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

Abstract

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,

• a = 4.7410 (9) Å

• b = 20.062 (4) Å

• c = 8.9860 (18) Å

• β = 99.60 (3)°

• V = 842.7 (3) ų

• 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[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 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)

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.

Supplementary Material

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

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) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The H atoms were positioned geometrically (N—H = 0.86 Å, C—H = 0.93-0.97Å) and refined as riding with U_iso(H) = xU_eq(carrier).

Figures

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.

Crystal data

C8H7ClFNO	F000 = 384
Mr = 187.60	Dx = 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 = 8–12º
b = 20.062 (4) Å	µ = 0.42 mm−1
c = 8.9860 (18) Å	T = 293 (2) K
β = 99.60 (3)º	Block, pink
V = 842.7 (3) Å3	0.30 × 0.20 × 0.05 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.016
Radiation source: fine-focus sealed tube	θmax = 25.2º
Monochromator: graphite	θmin = 2.0º
T = 293(2) K	h = 0→5
ω/2θ scans	k = 0→24
Absorption correction: ψ scan(North et al., 1968)	l = −10→10
Tmin = 0.885, Tmax = 0.980	3 standard reflections
974 measured reflections	every 200 reflections
861 independent reflections	intensity decay: none
610 reflections with I > 2σ(I)

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.046	w = 1/[σ2(Fo2) + (0.P)2 + 0.5P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.126	(Δ/σ)max < 0.001
S = 1.00	Δρmax = 0.16 e Å−3
861 reflections	Δρmin = −0.20 e Å−3
103 parameters	Extinction correction: none
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 92 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.18 (17)

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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 codes: (i) x+1/2, −y+1/2, z+1/2.