2-Chloro-N-(2,5-dichloro­phen­yl)acetamide

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

doi:10.1107/S1600536809019898

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1445

doi:10.1107/S1600536809019898

Open

access

2-Chloro-N-(2,5-dichlorophenyl)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 15 May 2009; accepted 25 May 2009; online 29 May 2009)

The conformation of the N—H bond in the structure of the title compound, C₈H₆Cl₃NO, is anti to the C=O bond. The N—H H atom shows close intramolecular N—H⋯Cl hydrogen bonds with both the ring Cl atom in the ortho position and the side-chain Cl atom. The molecules crystallize in planes parallel to (221).

Related literature

For the preparation, see: Shilpa & Gowda (2007 ); Pies et al. (1971 ). For our work on the effect of ring and side-chain substitutions on the solid-state geometries of aromatic amides, see: Gowda Foro & Fuess (2008 ); Gowda, Kožíšek et al. (2008 ); Gowda et al. (2009 ).

Experimental

Crystal data

C₈H₆Cl₃NO
M_r = 238.49
Triclinic, $[P \overline 1]$
a = 7.492 (2) Å
b = 8.496 (2) Å
c = 8.988 (2) Å
α = 69.68 (2)°
β = 67.54 (2)°
γ = 66.67 (2)°
V = 472.4 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.92 mm⁻¹
T = 299 K
0.38 × 0.28 × 0.22 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 = 0.720, T_max = 0.823
2735 measured reflections
1914 independent reflections
1359 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.098
S = 1.02
1914 reflections
122 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯Cl3	0.82 (3)	2.43 (3)	2.922 (2)	120 (2)
N1—H1N⋯Cl1	0.82 (3)	2.45 (3)	2.933 (2)	119 (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/S1600536809019898/bt2962sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809019898/bt2962Isup2.hkl

checkCIF report

Comment top

As part of a study of the effect of ring and side chain substitutions on the solid state geometries of aromatic amides (Gowda Foro & Fuess, 2008; Gowda, Kožíšek et al., 2008; Gowda et al., 2009), in the present work, the structure of 2-chloro-N-(2,5-dichlorophenyl)acetamide (25DCPCA)(I) has been determined. The conformation of the N—H bond in the structure (Fig. 1) is syn to the ortho-chloro and anti to the meta-chloro substituents in the aromatic ring, in contrast to the syn conformation observed with respect to both the 2-chloro and 3-chloro groups in 2-chloro-N-(2,3-dichlorophenyl)acetamide (Gowda, Kožíšek et al., 2008). Furthermore, the conformation of the C=O bond is anti to both the N—H bond and side chain Cl atom, compared to the anti conformation of the C=O bond with respect to the N–H bond and syn with respect to the side chain Cl atom, observed in 2-chloro-N-(2,3-dichlorophenyl)-acetamide (Gowda Foro & Fuess, 2008). But the conformations of the N–H bond and the side chain C–H bonds are anti to each other, while those of the ring C–Cl and the side chain C–Cl bonds are syn to each other. Further, the N—H H-atom shows simultaneous intramolecular hydrogen bonding with both the ring and side chain Cl atoms. The crystal packing is shown in Fig.2 (Table 1).

Related literature top

For the preparation, see: Shilpa & Gowda (2007); Pies et al. (1971). For our work on the effect of ring and side-chain substitutions on the solid-state geometries of aromatic amides, see: Gowda Foro & Fuess (2008); Gowda, Kožíšek et al. (2008); Gowda et al. (2009).

Experimental top

The title compound was prepared according to the literature method (Shilpa & Gowda, 2007). The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared, NMR and NQR spectra (Shilpa & Gowda, 2007; Pies et al., 1971). Single crystals of the title compound used for X-ray diffraction studies were grown by a slow evaporation of its ethanolic solution at room temperature.

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 labelling scheme. The displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing of the title compound with hydrogen bonding shown as dashed lines.

