Crystal structure of 2-chloro-N-(3-fluoro­phen­yl)acetamide

Abstract

In the title compound, C₈H₇ClFNO, the F atom is disordred over the meta positions of the benzene ring in a 0.574 (4):0.426 (4) ratio and the Cl atom is syn to the O atom [O—C—C—Cl = 5.6 (3)°]. A short intra­molecular C—H⋯O contact occurs. In the crystal, mol­ecules are linked into amide C(4) chains propagating in [101] by N—H⋯O hydrogen bonds.

Related literature  

For compounds in which the meta fluorine substituent of a benzene ring exhibits positional disorder, see: Nayak et al. (2012 ▸); Sanjeevarayappa et al. (2015 ▸).

Experimental  

Crystal data  

• C₈H₇ClFNO

• M _r = 187.60

• Monoclinic,

• a = 5.0441 (2) Å

• b = 18.2374 (7) Å

• c = 8.8653 (3) Å

• β = 99.843 (1)°

• V = 803.53 (5) ų

• Z = 4

• Cu Kα radiation

• μ = 3.95 mm⁻¹

• T = 293 K

• 0.31 × 0.24 × 0.19 mm

Data collection  

• Bruker APEXII diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T _min = 0.368, T _max = 0.472

• 6045 measured reflections

• 1304 independent reflections

• 1297 reflections with I > 2σ(I)

• R _int = 0.041

• 1 standard reflections every 1 reflections intensity decay: 1%

Refinement  

• R[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 0.105

• S = 1.15

• 1304 reflections

• 123 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.26 e Å⁻³

• Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT-Plus (Bruker, 2009 ▸); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL97.

Supplementary Material

CCDC reference: 1049536

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C2H2O1	0.93	2.33	2.885(3)	118
N1H1O1i	0.89(2)	1.99(3)	2.843(2)	160(2)

Symmetry code: (i) .

supplementary crystallographic information

S1. Synthesis and crystallization

The title compound (scheme 1) was synthesized by the reaction of 2-chloro­acetyl chloride with 3-fluoro­aniline at room temperature. The reaction mixture was poured into crushed ice and the resulting solid was washed thoroughly with water, dilute hydro­chloric acid and filtered.

A small portion of the resulting compound was taken in a 10.0 ml beaker and dissolved in a 1:1 ratio of a mixture of EtOH/H₂O to obtain colourless prisms by a slow evaporation method at ~24°C.

S2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms of the NH groups were located in a difference map and later restrained to N—H = 0.86 (4) Å. The other H atoms were positioned with idealized geometry using a riding model with C—H = 0.93–0.96 Å. All H atoms were refined with isotropic displacement parameters (set to 1.2 times of the Ueq of the parent atom).

Figures

Fig. 1.

A view of the molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level.

Fig. 2.

Crystal packing of (I). N—H···O hydrogen bonds are shown as dotted lines.

Crystal data

C8H7ClFNO	Prism
Mr = 187.60	Dx = 1.551 Mg m−3
Monoclinic, P21/n	Melting point: 385 K
Hall symbol: -P 2yn	Cu Kα radiation, λ = 1.54178 Å
a = 5.0441 (2) Å	Cell parameters from 1297 reflections
b = 18.2374 (7) Å	θ = 5.6–64.3°
c = 8.8653 (3) Å	µ = 3.95 mm−1
β = 99.843 (1)°	T = 293 K
V = 803.53 (5) Å3	Prism, colourless
Z = 4	0.31 × 0.24 × 0.19 mm
F(000) = 384

Data collection

Bruker APEXII diffractometer	1297 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.041
Graphite monochromator	θmax = 64.3°, θmin = 5.6°
phi and φ scans	h = −5→5
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −21→21
Tmin = 0.368, Tmax = 0.472	l = −9→10
6045 measured reflections	1 standard reflections every 1 reflections
1304 independent reflections	intensity decay: 1%

Refinement

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ2(Fo2) + (0.0565P)2 + 0.4965P] where P = (Fo2 + 2Fc2)/3
1304 reflections	(Δ/σ)max < 0.001
123 parameters	Δρmax = 0.26 e Å−3
1 restraint	Δρmin = −0.25 e Å−3

