2-Chloro-N-(4-fluoro­phen­yl)acetamide

Kang, S.; Zeng, H.; Li, H.; Wang, H.

doi:10.1107/S1600536808016152

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1194

doi:10.1107/S1600536808016152

Open

access

2-Chloro-N-(4-fluorophenyl)acetamide

Si-shun Kang,^a Hai-su Zeng,^a Hai-lin Li ^a and Hai-bo Wang ^a ^*

^aCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: wanghaibo@njut.edu.cn

(Received 27 May 2008; accepted 28 May 2008; online 7 June 2008)

In the title compound, C₈H₇ClFNO, an intramolecular C—H⋯O hydrogen bond forms a six-membered ring. In the crystal structure, molecules are linked by intermolecular N—H⋯O hydrogen bonds, forming infinite chains along the c axis.

Related literature

For related compounds, see: Wen et al. (2006 ); Zhang et al. (2006 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₇ClFNO
M_r = 187.60
Monoclinic, C c
a = 4.7410 (9) Å
b = 20.062 (4) Å
c = 8.9860 (18) Å
β = 99.60 (3)°
V = 842.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 293 (2) K
0.30 × 0.20 × 0.05 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.885, T_max = 0.980
974 measured reflections
861 independent reflections
610 reflections with I > 2σ(I)
R_int = 0.015
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.126
S = 1.00
861 reflections
103 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ), 92 Friedel pairs
Flack parameter: 0.18 (17)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯O	0.93	2.36	2.925 (8)	119
N—H1⋯Oⁱ	0.86	2.02	2.853 (6)	164
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808016152/hb2738sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808016152/hb2738Isup2.hkl

checkCIF report

Comment top

N-(substituted phenyl)-2-chloroacetamides are important intermediates in organic synthesis. They can be used in the synthesis of many derivatives such as (quinolin-8-yloxy) acetamide (Zhang et al., 2006) and 2,5-piperazinedione (Wen et al., 2006). In our studies in this area, the title compound,(I), was synthesized and structurally characterised.

The bond lengths and angles in (I) are within normal ranges (Allen et al., 1987). An intramolecular C—H···O interaction occurs (Fig. 1) and an intermolecular N—H···O hydrogen bond helps to establish the packing (Table 1).

Related literature top

For related compounds, see: Wen et al. (2006); Zhang et al. (2006). For reference structural data, see: Allen et al. (1987).

Experimental top

Chloroacetyl chloride (0.05 mol) was added to a solution of 4-nitrophenylamine (0.05 mol) and triethylamine (0.05 mol) in toluene (50 ml) over a period of 30 min, with cooling in an ice bath, and then the mixture was stirred at room remperature for 4 h. After separation of the triethylamine hydrochloride by filtration, the organic phase was washed three times with water. The toluene layer was removed and evaporated. Pink blocks of (I) were obtained by slow evaporation of a chloroform solution over a period of 7 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) with displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level. The intramolecular hydrogen bond is shown as a dashed line.

2-Chloro-N-(4-fluorophenyl)acetamide top

Crystal data top

C₈H₇ClFNO	F(000) = 384
M_r = 187.60	D_x = 1.479 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 25 reflections
a = 4.7410 (9) Å	θ = 8–12°
b = 20.062 (4) Å	µ = 0.42 mm⁻¹
c = 8.9860 (18) Å	T = 293 K
β = 99.60 (3)°	Block, pink
V = 842.7 (3) Å³	0.30 × 0.20 × 0.05 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	610 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.016
Graphite monochromator	θ_max = 25.2°, θ_min = 2.0°
ω/2θ scans	h = 0→5
Absorption correction: ψ scan (North et al., 1968)	k = 0→24
T_min = 0.885, T_max = 0.980	l = −10→10
974 measured reflections	3 standard reflections every 200 reflections
861 independent reflections	intensity decay: none

