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

Niu, J.-J.; Li, Z.-G.; Xu, J.-W.

doi:10.1107/S1600536809014779

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1305

doi:10.1107/S1600536809014779

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

Jia-Jia Niu,^a,^b Zhi-Gang Li ^a,^b and Jing-Wei Xu ^a ^*

^aNational Analytical Research Center of Electrochemistry and Spectroscopy, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of China, and ^bGraduate School of the Chinese Academy of Sciences, Beijing 100039, People's Republic of China
^*Correspondence e-mail: jwxu@ciac.jl.cn

(Received 14 March 2009; accepted 21 April 2009; online 14 May 2009)

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 ). For the van der Waals radii of chlorine and oxygen, see: Politzer et al. (2007 ).

Experimental

Crystal data

C₁₃H₁₁ClF₃NO₂
M_r = 305.68
Triclinic, $[P \overline 1]$
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 ) 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[F² > 2σ(F²)] = 0.052
wR(F²) = 0.136
S = 1.03
2562 reflections
177 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.38 e Å⁻³

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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

Computing details top

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

Figures top

	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.

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

Crystal data top

C₁₃H₁₁ClF₃NO₂	Z = 2
M_r = 305.68	F(000) = 312
Triclinic, P1	D_x = 1.524 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4408 (19) Å	Cell parameters from 1359 reflections
b = 9.385 (2) Å	θ = 2.3–24.8°
c = 9.455 (2) Å	µ = 0.32 mm⁻¹
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 top

Bruker APEX CCD area-detector diffractometer	2562 independent reflections
Radiation source: fine-focus sealed tube	2155 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.010
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.4°
Absorption correction: multi-scan (SAINT-Plus; Bruker, 2003)	h = −10→7
T_min = 0.958, T_max = 0.978	k = −11→10
3747 measured reflections	l = −11→11

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.06P)² + 0.4882P] where P = (F_o² + 2F_c²)/3
2562 reflections	(Δ/σ)_max < 0.001
177 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₁₃H₁₁ClF₃NO₂	γ = 89.756 (3)°
M_r = 305.68	V = 666.0 (3) Å³
Triclinic, P1	Z = 2
a = 8.4408 (19) Å	Mo Kα radiation
b = 9.385 (2) Å	µ = 0.32 mm⁻¹
c = 9.455 (2) Å	T = 293 K
α = 64.599 (3)°	0.13 × 0.13 × 0.07 mm
β = 80.727 (4)°

