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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1305.
Published online 2009 May 14. doi:  10.1107/S1600536809014779
PMCID: PMC2969518

N-Acetyl-N-{2-[(Z)-2-chloro-3,3,3-tri­fluoro­prop-1-en­yl]phen­yl}acetamide

Abstract

The title compound, C13H11ClF3NO2, adopts a Z conformation. Halogen(...)oxygen inter­actions [Cl(...)O = 2.967 (3) Å] in the crystal packing lead to the formation of a dimer joined by two Cl(...)O bonds.

Related literature

The title compound is an important medical inter­mediate, see: Zhou et al. (2009 [triangle]). For the van der Waals radii of chlorine and oxygen, see: Politzer et al. (2007 [triangle]).

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Object name is e-65-o1305-scheme1.jpg

Experimental

Crystal data

  • C13H11ClF3NO2
  • M r = 305.68
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1305-efi1.jpg
  • a = 8.4408 (19) Å
  • b = 9.385 (2) Å
  • c = 9.455 (2) Å
  • α = 64.599 (3)°
  • β = 80.727 (4)°
  • γ = 89.756 (3)°
  • V = 666.0 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.32 mm−1
  • T = 293 K
  • 0.13 × 0.13 × 0.07 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2003 [triangle]) T min = 0.958, T max = 0.978
  • 3747 measured reflections
  • 2562 independent reflections
  • 2155 reflections with I > 2σ(I)
  • R int = 0.010

Refinement

  • R[F 2 > 2σ(F 2)] = 0.052
  • wR(F 2) = 0.136
  • S = 1.03
  • 2562 reflections
  • 177 parameters
  • H-atom parameters constrained
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.38 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT-Plus (Bruker, 1998 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809014779/kj2121sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014779/kj2121Isup2.hkl

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

Acknowledgments

This work was supported by the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences.

supplementary crystallographic information

Comment

The title compoud is an important medical intermediate (Zhou et al., 2009). The conformation of the C=C bond (Z or E) is usually determined by 1H and 19F NMR. Here we report the crystal structure of title compound to establish the conformation.

The title compound, as shown in Fig. 1, a has Z conformation, with the benzene ring and the Cl atom on the same side of C=C bond. In the crystal packing a distance between Cl and O3[-x,-y,1-z) of 2.967 (3) Å is observed, which is obviously shorter than the sum of van der Waals radii of chlorine and oxygen (3.27 Å, Politzer et al., 2007), showing the strong Cl···O interaction indicative of a halogen bond with a nearly linear C12—Cl1···O3[-x,-y,1-z] angle of 173.5 (4)°. Two monomers, related by a centre of symmetry, are linked into a dimer by two Cl···O halogen bonds (Fig. 2). There are no distinct interactions between the dimers in the crystal packing.

Experimental

N-(2-formylphenyl)acetamide (1 mmol) and zinc powder (5 mmol) were added to DMF (5 ml, distilled from CaH2), the flash was then evacuated and backfilled with argon (3 cycles). Acetic anhydride (3 mmol) was added by syringe at room temperature, and then 3 mmol 1,1,1-trichloro-2,2,2-trifluoro-ethane was added to the reaction mixture slowly in 10 minutes. The reaction mixture was stirred at room temperature for 3 h. The mixture was partitioned between ethyl acetate and water. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo. The residual oil was loaded on a silica gel column and eluted with ethyl acetate/petroleum ether (1/9) to afford the product (55%). The purified product was recrystallized from petroleum ether to get colorless block crystals

Refinement

H atoms were placed geometrically and refined with fixed individual displacement parameters [Uiso(H) = 1.2Ueq(C,N)], using a riding model, with C—H distances of 0.93 Å for Csp2 [Uiso(H) = 1.2Ueq(C)] and 0.96 Å for methyl C [Uiso(H) = 1.5Ueq(C)].

Figures

Fig. 1.
The structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
Perspective view of the packing structure of the title compound along the c axis. Dashed lines indicate Cl···O interactions.

