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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1719.
Published online 2009 June 27. doi:  10.1107/S1600536809024052
PMCID: PMC2969282

2-Chloro-N,N-diphenyl­acetamide

Abstract

In the title compound, C14H12ClNO, the central acetamide plane forms dihedral angles of 76.0 (2) and 64.0 (2)° with the phenyl rings and the phenyl rings form a dihedral angle of 71.8 (2)° with each other.

Related literature

The title compound is an important inter­mediate in the synthesis of N-phenyl-indolin-2-one, which can be further transformed to l-aryl-3-(amino­alkyl­idene)oxindoles, a new class of ‘GABAergic’ agents (Shindikar et al., 2006 [triangle]; Sarges et al., 1989 [triangle]) using a new variant of the Friedel–Crafts cyclization (Hennessy & Buchwald, 2003 [triangle]; Trost & Frederiksen, 2005 [triangle]; Trost & Yong, 2006 [triangle]).

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Object name is e-65-o1719-scheme1.jpg

Experimental

Crystal data

  • C14H12ClNO
  • M r = 245.70
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1719-efi1.jpg
  • a = 6.4350 (13) Å
  • b = 12.799 (3) Å
  • c = 14.944 (3) Å
  • V = 1230.8 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.29 mm−1
  • T = 293 K
  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.917, T max = 0.971
  • 2519 measured reflections
  • 2231 independent reflections
  • 1842 reflections with I > 2σ(I)
  • R int = 0.064
  • 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.112
  • S = 1.00
  • 2231 reflections
  • 154 parameters
  • H-atom parameters constrained
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.21 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 912 Friedel pairs
  • Flack parameter: −0.14 (9)

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); 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 and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809024052/ya2097sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809024052/ya2097Isup2.hkl

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

Acknowledgments

The authors thank the Center of Testing and Analysis of Nanjing University for support of this study.

supplementary crystallographic information

Comment

The title compound is an important intermediate in the synthesis of N-phenyl-indolin-2-one, which can be further transformed to l-aryl-3-(aminoalkylidene)oxindoles, a new class of "GABAergic" agents (Shindikar et al., 2006; Sarges et al., 1989) using the new variant of the Friedel-Crafts cyclization (Hennessy & Buchwald, 2003; Trost & Frederiksen, 2005; Trost & Yong, 2006).

In the molecule of the title compound (Fig 1), dihedral angles formed by the central plane C14/C13/N/O with phenyl rings C1—C6 and C7—C12 are equal to 104.0 (2)° and 116.0 (2)° respectively; phenyl rings form dihedral angle 108.2 (2)° with each other.

Experimental

The title compound was prepared by refluxing for 2 hrs of the mixture of diphenylamine (1.69 g, 0.01 mol) and chloroacetyl chloride (1.13 g, 0.01 mol) in 50 ml of toluene. 150 ml of water was then added to the reaction mixture causing precipitation of the product, which was filtered, washed with water, dried and and recrystallized from ethanol (yield 97%). Crystals suitable for X-ray analysis were obtained by slow evaporation of a chloroform solution (yield 96%, m.p.413 K).

Refinement

The H atoms were positioned geometrically (C—H 0.97 and 0.93 Å for methylene and aromatic H, respectively), and included in the refinement in the riding motion approximation with Uiso(H) = 1.2Ueq of the carrying atom.

Figures

Fig. 1.
Molecular structure of the title compound; thermal displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small circles of arbitrary radius.

Crystal data

C14H12ClNODx = 1.326 Mg m3
Mr = 245.70Melting point: 393 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 25 reflections
a = 6.4350 (13) Åθ = 9.0–13.0°
b = 12.799 (3) ŵ = 0.29 mm1
c = 14.944 (3) ÅT = 293 K
V = 1230.8 (5) Å3Block, colorless
Z = 40.30 × 0.20 × 0.10 mm
F(000) = 512

Data collection

Enraf–Nonius CAD-4 diffractometer1842 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.064
graphiteθmax = 25.3°, θmin = 2.1°
ω/2θ scansh = −7→0
Absorption correction: ψ scan (North et al., 1968)k = −15→15
Tmin = 0.917, Tmax = 0.971l = −17→0
2519 measured reflections3 standard reflections every 200 reflections
2231 independent reflections intensity decay: 1%

