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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1445.
Published online 2009 May 29. doi:  10.1107/S1600536809019898
PMCID: PMC2969621

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

Abstract

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 [triangle]); Pies et al. (1971 [triangle]). 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 [triangle]); Gowda, Kožíšek et al. (2008 [triangle]); Gowda et al. (2009 [triangle]).

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Object name is e-65-o1445-scheme1.jpg

Experimental

Crystal data

  • C8H6Cl3NO
  • M r = 238.49
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1445-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.098
  • S = 1.02
  • 1914 reflections
  • 122 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.31 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809019898/bt2962sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The N-bound H atom was located in difference map and its positional parameters were refined freely. The other H atoms were positioned with idealized geometry using a riding model [C—H = 0.93–0.97 Å]. All H atoms were refined with isotropic displacement parameters set to 1.2 times of the Ueq of the parent atom.

Figures

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.

Crystal data

C8H6Cl3NOZ = 2
Mr = 238.49F(000) = 240
Triclinic, P1Dx = 1.677 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.492 (2) ÅCell parameters from 698 reflections
b = 8.496 (2) Åθ = 3.2–27.9°
c = 8.988 (2) ŵ = 0.92 mm1
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

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector1914 independent reflections
Radiation source: fine-focus sealed tube1359 reflections with I > 2σ(I)
graphiteRint = 0.018
Rotation method data acquisition using ω and [var phi] scansθmax = 26.4°, θmin = 3.2°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)h = −8→9
Tmin = 0.720, Tmax = 0.823k = −10→9
2735 measured reflectionsl = −10→11

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.098w = 1/[σ2(Fo2) + (0.0433P)2 + 0.1195P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
1914 reflectionsΔρmax = 0.28 e Å3
122 parametersΔρmin = −0.31 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.043 (4)

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 (Å2)

xyzUiso*/Ueq
Cl11.03470 (12)0.29507 (9)−0.22746 (8)0.0527 (2)
Cl20.72031 (12)0.28513 (10)0.52153 (8)0.0594 (3)
Cl30.68240 (12)0.81217 (11)−0.40685 (9)0.0608 (3)
O10.4705 (3)0.7757 (2)0.0703 (2)0.0531 (6)
N10.7131 (3)0.5825 (3)−0.0831 (3)0.0375 (5)
H1N0.772 (4)0.572 (3)−0.178 (3)0.045*
C10.7880 (4)0.4371 (3)0.0367 (3)0.0322 (6)
C20.9420 (4)0.2924 (3)−0.0178 (3)0.0335 (6)
C31.0238 (4)0.1464 (3)0.0928 (3)0.0389 (6)
H31.12610.05060.05480.047*
C40.9541 (4)0.1425 (3)0.2590 (3)0.0395 (6)
H41.00760.04430.33430.047*
C50.8036 (4)0.2866 (3)0.3124 (3)0.0376 (6)
C60.7181 (4)0.4339 (3)0.2045 (3)0.0370 (6)
H60.61580.52900.24360.044*
C70.5703 (4)0.7374 (3)−0.0617 (3)0.0343 (6)
C80.5319 (4)0.8743 (3)−0.2174 (3)0.0436 (7)
H8A0.55400.9800−0.21900.052*
H8B0.39050.9042−0.21090.052*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0643 (5)0.0476 (4)0.0356 (4)−0.0068 (4)−0.0059 (3)−0.0184 (3)
Cl20.0708 (5)0.0553 (5)0.0319 (4)0.0043 (4)−0.0182 (3)−0.0098 (3)
Cl30.0635 (5)0.0648 (5)0.0333 (4)−0.0041 (4)−0.0140 (3)−0.0049 (3)
O10.0577 (13)0.0443 (11)0.0350 (10)0.0045 (10)−0.0100 (10)−0.0104 (9)
N10.0410 (13)0.0352 (12)0.0268 (11)−0.0026 (10)−0.0082 (10)−0.0081 (9)
C10.0309 (13)0.0310 (13)0.0336 (13)−0.0067 (11)−0.0102 (10)−0.0079 (10)
C20.0337 (13)0.0358 (14)0.0321 (13)−0.0114 (11)−0.0053 (11)−0.0126 (11)
C30.0341 (14)0.0336 (14)0.0468 (16)−0.0013 (11)−0.0138 (12)−0.0146 (12)
C40.0402 (15)0.0333 (14)0.0431 (15)−0.0042 (12)−0.0196 (12)−0.0060 (11)
C50.0394 (15)0.0384 (14)0.0327 (13)−0.0063 (12)−0.0129 (11)−0.0090 (11)
C60.0356 (14)0.0358 (14)0.0338 (13)−0.0018 (11)−0.0105 (11)−0.0111 (11)
C70.0334 (14)0.0313 (13)0.0352 (14)−0.0073 (11)−0.0095 (11)−0.0077 (11)
C80.0405 (15)0.0421 (15)0.0369 (15)−0.0039 (13)−0.0109 (12)−0.0062 (12)