Special details

Experimental. Melting point was determined by using open capillary. FT—IR Spectrum was recorded on Jasco FT—IR Spectrometer. 1H-NMR and 13C-NMR spectra were recorded on Jeol-400 MHz NMR instrument using DMSO-d6 as solvent. Chemical shift values were expressed in δ (p.p.m.) relative to tetramethylsilane (TMS) as an internal reference standard. Mass spectrum of the compound was recorded on Shimadzu LC-2010EV with ESI probe. The analysis of various spectra are as follows.IR wavenumbers (cm-1): C=O 1674.9, C—N 1348–1060, N—H 3510–3120, C—N—C 515–409, C—Cl 850–550, C—Cl 650–515. 1H-NMR (399.6 MHz, DMSO-d6) δ: 10.49 (s, 1H, NH), 7.57–7,55 (dd, 1H, Ar—H), 7.34–7.27 (m, 2H, Ar—H), 6.88–6.83 (m, 1H, Ar—H), 2.47 (s, 2H, –CH2-). 13C-NMR (100 MHz, DMSO-d6) δ: 165.41, 163.76, 140.67, 130.89, 115.54, 110.80, 106.77, 43.92. MS: Predicted Mass: 187.07; Obtained Mass 188.07 (M+1).

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
H1	−0.643 (5)	0.2133 (14)	0.515 (3)	0.032 (7)*
Cl1	−0.02090 (10)	0.34713 (3)	0.71994 (6)	0.0279 (2)
O1	−0.3206 (3)	0.22817 (8)	0.83631 (16)	0.0277 (4)
N1	−0.5907 (3)	0.19920 (9)	0.61148 (19)	0.0191 (4)
C1	−0.7435 (4)	0.14033 (11)	0.6567 (2)	0.0193 (4)
C7	−0.3994 (4)	0.23849 (10)	0.7000 (2)	0.0200 (4)
C6	−0.9766 (4)	0.12164 (11)	0.5553 (2)	0.0222 (5)
H6	−1.0266	0.1475	0.4645	0.027*
C2	−0.6672 (4)	0.10139 (11)	0.7913 (2)	0.0220 (5)
H2	−0.5110	0.1133	0.8589	0.026*
C4	−1.0643 (4)	0.02475 (12)	0.7255 (3)	0.0286 (5)
H4	−1.1717	−0.0135	0.7496	0.034*
C8	−0.2919 (4)	0.29966 (12)	0.6089 (2)	0.0271 (5)
H8A	−0.4359	0.3340	0.5733	0.032*
H8B	−0.2326	0.2787	0.5198	0.032*
C5	−1.1321 (4)	0.06407 (12)	0.5923 (3)	0.0271 (5)
H5	−1.2875	0.0516	0.5247	0.033*	0.574 (4)
F1A	−1.3441 (5)	0.04244 (15)	0.5018 (3)	0.0275 (9)	0.426 (4)
C3	−0.8308 (5)	0.04424 (12)	0.8222 (3)	0.0273 (5)
H3	−0.7808	0.0178	0.9122	0.033*	0.426 (4)
F1	−0.7655 (5)	0.00473 (14)	0.9442 (3)	0.0394 (8)	0.574 (4)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0277 (3)	0.0285 (4)	0.0258 (4)	−0.00754 (18)	−0.0003 (2)	−0.00248 (19)
O1	0.0374 (9)	0.0285 (8)	0.0142 (8)	−0.0067 (6)	−0.0040 (6)	0.0009 (6)
N1	0.0232 (9)	0.0215 (8)	0.0118 (9)	−0.0014 (6)	0.0003 (6)	0.0004 (6)
C1	0.0211 (10)	0.0193 (9)	0.0185 (10)	0.0015 (8)	0.0065 (8)	−0.0045 (8)
C7	0.0231 (10)	0.0214 (10)	0.0148 (10)	0.0020 (8)	0.0017 (8)	−0.0019 (8)
C6	0.0231 (10)	0.0247 (11)	0.0187 (10)	0.0012 (8)	0.0036 (8)	−0.0030 (8)
C2	0.0234 (10)	0.0259 (10)	0.0172 (10)	0.0009 (8)	0.0046 (8)	−0.0022 (8)
C4	0.0306 (12)	0.0244 (11)	0.0348 (13)	−0.0028 (9)	0.0166 (10)	−0.0036 (9)
C8	0.0321 (12)	0.0276 (11)	0.0193 (11)	−0.0079 (9)	−0.0020 (9)	0.0015 (9)
C5	0.0229 (11)	0.0278 (11)	0.0319 (12)	−0.0040 (8)	0.0080 (9)	−0.0111 (9)
F1A	0.0209 (15)	0.0318 (17)	0.0282 (17)	−0.0062 (11)	−0.0001 (11)	−0.0039 (12)
C3	0.0348 (12)	0.0252 (11)	0.0252 (11)	0.0023 (9)	0.0143 (9)	0.0017 (9)
F1	0.0487 (16)	0.0436 (15)	0.0266 (13)	−0.0043 (11)	0.0082 (10)	0.0146 (11)