2-Chloro-N-(2,5-dichlorophenyl)acetamide top

Crystal data top

C₈H₆Cl₃NO	Z = 2
M_r = 238.49	F(000) = 240
Triclinic, P1	D_x = 1.677 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.492 (2) Å	Cell parameters from 698 reflections
b = 8.496 (2) Å	θ = 3.2–27.9°
c = 8.988 (2) Å	µ = 0.92 mm⁻¹
α = 69.68 (2)°	T = 299 K
β = 67.54 (2)°	Prism, colourless
γ = 66.67 (2)°	0.38 × 0.28 × 0.22 mm
V = 472.4 (2) Å³

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	1914 independent reflections
Radiation source: fine-focus sealed tube	1359 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Rotation method data acquisition using ω and ϕ scans	θ_max = 26.4°, θ_min = 3.2°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	h = −8→9
T_min = 0.720, T_max = 0.823	k = −10→9
2735 measured reflections	l = −10→11

Refinement top

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)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0433P)² + 0.1195P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
1914 reflections	Δρ_max = 0.28 e Å⁻³
122 parameters	Δρ_min = −0.31 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: 0.043 (4)

Crystal data top

C₈H₆Cl₃NO	γ = 66.67 (2)°
M_r = 238.49	V = 472.4 (2) Å³
Triclinic, P1	Z = 2
a = 7.492 (2) Å	Mo Kα radiation
b = 8.496 (2) Å	µ = 0.92 mm⁻¹
c = 8.988 (2) Å	T = 299 K
α = 69.68 (2)°	0.38 × 0.28 × 0.22 mm
β = 67.54 (2)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	1914 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	1359 reflections with I > 2σ(I)
T_min = 0.720, T_max = 0.823	R_int = 0.018
2735 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.28 e Å⁻³
1914 reflections	Δρ_min = −0.31 e Å⁻³
122 parameters

Special details top

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	1.03470 (12)	0.29507 (9)	−0.22746 (8)	0.0527 (2)
Cl2	0.72031 (12)	0.28513 (10)	0.52153 (8)	0.0594 (3)
Cl3	0.68240 (12)	0.81217 (11)	−0.40685 (9)	0.0608 (3)
O1	0.4705 (3)	0.7757 (2)	0.0703 (2)	0.0531 (6)
N1	0.7131 (3)	0.5825 (3)	−0.0831 (3)	0.0375 (5)
H1N	0.772 (4)	0.572 (3)	−0.178 (3)	0.045*
C1	0.7880 (4)	0.4371 (3)	0.0367 (3)	0.0322 (6)
C2	0.9420 (4)	0.2924 (3)	−0.0178 (3)	0.0335 (6)
C3	1.0238 (4)	0.1464 (3)	0.0928 (3)	0.0389 (6)
H3	1.1261	0.0506	0.0548	0.047*
C4	0.9541 (4)	0.1425 (3)	0.2590 (3)	0.0395 (6)
H4	1.0076	0.0443	0.3343	0.047*
C5	0.8036 (4)	0.2866 (3)	0.3124 (3)	0.0376 (6)
C6	0.7181 (4)	0.4339 (3)	0.2045 (3)	0.0370 (6)
H6	0.6158	0.5290	0.2436	0.044*
C7	0.5703 (4)	0.7374 (3)	−0.0617 (3)	0.0343 (6)
C8	0.5319 (4)	0.8743 (3)	−0.2174 (3)	0.0436 (7)
H8A	0.5540	0.9800	−0.2190	0.052*
H8B	0.3905	0.9042	−0.2109	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0643 (5)	0.0476 (4)	0.0356 (4)	−0.0068 (4)	−0.0059 (3)	−0.0184 (3)
Cl2	0.0708 (5)	0.0553 (5)	0.0319 (4)	0.0043 (4)	−0.0182 (3)	−0.0098 (3)
Cl3	0.0635 (5)	0.0648 (5)	0.0333 (4)	−0.0041 (4)	−0.0140 (3)	−0.0049 (3)
O1	0.0577 (13)	0.0443 (11)	0.0350 (10)	0.0045 (10)	−0.0100 (10)	−0.0104 (9)
N1	0.0410 (13)	0.0352 (12)	0.0268 (11)	−0.0026 (10)	−0.0082 (10)	−0.0081 (9)
C1	0.0309 (13)	0.0310 (13)	0.0336 (13)	−0.0067 (11)	−0.0102 (10)	−0.0079 (10)
C2	0.0337 (13)	0.0358 (14)	0.0321 (13)	−0.0114 (11)	−0.0053 (11)	−0.0126 (11)
C3	0.0341 (14)	0.0336 (14)	0.0468 (16)	−0.0013 (11)	−0.0138 (12)	−0.0146 (12)
C4	0.0402 (15)	0.0333 (14)	0.0431 (15)	−0.0042 (12)	−0.0196 (12)	−0.0060 (11)
C5	0.0394 (15)	0.0384 (14)	0.0327 (13)	−0.0063 (12)	−0.0129 (11)	−0.0090 (11)
C6	0.0356 (14)	0.0358 (14)	0.0338 (13)	−0.0018 (11)	−0.0105 (11)	−0.0111 (11)
C7	0.0334 (14)	0.0313 (13)	0.0352 (14)	−0.0073 (11)	−0.0095 (11)	−0.0077 (11)
C8	0.0405 (15)	0.0421 (15)	0.0369 (15)	−0.0039 (13)	−0.0109 (12)	−0.0062 (12)