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.112w = 1/[σ2(Fo2) + (0.065P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2231 reflectionsΔρmax = 0.18 e Å3
154 parametersΔρmin = −0.21 e Å3
0 restraintsAbsolute structure: Flack (1983), 912 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.14 (9)

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
Cl0.97222 (13)0.79305 (6)0.11836 (6)0.0621 (3)
O1.0050 (3)0.63002 (15)−0.01779 (12)0.0490 (5)
N1.2460 (3)0.52988 (16)0.05137 (14)0.0354 (5)
C11.6477 (5)0.4811 (2)0.2686 (2)0.0543 (8)
H1A1.73590.47110.31720.065*
C21.4544 (5)0.4359 (2)0.26845 (19)0.0514 (8)
H2A1.41110.39560.31670.062*
C31.3243 (5)0.4509 (2)0.19570 (17)0.0410 (7)
H3A1.19430.41930.19430.049*
C41.3879 (4)0.51270 (19)0.12568 (16)0.0343 (6)
C51.5827 (5)0.5572 (2)0.1258 (2)0.0485 (7)
H5A1.62630.59780.07770.058*
C61.7120 (5)0.5409 (3)0.1976 (2)0.0596 (9)
H6A1.84390.57060.19810.072*
C71.1939 (8)0.2816 (3)−0.1312 (2)0.0726 (12)
H7A1.18340.2270−0.17190.087*
C81.0262 (7)0.3081 (3)−0.0781 (3)0.0695 (11)
H8A0.90340.2702−0.08250.083*
C91.0392 (5)0.3908 (2)−0.0181 (2)0.0527 (8)
H9A0.92610.40900.01740.063*
C101.2238 (5)0.4453 (2)−0.01240 (17)0.0381 (7)
C111.3920 (5)0.4182 (2)−0.06415 (18)0.0500 (8)
H11A1.51650.4546−0.05940.060*
C121.3728 (7)0.3355 (3)−0.1236 (2)0.0626 (9)
H12A1.48580.3170−0.15900.075*
C131.1327 (4)0.6186 (2)0.04201 (16)0.0341 (6)
C141.1818 (4)0.7040 (2)0.10923 (18)0.0410 (6)
H14A1.30580.74120.09050.049*
H14B1.20920.67290.16720.049*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl0.0602 (5)0.0518 (5)0.0743 (6)0.0188 (4)−0.0070 (4)−0.0153 (4)
O0.0505 (12)0.0557 (12)0.0409 (10)0.0128 (10)−0.0121 (10)−0.0018 (9)
N0.0378 (12)0.0378 (12)0.0306 (11)0.0016 (11)−0.0061 (10)−0.0002 (10)
C10.055 (2)0.063 (2)0.0450 (17)0.0191 (17)−0.0191 (17)−0.0039 (16)
C20.066 (2)0.0570 (18)0.0315 (15)0.0058 (16)−0.0011 (15)0.0079 (13)
C30.0404 (16)0.0448 (15)0.0377 (15)−0.0018 (13)0.0028 (13)0.0058 (13)
C40.0360 (14)0.0374 (13)0.0295 (13)0.0037 (11)−0.0034 (12)−0.0008 (11)
C50.0403 (16)0.0593 (18)0.0459 (17)−0.0076 (13)−0.0032 (14)0.0137 (15)
C60.0380 (18)0.078 (2)0.063 (2)−0.0050 (16)−0.0138 (17)−0.0025 (19)
C70.122 (4)0.0484 (19)0.047 (2)0.006 (2)−0.023 (2)−0.0115 (16)
C80.086 (3)0.0488 (19)0.073 (2)−0.020 (2)−0.029 (2)0.0012 (17)
C90.057 (2)0.0487 (17)0.0525 (17)−0.0111 (16)−0.0092 (16)0.0001 (15)
C100.0508 (17)0.0327 (14)0.0307 (14)0.0016 (13)−0.0058 (13)0.0035 (11)
C110.060 (2)0.0472 (17)0.0429 (16)0.0021 (15)0.0058 (16)−0.0007 (14)
C120.086 (3)0.0569 (19)0.0447 (18)0.012 (2)0.000 (2)−0.0085 (16)
C130.0329 (14)0.0406 (14)0.0288 (13)0.0003 (12)0.0009 (12)0.0045 (11)
C140.0385 (14)0.0403 (15)0.0443 (15)0.0026 (12)0.0001 (13)−0.0028 (13)