Data collection top

Bruker APEX CCD area-detector diffractometer	2562 independent reflections
Absorption correction: multi-scan (SAINT-Plus; Bruker, 2003)	2155 reflections with I > 2σ(I)
T_min = 0.958, T_max = 0.978	R_int = 0.010
3747 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.03	Δρ_max = 0.37 e Å⁻³
2562 reflections	Δρ_min = −0.38 e Å⁻³
177 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	0.34597 (9)	0.48032 (9)	1.17904 (9)	0.0624 (3)
F1	0.1487 (3)	0.0570 (2)	1.3535 (2)	0.0876 (7)
F2	0.3488 (2)	0.1468 (2)	1.4086 (2)	0.0839 (6)
F3	0.1179 (3)	0.2263 (3)	1.4482 (2)	0.0849 (6)
N1	0.2505 (2)	0.2173 (2)	0.8013 (2)	0.0395 (5)
O1	0.1014 (3)	−0.0027 (2)	0.8367 (3)	0.0615 (5)
O2	0.5147 (2)	0.2397 (3)	0.8026 (3)	0.0669 (6)
C1	−0.0380 (4)	0.2291 (4)	0.7833 (4)	0.0625 (6)
H1A	−0.1288	0.1624	0.7927	0.094*
H1B	−0.0184	0.3158	0.6790	0.094*
H1C	−0.0600	0.2692	0.8617	0.094*
C2	0.1066 (3)	0.1358 (3)	0.8087 (3)	0.0439 (6)
C3	0.4252 (4)	−0.0064 (4)	0.8221 (4)	0.0625 (6)
H3A	0.5363	−0.0280	0.8237	0.094*
H3B	0.3932	−0.0141	0.7325	0.094*
H3C	0.3602	−0.0820	0.9185	0.094*
C4	0.4031 (3)	0.1564 (3)	0.8091 (3)	0.0462 (6)
C5	0.2485 (3)	0.3838 (3)	0.7692 (3)	0.0387 (5)
C6	0.2754 (3)	0.4964 (3)	0.6127 (3)	0.0501 (6)
H6	0.2997	0.4655	0.5310	0.060*
C7	0.2665 (4)	0.6545 (3)	0.5773 (3)	0.0585 (7)
H7	0.2850	0.7301	0.4720	0.070*
C8	0.2300 (4)	0.6998 (3)	0.6988 (4)	0.0564 (7)
H8	0.2196	0.8059	0.6753	0.068*
C9	0.2089 (3)	0.5884 (3)	0.8548 (3)	0.0483 (6)
H9	0.1863	0.6208	0.9356	0.058*
C10	0.2205 (3)	0.4277 (3)	0.8945 (3)	0.0376 (5)
C11	0.2003 (3)	0.3065 (3)	1.0601 (3)	0.0401 (5)
H11	0.1495	0.2099	1.0813	0.048*
C12	0.2460 (3)	0.3182 (3)	1.1831 (3)	0.0419 (5)
C13	0.2142 (4)	0.1867 (4)	1.3472 (3)	0.0559 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0723 (5)	0.0633 (5)	0.0603 (5)	−0.0114 (3)	−0.0172 (3)	−0.0328 (4)
F1	0.1321 (18)	0.0637 (11)	0.0503 (10)	−0.0312 (11)	−0.0168 (11)	−0.0086 (9)
F2	0.0850 (13)	0.0953 (15)	0.0632 (12)	0.0159 (11)	−0.0323 (10)	−0.0202 (11)
F3	0.0907 (14)	0.1127 (16)	0.0463 (10)	0.0056 (12)	0.0090 (9)	−0.0369 (10)
N1	0.0450 (11)	0.0410 (10)	0.0386 (11)	0.0010 (8)	−0.0083 (8)	−0.0226 (9)
O1	0.0679 (12)	0.0511 (11)	0.0724 (14)	−0.0081 (9)	−0.0115 (10)	−0.0334 (10)
O2	0.0480 (11)	0.0663 (13)	0.0952 (17)	0.0048 (9)	−0.0180 (11)	−0.0414 (12)
C1	0.0555 (12)	0.0646 (13)	0.0786 (15)	0.0087 (10)	−0.0172 (10)	−0.0398 (12)
C2	0.0502 (14)	0.0494 (14)	0.0369 (13)	−0.0043 (11)	−0.0062 (10)	−0.0235 (11)
C3	0.0555 (12)	0.0646 (13)	0.0786 (15)	0.0087 (10)	−0.0172 (10)	−0.0398 (12)
C4	0.0487 (14)	0.0510 (14)	0.0452 (14)	0.0062 (11)	−0.0096 (11)	−0.0263 (12)
C5	0.0398 (12)	0.0399 (12)	0.0389 (12)	0.0010 (9)	−0.0073 (10)	−0.0193 (10)
C6	0.0584 (16)	0.0553 (15)	0.0371 (13)	0.0008 (12)	−0.0074 (11)	−0.0208 (12)
C7	0.0726 (19)	0.0469 (15)	0.0438 (15)	−0.0042 (13)	−0.0144 (13)	−0.0067 (12)
C8	0.0687 (18)	0.0388 (14)	0.0620 (18)	0.0044 (12)	−0.0221 (14)	−0.0184 (13)
C9	0.0547 (15)	0.0457 (14)	0.0532 (15)	0.0074 (11)	−0.0149 (12)	−0.0277 (12)
C10	0.0375 (12)	0.0399 (12)	0.0391 (12)	0.0006 (9)	−0.0080 (9)	−0.0202 (10)
C11	0.0433 (12)	0.0404 (12)	0.0404 (13)	−0.0009 (10)	−0.0045 (10)	−0.0219 (11)
C12	0.0416 (12)	0.0485 (13)	0.0402 (13)	0.0009 (10)	−0.0040 (10)	−0.0247 (11)
C13	0.0649 (17)	0.0642 (18)	0.0407 (14)	−0.0006 (14)	−0.0095 (13)	−0.0246 (13)