Geometric parameters (Å, º) top

Cl1—C2	1.737 (2)	C3—C4	1.374 (4)
Cl2—C5	1.737 (3)	C3—H3	0.9300
Cl3—C8	1.771 (3)	C4—C5	1.379 (4)
O1—C7	1.212 (3)	C4—H4	0.9300
N1—C7	1.348 (3)	C5—C6	1.383 (3)
N1—C1	1.410 (3)	C6—H6	0.9300
N1—H1N	0.82 (3)	C7—C8	1.518 (3)
C1—C6	1.389 (3)	C8—H8A	0.9700
C1—C2	1.395 (3)	C8—H8B	0.9700
C2—C3	1.382 (3)

C7—N1—C1	128.8 (2)	C4—C5—C6	122.2 (2)
C7—N1—H1N	117.0 (19)	C4—C5—Cl2	119.14 (19)
C1—N1—H1N	114.0 (19)	C6—C5—Cl2	118.7 (2)
C6—C1—C2	119.1 (2)	C5—C6—C1	118.8 (2)
C6—C1—N1	122.9 (2)	C5—C6—H6	120.6
C2—C1—N1	117.9 (2)	C1—C6—H6	120.6
C3—C2—C1	120.9 (2)	O1—C7—N1	125.7 (2)
C3—C2—Cl1	119.2 (2)	O1—C7—C8	117.8 (2)
C1—C2—Cl1	119.91 (19)	N1—C7—C8	116.5 (2)
C4—C3—C2	120.1 (2)	C7—C8—Cl3	115.98 (18)
C4—C3—H3	120.0	C7—C8—H8A	108.3
C2—C3—H3	120.0	Cl3—C8—H8A	108.3
C3—C4—C5	119.0 (2)	C7—C8—H8B	108.3
C3—C4—H4	120.5	Cl3—C8—H8B	108.3
C5—C4—H4	120.5	H8A—C8—H8B	107.4

C7—N1—C1—C6	0.5 (4)	C3—C4—C5—Cl2	−178.1 (2)
C7—N1—C1—C2	−178.1 (3)	C4—C5—C6—C1	−0.7 (4)
C6—C1—C2—C3	0.6 (4)	Cl2—C5—C6—C1	178.5 (2)
N1—C1—C2—C3	179.3 (2)	C2—C1—C6—C5	−0.1 (4)
C6—C1—C2—Cl1	−178.90 (19)	N1—C1—C6—C5	−178.7 (2)
N1—C1—C2—Cl1	−0.2 (3)	C1—N1—C7—O1	−4.4 (5)
C1—C2—C3—C4	−0.2 (4)	C1—N1—C7—C8	175.9 (2)
Cl1—C2—C3—C4	179.3 (2)	O1—C7—C8—Cl3	179.7 (2)
C2—C3—C4—C5	−0.6 (4)	N1—C7—C8—Cl3	−0.5 (3)
C3—C4—C5—C6	1.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl3	0.82 (3)	2.43 (3)	2.922 (2)	120 (2)
N1—H1N···Cl1	0.82 (3)	2.45 (3)	2.933 (2)	119 (2)

Experimental details

Crystal data
Chemical formula	C₈H₆Cl₃NO
M_r	238.49
Crystal system, space group	Triclinic, P1
Temperature (K)	299
a, b, c (Å)	7.492 (2), 8.496 (2), 8.988 (2)
α, β, γ (°)	69.68 (2), 67.54 (2), 66.67 (2)
V (Å³)	472.4 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.92
Crystal size (mm)	0.38 × 0.28 × 0.22

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	0.720, 0.823
No. of measured, independent and observed [I > 2σ(I)] reflections	2735, 1914, 1359
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.098, 1.02
No. of reflections	1914
No. of parameters	122
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.31

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···Cl3	0.82 (3)	2.43 (3)	2.922 (2)	120 (2)
N1—H1N···Cl1	0.82 (3)	2.45 (3)	2.933 (2)	119 (2)

Acknowledgements

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

References

Gowda, B. T., Foro, S. & Fuess, H. (2008). Acta Cryst. E64, o419. 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. (2008). Acta Cryst. E64, o987. 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
Pies, W., Rager, H. & Weiss, A. (1971). Org. Magn. Reson. 3, 147–176. CrossRef CAS Web of Science 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