Crystal data

C13H11ClF3NO2Z = 2
Mr = 305.68F(000) = 312
Triclinic, P1Dx = 1.524 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.4408 (19) ÅCell parameters from 1359 reflections
b = 9.385 (2) Åθ = 2.3–24.8°
c = 9.455 (2) ŵ = 0.32 mm1
α = 64.599 (3)°T = 293 K
β = 80.727 (4)°Block, colorless
γ = 89.756 (3)°0.13 × 0.13 × 0.07 mm
V = 666.0 (3) Å3

Data collection

Bruker APEX CCD area-detector diffractometer2562 independent reflections
Radiation source: fine-focus sealed tube2155 reflections with I > 2σ(I)
graphiteRint = 0.010
[var phi] and ω scansθmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan (SAINT-Plus; Bruker, 2003)h = −10→7
Tmin = 0.958, Tmax = 0.978k = −11→10
3747 measured reflectionsl = −11→11

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.06P)2 + 0.4882P] where P = (Fo2 + 2Fc2)/3
2562 reflections(Δ/σ)max < 0.001
177 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = −0.38 e Å3

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
Cl10.34597 (9)0.48032 (9)1.17904 (9)0.0624 (3)
F10.1487 (3)0.0570 (2)1.3535 (2)0.0876 (7)
F20.3488 (2)0.1468 (2)1.4086 (2)0.0839 (6)
F30.1179 (3)0.2263 (3)1.4482 (2)0.0849 (6)
N10.2505 (2)0.2173 (2)0.8013 (2)0.0395 (5)
O10.1014 (3)−0.0027 (2)0.8367 (3)0.0615 (5)
O20.5147 (2)0.2397 (3)0.8026 (3)0.0669 (6)
C1−0.0380 (4)0.2291 (4)0.7833 (4)0.0625 (6)
H1A−0.12880.16240.79270.094*
H1B−0.01840.31580.67900.094*
H1C−0.06000.26920.86170.094*
C20.1066 (3)0.1358 (3)0.8087 (3)0.0439 (6)
C30.4252 (4)−0.0064 (4)0.8221 (4)0.0625 (6)
H3A0.5363−0.02800.82370.094*
H3B0.3932−0.01410.73250.094*
H3C0.3602−0.08200.91850.094*
C40.4031 (3)0.1564 (3)0.8091 (3)0.0462 (6)
C50.2485 (3)0.3838 (3)0.7692 (3)0.0387 (5)
C60.2754 (3)0.4964 (3)0.6127 (3)0.0501 (6)
H60.29970.46550.53100.060*
C70.2665 (4)0.6545 (3)0.5773 (3)0.0585 (7)
H70.28500.73010.47200.070*
C80.2300 (4)0.6998 (3)0.6988 (4)0.0564 (7)
H80.21960.80590.67530.068*
C90.2089 (3)0.5884 (3)0.8548 (3)0.0483 (6)
H90.18630.62080.93560.058*
C100.2205 (3)0.4277 (3)0.8945 (3)0.0376 (5)
C110.2003 (3)0.3065 (3)1.0601 (3)0.0401 (5)
H110.14950.20991.08130.048*
C120.2460 (3)0.3182 (3)1.1831 (3)0.0419 (5)
C130.2142 (4)0.1867 (4)1.3472 (3)0.0559 (7)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0723 (5)0.0633 (5)0.0603 (5)−0.0114 (3)−0.0172 (3)−0.0328 (4)
F10.1321 (18)0.0637 (11)0.0503 (10)−0.0312 (11)−0.0168 (11)−0.0086 (9)
F20.0850 (13)0.0953 (15)0.0632 (12)0.0159 (11)−0.0323 (10)−0.0202 (11)
F30.0907 (14)0.1127 (16)0.0463 (10)0.0056 (12)0.0090 (9)−0.0369 (10)
N10.0450 (11)0.0410 (10)0.0386 (11)0.0010 (8)−0.0083 (8)−0.0226 (9)
O10.0679 (12)0.0511 (11)0.0724 (14)−0.0081 (9)−0.0115 (10)−0.0334 (10)
O20.0480 (11)0.0663 (13)0.0952 (17)0.0048 (9)−0.0180 (11)−0.0414 (12)
C10.0555 (12)0.0646 (13)0.0786 (15)0.0087 (10)−0.0172 (10)−0.0398 (12)
C20.0502 (14)0.0494 (14)0.0369 (13)−0.0043 (11)−0.0062 (10)−0.0235 (11)
C30.0555 (12)0.0646 (13)0.0786 (15)0.0087 (10)−0.0172 (10)−0.0398 (12)
C40.0487 (14)0.0510 (14)0.0452 (14)0.0062 (11)−0.0096 (11)−0.0263 (12)
C50.0398 (12)0.0399 (12)0.0389 (12)0.0010 (9)−0.0073 (10)−0.0193 (10)
C60.0584 (16)0.0553 (15)0.0371 (13)0.0008 (12)−0.0074 (11)−0.0208 (12)
C70.0726 (19)0.0469 (15)0.0438 (15)−0.0042 (13)−0.0144 (13)−0.0067 (12)
C80.0687 (18)0.0388 (14)0.0620 (18)0.0044 (12)−0.0221 (14)−0.0184 (13)
C90.0547 (15)0.0457 (14)0.0532 (15)0.0074 (11)−0.0149 (12)−0.0277 (12)
C100.0375 (12)0.0399 (12)0.0391 (12)0.0006 (9)−0.0080 (9)−0.0202 (10)
C110.0433 (12)0.0404 (12)0.0404 (13)−0.0009 (10)−0.0045 (10)−0.0219 (11)
C120.0416 (12)0.0485 (13)0.0402 (13)0.0009 (10)−0.0040 (10)−0.0247 (11)
C130.0649 (17)0.0642 (18)0.0407 (14)−0.0006 (14)−0.0095 (13)−0.0246 (13)