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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.P)² + 0.5P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
861 reflections	Δρ_max = 0.16 e Å⁻³
103 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 92 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.18 (17)

Crystal data top

C₈H₇ClFNO	V = 842.7 (3) Å³
M_r = 187.60	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 4.7410 (9) Å	µ = 0.42 mm⁻¹
b = 20.062 (4) Å	T = 293 K
c = 8.9860 (18) Å	0.30 × 0.20 × 0.05 mm
β = 99.60 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	610 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.016
T_min = 0.885, T_max = 0.980	3 standard reflections every 200 reflections
974 measured reflections	intensity decay: none
861 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.126	Δρ_max = 0.16 e Å⁻³
S = 1.00	Δρ_min = −0.20 e Å⁻³
861 reflections	Absolute structure: Flack (1983), 92 Friedel pairs
103 parameters	Absolute structure parameter: 0.18 (17)
0 restraints

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
Cl	−0.4033 (4)	0.15199 (10)	0.5685 (2)	0.1096 (7)
N	0.1497 (11)	0.2970 (2)	0.6731 (5)	0.0738 (14)
H1	0.2033	0.2848	0.7653	0.089*
O	−0.1268 (10)	0.2652 (2)	0.4535 (5)	0.084
F	0.6949 (14)	0.5279 (2)	0.5602 (6)	0.147 (2)
C1	0.5590 (19)	0.4687 (3)	0.5826 (8)	0.095 (2)
C2	0.3302 (19)	0.4493 (4)	0.4775 (8)	0.097 (2)
H2A	0.2684	0.4749	0.3920	0.116*
C3	0.1935 (15)	0.3901 (3)	0.5030 (6)	0.0817 (18)
H3A	0.0450	0.3743	0.4308	0.098*
C4	0.2759 (13)	0.3546 (3)	0.6344 (6)	0.0707 (15)
C5	0.5091 (15)	0.3787 (3)	0.7356 (7)	0.0798 (17)
H5A	0.5715	0.3539	0.8224	0.096*
C6	0.6503 (19)	0.4357 (4)	0.7157 (8)	0.099 (2)
H6A	0.7995	0.4516	0.7874	0.119*
C7	−0.0366 (13)	0.2576 (3)	0.5950 (5)	0.0710 (16)
C8	−0.1284 (15)	0.1998 (3)	0.6748 (6)	0.089 (2)
H8A	−0.1937	0.2153	0.7654	0.107*
H8B	0.0358	0.1712	0.7058	0.107*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.1293 (15)	0.1275 (15)	0.0742 (9)	−0.0277 (13)	0.0237 (9)	−0.0087 (10)
N	0.089 (3)	0.082 (3)	0.051 (2)	0.010 (3)	0.013 (2)	0.004 (2)
O	0.084	0.084	0.084	0.000	0.014	0.000
F	0.213 (7)	0.120 (3)	0.121 (3)	−0.062 (4)	0.067 (4)	0.001 (3)
C1	0.117 (6)	0.091 (5)	0.086 (5)	−0.031 (5)	0.043 (5)	0.001 (4)
C2	0.121 (6)	0.103 (5)	0.074 (4)	0.000 (5)	0.039 (4)	0.017 (4)
C3	0.090 (4)	0.096 (5)	0.063 (3)	−0.006 (4)	0.025 (3)	0.002 (3)
C4	0.078 (4)	0.080 (4)	0.058 (3)	0.008 (3)	0.020 (3)	0.008 (3)
C5	0.095 (4)	0.083 (4)	0.067 (3)	−0.016 (4)	0.029 (3)	0.000 (3)
C6	0.115 (6)	0.116 (5)	0.074 (4)	−0.007 (5)	0.038 (4)	0.010 (4)
C7	0.072 (3)	0.102 (4)	0.039 (2)	−0.003 (3)	0.009 (2)	−0.011 (3)
C8	0.111 (5)	0.110 (5)	0.044 (3)	−0.017 (4)	0.005 (3)	0.013 (3)

