 (2)	0.057 (2)	0.084 (3)	0.0139 (17)	0.0217 (19)	0.0043 (19)

Geometric parameters (Å, º) top

Cl1—C8	1.741 (3)	C4—C5	1.389 (5)
Cl2—C8	1.759 (3)	C4—C10	1.507 (4)
Cl3—C8	1.755 (3)	C5—C6	1.373 (5)
O1—C7	1.209 (3)	C5—H5	0.9300
N1—C7	1.327 (3)	C6—H6	0.9300
N1—C1	1.431 (3)	C7—C8	1.555 (4)
N1—H1N	0.8600	C9—H9A	0.9600
C1—C6	1.383 (4)	C9—H9B	0.9600
C1—C2	1.387 (4)	C9—H9C	0.9600
C2—C3	1.386 (4)	C10—H10A	0.9600
C2—H2	0.9300	C10—H10B	0.9600
C3—C4	1.395 (4)	C10—H10C	0.9600
C3—C9	1.504 (4)

C7—N1—C1	123.9 (2)	O1—C7—N1	125.6 (3)
C7—N1—H1N	118.0	O1—C7—C8	118.7 (2)
C1—N1—H1N	118.0	N1—C7—C8	115.5 (2)
C6—C1—C2	119.6 (3)	C7—C8—Cl1	114.0 (2)
C6—C1—N1	118.7 (2)	C7—C8—Cl3	107.0 (2)
C2—C1—N1	121.7 (2)	Cl1—C8—Cl3	108.74 (17)
C3—C2—C1	120.8 (3)	C7—C8—Cl2	109.6 (2)
C3—C2—H2	119.6	Cl1—C8—Cl2	109.15 (17)
C1—C2—H2	119.6	Cl3—C8—Cl2	108.17 (17)
C2—C3—C4	120.0 (3)	C3—C9—H9A	109.5
C2—C3—C9	119.3 (3)	C3—C9—H9B	109.5
C4—C3—C9	120.8 (3)	H9A—C9—H9B	109.5
C5—C4—C3	118.1 (3)	C3—C9—H9C	109.5
C5—C4—C10	120.6 (3)	H9A—C9—H9C	109.5
C3—C4—C10	121.3 (3)	H9B—C9—H9C	109.5
C6—C5—C4	122.2 (3)	C4—C10—H10A	109.5
C6—C5—H5	118.9	C4—C10—H10B	109.5
C4—C5—H5	118.9	H10A—C10—H10B	109.5
C5—C6—C1	119.4 (3)	C4—C10—H10C	109.5
C5—C6—H6	120.3	H10A—C10—H10C	109.5
C1—C6—H6	120.3	H10B—C10—H10C	109.5

C7—N1—C1—C6	140.0 (3)	C4—C5—C6—C1	0.3 (5)
C7—N1—C1—C2	−39.4 (4)	C2—C1—C6—C5	0.6 (5)
C6—C1—C2—C3	−1.0 (4)	N1—C1—C6—C5	−178.9 (3)
N1—C1—C2—C3	178.5 (3)	C1—N1—C7—O1	3.8 (5)
C1—C2—C3—C4	0.4 (4)	C1—N1—C7—C8	−172.3 (2)
C1—C2—C3—C9	−177.9 (3)	O1—C7—C8—Cl1	145.1 (3)
C2—C3—C4—C5	0.5 (4)	N1—C7—C8—Cl1	−38.5 (3)
C9—C3—C4—C5	178.7 (3)	O1—C7—C8—Cl3	−94.6 (3)
C2—C3—C4—C10	−179.4 (3)	N1—C7—C8—Cl3	81.8 (3)
C9—C3—C4—C10	−1.1 (5)	O1—C7—C8—Cl2	22.4 (4)
C3—C4—C5—C6	−0.8 (5)	N1—C7—C8—Cl2	−161.1 (2)
C10—C4—C5—C6	179.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.86	2.14	2.917 (3)	149
N1—H1N···Cl1	0.86	2.57	3.003 (3)	112

Symmetry code: (i) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀Cl₃NO
M_r	266.54
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	299
a, b, c (Å)	5.9003 (8), 20.843 (2), 9.996 (1)
β (°)	105.53 (1)
V (Å³)	1184.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.75
Crystal size (mm)	0.46 × 0.40 × 0.30

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	0.726, 0.807
No. of measured, independent and observed [I > 2σ(I)] reflections	9395, 2407, 1952
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.151, 1.08
No. of reflections	2407
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.96, −0.88

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	0.86	2.14	2.917 (3)	149.4
N1—H1N···Cl1	0.86	2.57	3.003 (3)	111.8

Symmetry code: (i) x, −y+1/2, z+1/2.

References

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, o949. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gowda, B. T., Kožíšek, J., Tokarčík, M. & Fuess, H. (2007). Acta Cryst. E63, o2567–o2568. 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 & 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

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1041

doi:10.1107/S1600536809013075

Open

access