Geometric parameters (Å, º)

Cl1—C8	1.768 (2)	C2—H2	0.9300
O1—C7	1.221 (2)	C4—C5	1.374 (3)
N1—C7	1.342 (3)	C4—C3	1.380 (3)
N1—C1	1.419 (3)	C4—H4	0.9300
N1—H1	0.89 (2)	C8—H8A	0.9700
C1—C2	1.386 (3)	C8—H8B	0.9700
C1—C6	1.394 (3)	C5—F1A	1.284 (4)
C7—C8	1.530 (3)	C5—H5	0.9300
C6—C5	1.383 (3)	C3—F1	1.295 (3)
C6—H6	0.9300	C3—H3	0.9300
C2—C3	1.385 (3)
C7—N1—C1	127.59 (17)	C3—C4—H4	121.3
C7—N1—H1	118.2 (17)	C7—C8—Cl1	111.91 (14)
C1—N1—H1	113.9 (17)	C7—C8—H8A	109.2
C2—C1—C6	120.61 (19)	Cl1—C8—H8A	109.2
C2—C1—N1	123.14 (18)	C7—C8—H8B	109.2
C6—C1—N1	116.23 (18)	Cl1—C8—H8B	109.2
O1—C7—N1	125.18 (19)	H8A—C8—H8B	107.9
O1—C7—C8	123.40 (18)	F1A—C5—C4	115.8 (2)
N1—C7—C8	111.42 (16)	F1A—C5—C6	122.1 (2)
C5—C6—C1	118.9 (2)	C4—C5—C6	122.1 (2)
C5—C6—H6	120.6	C4—C5—H5	118.9
C1—C6—H6	120.6	C6—C5—H5	118.9
C3—C2—C1	117.9 (2)	F1—C3—C4	116.4 (2)
C3—C2—H2	121.0	F1—C3—C2	120.6 (2)
C1—C2—H2	121.0	C4—C3—C2	123.1 (2)
C5—C4—C3	117.4 (2)	C4—C3—H3	118.5
C5—C4—H4	121.3	C2—C3—H3	118.5
C7—N1—C1—C2	−18.4 (3)	N1—C7—C8—Cl1	−175.19 (14)
C7—N1—C1—C6	163.16 (19)	C3—C4—C5—F1A	177.0 (2)
C1—N1—C7—O1	1.9 (3)	C3—C4—C5—C6	−0.8 (3)
C1—N1—C7—C8	−177.30 (18)	C1—C6—C5—F1A	−177.6 (2)
C2—C1—C6—C5	0.7 (3)	C1—C6—C5—C4	0.0 (3)
N1—C1—C6—C5	179.19 (17)	C5—C4—C3—F1	−177.5 (2)
C6—C1—C2—C3	−0.7 (3)	C5—C4—C3—C2	0.8 (3)
N1—C1—C2—C3	−179.04 (18)	C1—C2—C3—F1	178.1 (2)
O1—C7—C8—Cl1	5.6 (3)	C1—C2—C3—C4	−0.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1	0.93	2.33	2.885 (3)	118
N1—H1···O1i	0.89 (2)	1.99 (3)	2.843 (2)	160 (2)

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