Geometric parameters (Å, º) top

Cl—C8	1.765 (7)	C3—C4	1.379 (8)
N—C7	1.300 (7)	C3—H3A	0.9300
N—C4	1.373 (8)	C4—C5	1.396 (9)
N—H1	0.8600	C5—C6	1.353 (10)
O—C7	1.281 (6)	C5—H5A	0.9300
F—C1	1.381 (7)	C6—H6A	0.9300
C1—C2	1.371 (10)	C7—C8	1.467 (8)
C1—C6	1.372 (10)	C8—H8A	0.9700
C2—C3	1.390 (9)	C8—H8B	0.9700
C2—H2A	0.9300

C7—N—C4	131.3 (5)	C6—C5—C4	124.2 (6)
C7—N—H1	114.3	C6—C5—H5A	117.9
C4—N—H1	114.3	C4—C5—H5A	117.9
C2—C1—C6	124.2 (7)	C5—C6—C1	115.6 (7)
C2—C1—F	118.6 (7)	C5—C6—H6A	122.2
C6—C1—F	117.0 (7)	C1—C6—H6A	122.2
C1—C2—C3	117.7 (6)	O—C7—N	123.2 (6)
C1—C2—H2A	121.1	O—C7—C8	120.1 (5)
C3—C2—H2A	121.1	N—C7—C8	116.5 (4)
C4—C3—C2	120.7 (6)	C7—C8—Cl	114.7 (4)
C4—C3—H3A	119.7	C7—C8—H8A	108.6
C2—C3—H3A	119.7	Cl—C8—H8A	108.6
N—C4—C3	125.4 (6)	C7—C8—H8B	108.6
N—C4—C5	117.3 (5)	Cl—C8—H8B	108.6
C3—C4—C5	117.3 (6)	H8A—C8—H8B	107.6

C6—C1—C2—C3	−4.3 (12)	C3—C4—C5—C6	2.8 (10)
F—C1—C2—C3	−179.1 (7)	C4—C5—C6—C1	−3.0 (11)
C1—C2—C3—C4	3.9 (11)	C2—C1—C6—C5	3.8 (12)
C7—N—C4—C3	11.2 (11)	F—C1—C6—C5	178.7 (7)
C7—N—C4—C5	−168.0 (7)	C4—N—C7—O	4.7 (11)
C2—C3—C4—N	177.7 (6)	C4—N—C7—C8	−179.3 (6)
C2—C3—C4—C5	−3.1 (10)	O—C7—C8—Cl	−9.0 (9)
N—C4—C5—C6	−177.9 (7)	N—C7—C8—Cl	174.8 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O	0.93	2.36	2.925 (8)	119
N—H1···Oⁱ	0.86	2.02	2.853 (6)	164

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₇ClFNO
M_r	187.60
Crystal system, space group	Monoclinic, Cc
Temperature (K)	293
a, b, c (Å)	4.7410 (9), 20.062 (4), 8.9860 (18)
β (°)	99.60 (3)
V (Å³)	842.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.42
Crystal size (mm)	0.30 × 0.20 × 0.05

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.885, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	974, 861, 610
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.126, 1.00
No. of reflections	861
No. of parameters	103
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.20
Absolute structure	Flack (1983), 92 Friedel pairs
Absolute structure parameter	0.18 (17)

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O	0.93	2.36	2.925 (8)	119
N—H1···Oⁱ	0.86	2.02	2.853 (6)	164

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wen, Y. H., Zhang, S. S., Yu, B. H., Li, X. M. & Liu, Q. (2006). Asian J. Chem. 18, 1032–1038. CAS Google Scholar
Zhang, S.-S., Wen, H.-L., Li, X.-M., Xu, L.-L. & Wen, Y.-H. (2006). Acta Cryst. E62, o3412–o3413. Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1194

doi:10.1107/S1600536808016152

Open

access