Geometric parameters (Å, °)

Cl—C141.771 (3)C6—H6A0.9300
O—C131.223 (3)C7—C121.347 (6)
N—C131.357 (3)C7—C81.382 (6)
N—C101.449 (3)C7—H7A0.9300
N—C41.454 (3)C8—C91.390 (5)
C1—C21.372 (5)C8—H8A0.9300
C1—C61.372 (5)C9—C101.380 (4)
C1—H1A0.9300C9—H9A0.9300
C2—C31.386 (4)C10—C111.375 (4)
C2—H2A0.9300C11—C121.386 (4)
C3—C41.374 (4)C11—H11A0.9300
C3—H3A0.9300C12—H12A0.9300
C4—C51.377 (4)C13—C141.518 (4)
C5—C61.374 (4)C14—H14A0.9700
C5—H5A0.9300C14—H14B0.9700
C13—N—C10120.3 (2)C7—C8—C9120.7 (3)
C13—N—C4122.9 (2)C7—C8—H8A119.7
C10—N—C4116.8 (2)C9—C8—H8A119.7
C2—C1—C6120.5 (3)C10—C9—C8118.5 (3)
C2—C1—H1A119.8C10—C9—H9A120.8
C6—C1—H1A119.8C8—C9—H9A120.8
C1—C2—C3119.4 (3)C11—C10—C9121.0 (3)
C1—C2—H2A120.3C11—C10—N118.7 (3)
C3—C2—H2A120.3C9—C10—N120.2 (3)
C4—C3—C2119.8 (3)C10—C11—C12118.9 (3)
C4—C3—H3A120.1C10—C11—H11A120.6
C2—C3—H3A120.1C12—C11—H11A120.6
C3—C4—C5120.6 (3)C7—C12—C11121.4 (4)
C3—C4—N118.8 (2)C7—C12—H12A119.3
C5—C4—N120.7 (2)C11—C12—H12A119.3
C6—C5—C4119.3 (3)O—C13—N122.4 (2)
C6—C5—H5A120.3O—C13—C14122.5 (2)
C4—C5—H5A120.3N—C13—C14115.0 (2)
C1—C6—C5120.4 (3)C13—C14—Cl110.84 (19)
C1—C6—H6A119.8C13—C14—H14A109.5
C5—C6—H6A119.8Cl—C14—H14A109.5
C12—C7—C8119.6 (3)C13—C14—H14B109.5
C12—C7—H7A120.2Cl—C14—H14B109.5
C8—C7—H7A120.2H14A—C14—H14B108.1
C6—C1—C2—C30.2 (5)C8—C9—C10—N−178.0 (3)
C1—C2—C3—C4−1.6 (4)C13—N—C10—C11116.2 (3)
C2—C3—C4—C52.1 (4)C4—N—C10—C11−65.9 (3)
C2—C3—C4—N−178.1 (2)C13—N—C10—C9−66.3 (3)
C13—N—C4—C3100.9 (3)C4—N—C10—C9111.6 (3)
C10—N—C4—C3−77.0 (3)C9—C10—C11—C120.9 (4)
C13—N—C4—C5−79.4 (3)N—C10—C11—C12178.4 (2)
C10—N—C4—C5102.8 (3)C8—C7—C12—C11−0.7 (5)
C3—C4—C5—C6−1.3 (4)C10—C11—C12—C7−0.2 (5)
N—C4—C5—C6179.0 (3)C10—N—C13—O2.1 (4)
C2—C1—C6—C50.7 (5)C4—N—C13—O−175.7 (2)
C4—C5—C6—C1−0.1 (5)C10—N—C13—C14−175.8 (2)
C12—C7—C8—C91.1 (5)C4—N—C13—C146.4 (4)
C7—C8—C9—C10−0.4 (5)O—C13—C14—Cl23.3 (3)
C8—C9—C10—C11−0.6 (4)N—C13—C14—Cl−158.8 (2)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: YA2097).

References

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  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
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  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sarges, R., Howard, H. R., Koe, K. B. & Weissman, A. (1989). J. Med. Chem.2, 437–444. [PubMed]
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Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography