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

Sreenivasa, S.; Suchetan, P.A.; Naveen, S.; Lokanath, N.K.; Srivishnu, K.S.

doi:10.1107/S2056989015007240

organic compounds

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https://doi.org/10.1107/S2056989015007240

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

S. Sreenivasa,^a P. A. Suchetan,^b ^* S. Naveen,^c N. K. Lokanath ^d and K. S. Srivishnu ^e

^aDepartment of Studies and Research in Chemistry, Tumkur University, Tumkur, India, ^bDepartment of Chemistry, University College of Science, Tumkur University, Tumkur 572 013, India, ^cInstitution of Excellence, University of Mysore, Mysuru-6, India, ^dDepartment of Physics, University of Mysore, Mysuru-6, India, and ^eUniversity College of Science, Tumkur, India
^*Correspondence e-mail: pasuchetan@yahoo.co.in

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 7 April 2015; accepted 11 April 2015; online 18 April 2015)

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.

Keywords: crystal structure; disordered F atom; N-arylamides; hydrogen bonding.

CCDC reference: 1049536

1. 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 ).

2. Experimental

2.1. Crystal data

C₈H₇ClFNO
M_r = 187.60
Monoclinic, P 2₁ /n
a = 5.0441 (2) Å
b = 18.2374 (7) Å
c = 8.8653 (3) Å
β = 99.843 (1)°
V = 803.53 (5) Å³
Z = 4
Cu Kα radiation
μ = 3.95 mm⁻¹
T = 293 K
0.31 × 0.24 × 0.19 mm

2.2. 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%

2.3. Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 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

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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.

Supporting information

CCDC reference: 1049536

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015007240/hb7400sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015007240/hb7400Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015007240/hb7400Isup3.cml

checkCIF report

Synthesis and crystallization top

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.

Refinement top

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).

Related literature top

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

Structure description top

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

Synthesis and crystallization top

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.

Refinement details top

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); 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 (Sheldrick, 2008).

Figures top

	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.

2-Chloro-N-(3-fluorophenyl)acetamide top

Crystal data top

C₈H₇ClFNO	Prism
M_r = 187.60	D_x = 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 top

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

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)] = 0.039	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(F_o²) + (0.0565P)² + 0.4965P] where P = (F_o² + 2F_c²)/3
1304 reflections	(Δ/σ)_max < 0.001
123 parameters	Δρ_max = 0.26 e Å⁻³
1 restraint	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₈H₇ClFNO	V = 803.53 (5) Å³
M_r = 187.60	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 5.0441 (2) Å	µ = 3.95 mm⁻¹
b = 18.2374 (7) Å	T = 293 K
c = 8.8653 (3) Å	0.31 × 0.24 × 0.19 mm
β = 99.843 (1)°

Data collection top

Bruker APEXII diffractometer	1297 reflections with I > 2σ(I)
Absorption correction: multi-scan (SADABS; Bruker, 2009)	R_int = 0.041
T_min = 0.368, T_max = 0.472	1 standard reflections every 1 reflections
6045 measured reflections	intensity decay: 1%
1304 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	1 restraint
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	Δρ_max = 0.26 e Å⁻³
1304 reflections	Δρ_min = −0.25 e Å⁻³
123 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	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 (Å²) top

	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) top

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) top

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.

Hydrogen-bond geometry (Å, º) top

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.

Acknowledgements

The authors are thankful to the Institution of Excellence, Vijnana Bhavana, University of Mysore, Mysuru, for providing the single-crystal X-ray diffraction facility.

References

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ISSN: 2056-9890

Volume 71| Part 5| May 2015| Page o315

https://doi.org/10.1107/S2056989015007240

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