Geometric parameters (Å, °)

Cl1—C21.737 (2)C3—C41.374 (4)
Cl2—C51.737 (3)C3—H30.9300
Cl3—C81.771 (3)C4—C51.379 (4)
O1—C71.212 (3)C4—H40.9300
N1—C71.348 (3)C5—C61.383 (3)
N1—C11.410 (3)C6—H60.9300
N1—H1N0.82 (3)C7—C81.518 (3)
C1—C61.389 (3)C8—H8A0.9700
C1—C21.395 (3)C8—H8B0.9700
C2—C31.382 (3)
C7—N1—C1128.8 (2)C4—C5—C6122.2 (2)
C7—N1—H1N117.0 (19)C4—C5—Cl2119.14 (19)
C1—N1—H1N114.0 (19)C6—C5—Cl2118.7 (2)
C6—C1—C2119.1 (2)C5—C6—C1118.8 (2)
C6—C1—N1122.9 (2)C5—C6—H6120.6
C2—C1—N1117.9 (2)C1—C6—H6120.6
C3—C2—C1120.9 (2)O1—C7—N1125.7 (2)
C3—C2—Cl1119.2 (2)O1—C7—C8117.8 (2)
C1—C2—Cl1119.91 (19)N1—C7—C8116.5 (2)
C4—C3—C2120.1 (2)C7—C8—Cl3115.98 (18)
C4—C3—H3120.0C7—C8—H8A108.3
C2—C3—H3120.0Cl3—C8—H8A108.3
C3—C4—C5119.0 (2)C7—C8—H8B108.3
C3—C4—H4120.5Cl3—C8—H8B108.3
C5—C4—H4120.5H8A—C8—H8B107.4
C7—N1—C1—C60.5 (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—C30.6 (4)Cl2—C5—C6—C1178.5 (2)
N1—C1—C2—C3179.3 (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—C8175.9 (2)
Cl1—C2—C3—C4179.3 (2)O1—C7—C8—Cl3179.7 (2)
C2—C3—C4—C5−0.6 (4)N1—C7—C8—Cl3−0.5 (3)
C3—C4—C5—C61.1 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N···Cl30.82 (3)2.43 (3)2.922 (2)120 (2)
N1—H1N···Cl10.82 (3)2.45 (3)2.933 (2)119 (2)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2962).

References

  • Gowda, B. T., Foro, S. & Fuess, H. (2008). Acta Cryst. E64, o419. [PMC free article] [PubMed]
  • Gowda, B. T., Foro, S., Terao, H. & Fuess, H. (2009). Acta Cryst. E65, o949. [PMC free article] [PubMed]
  • Gowda, B. T., Kožíšek, J., Tokarčík, M. & Fuess, H. (2008). Acta Cryst. E64, o987. [PMC free article] [PubMed]
  • Oxford Diffraction (2004). CrysAlis CCD Oxford Diffraction Ltd, Köln, Germany.
  • Oxford Diffraction (2007). CrysAlis RED Oxford Diffraction Ltd, Köln, Germany.
  • Pies, W., Rager, H. & Weiss, A. (1971). Org. Magn. Reson.3, 147–176.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Shilpa & Gowda, B. T. (2007). Z. Naturforsch. Teil A, 62, 84–90.
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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