Geometric parameters (Å, °)

Cl1—C121.726 (2)C3—H3C0.9600
F1—C131.312 (3)C5—C61.382 (3)
F2—C131.338 (3)C5—C101.399 (3)
F3—C131.328 (3)C6—C71.378 (4)
N1—C41.407 (3)C6—H60.9300
N1—C21.414 (3)C7—C81.378 (4)
N1—C51.458 (3)C7—H70.9300
O1—C21.209 (3)C8—C91.377 (4)
O2—C41.204 (3)C8—H80.9300
C1—C21.489 (4)C9—C101.396 (3)
C1—H1A0.9600C9—H90.9300
C1—H1B0.9600C10—C111.471 (3)
C1—H1C0.9600C11—C121.329 (3)
C3—C41.493 (4)C11—H110.9300
C3—H3A0.9600C12—C131.493 (4)
C3—H3B0.9600
C4—N1—C2125.8 (2)C5—C6—H6119.9
C4—N1—C5115.01 (19)C8—C7—C6119.7 (3)
C2—N1—C5119.0 (2)C8—C7—H7120.2
C2—C1—H1A109.5C6—C7—H7120.2
C2—C1—H1B109.5C9—C8—C7120.1 (2)
H1A—C1—H1B109.5C9—C8—H8119.9
C2—C1—H1C109.5C7—C8—H8119.9
H1A—C1—H1C109.5C8—C9—C10121.5 (2)
H1B—C1—H1C109.5C8—C9—H9119.3
O1—C2—N1121.5 (2)C10—C9—H9119.3
O1—C2—C1122.1 (2)C9—C10—C5117.2 (2)
N1—C2—C1116.3 (2)C9—C10—C11122.6 (2)
C4—C3—H3A109.5C5—C10—C11120.2 (2)
C4—C3—H3B109.5C12—C11—C10127.9 (2)
H3A—C3—H3B109.5C12—C11—H11116.1
C4—C3—H3C109.5C10—C11—H11116.1
H3A—C3—H3C109.5C11—C12—C13122.5 (2)
H3B—C3—H3C109.5C11—C12—Cl1126.5 (2)
O2—C4—N1118.3 (2)C13—C12—Cl1111.00 (18)
O2—C4—C3121.3 (2)F1—C13—F3107.5 (2)
N1—C4—C3120.4 (2)F1—C13—F2106.4 (3)
C6—C5—C10121.0 (2)F3—C13—F2105.2 (2)
C6—C5—N1118.5 (2)F1—C13—C12113.0 (2)
C10—C5—N1120.5 (2)F3—C13—C12112.0 (2)
C7—C6—C5120.3 (2)F2—C13—C12112.2 (2)
C7—C6—H6119.9

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: KJ2121).

References

  • Bruker (1998). SMART and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2003). SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Politzer, P., Lane, P., Concha, M. C., Ma, Y. & Murray, J. S. (2007). J. Mol. Model.13, 305–311. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhou, H., Niu, J.-J., Xu, J.-W. & Hu, S.-J. (2009). Synth. Commun.39, 716–732.

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