Geometric parameters (Å, º) top

Cl1—C12	1.726 (2)	C3—H3C	0.9600
F1—C13	1.312 (3)	C5—C6	1.382 (3)
F2—C13	1.338 (3)	C5—C10	1.399 (3)
F3—C13	1.328 (3)	C6—C7	1.378 (4)
N1—C4	1.407 (3)	C6—H6	0.9300
N1—C2	1.414 (3)	C7—C8	1.378 (4)
N1—C5	1.458 (3)	C7—H7	0.9300
O1—C2	1.209 (3)	C8—C9	1.377 (4)
O2—C4	1.204 (3)	C8—H8	0.9300
C1—C2	1.489 (4)	C9—C10	1.396 (3)
C1—H1A	0.9600	C9—H9	0.9300
C1—H1B	0.9600	C10—C11	1.471 (3)
C1—H1C	0.9600	C11—C12	1.329 (3)
C3—C4	1.493 (4)	C11—H11	0.9300
C3—H3A	0.9600	C12—C13	1.493 (4)
C3—H3B	0.9600

C4—N1—C2	125.8 (2)	C5—C6—H6	119.9
C4—N1—C5	115.01 (19)	C8—C7—C6	119.7 (3)
C2—N1—C5	119.0 (2)	C8—C7—H7	120.2
C2—C1—H1A	109.5	C6—C7—H7	120.2
C2—C1—H1B	109.5	C9—C8—C7	120.1 (2)
H1A—C1—H1B	109.5	C9—C8—H8	119.9
C2—C1—H1C	109.5	C7—C8—H8	119.9
H1A—C1—H1C	109.5	C8—C9—C10	121.5 (2)
H1B—C1—H1C	109.5	C8—C9—H9	119.3
O1—C2—N1	121.5 (2)	C10—C9—H9	119.3
O1—C2—C1	122.1 (2)	C9—C10—C5	117.2 (2)
N1—C2—C1	116.3 (2)	C9—C10—C11	122.6 (2)
C4—C3—H3A	109.5	C5—C10—C11	120.2 (2)
C4—C3—H3B	109.5	C12—C11—C10	127.9 (2)
H3A—C3—H3B	109.5	C12—C11—H11	116.1
C4—C3—H3C	109.5	C10—C11—H11	116.1
H3A—C3—H3C	109.5	C11—C12—C13	122.5 (2)
H3B—C3—H3C	109.5	C11—C12—Cl1	126.5 (2)
O2—C4—N1	118.3 (2)	C13—C12—Cl1	111.00 (18)
O2—C4—C3	121.3 (2)	F1—C13—F3	107.5 (2)
N1—C4—C3	120.4 (2)	F1—C13—F2	106.4 (3)
C6—C5—C10	121.0 (2)	F3—C13—F2	105.2 (2)
C6—C5—N1	118.5 (2)	F1—C13—C12	113.0 (2)
C10—C5—N1	120.5 (2)	F3—C13—C12	112.0 (2)
C7—C6—C5	120.3 (2)	F2—C13—C12	112.2 (2)
C7—C6—H6	119.9

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁ClF₃NO₂
M_r	305.68
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.4408 (19), 9.385 (2), 9.455 (2)
α, β, γ (°)	64.599 (3), 80.727 (4), 89.756 (3)
V (Å³)	666.0 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.13 × 0.13 × 0.07

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SAINT-Plus; Bruker, 2003)
T_min, T_max	0.958, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	3747, 2562, 2155
R_int	0.010
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.136, 1.03
No. of reflections	2562
No. of parameters	177
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.38

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

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

References

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