N-(3-Chloro-4-fluoro­phen­yl)acetamide

Fun, H.-K.; Loh, W.-S.; Shetty, D.N.; Narayana, B.; Sarojini, B.K.

doi:10.1107/S160053681201416X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1348

doi:10.1107/S160053681201416X

Open

access

N-(3-Chloro-4-fluorophenyl)acetamide

Hoong-Kun Fun,^a ^*‡ Wan-Sin Loh,^a § Divya N. Shetty,^b B. Narayana ^b and B. K. Sarojini ^c

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India, and ^cDepartment of Chemistry, P.A. College of Engineering, Nadupadavu, Mangalore 574 153, India
^*Correspondence e-mail: hkfun@usm.my

(Received 26 March 2012; accepted 1 April 2012; online 13 April 2012)

In the title compound, C₈H₇ClFNO, the dihedral angle between the benzene ring and the acetamide side chain is 5.47 (6)°. An S(6) ring motif is formed via an intramolecular C—H⋯O hydrogen bond. In the crystal, N—H⋯O hydrogen bonds link the molecules into C(4) chains along [001].

Related literature

For background to acetamides, see: Khan et al. (2010 ); Tahir & Shad (2011 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For a related structure, see: Rosli et al. (2007 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₈H₇ClFNO
M_r = 187.60
Monoclinic, P 2₁ /c
a = 7.6776 (4) Å
b = 12.7671 (7) Å
c = 9.8130 (4) Å
β = 124.432 (3)°
V = 793.35 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.44 mm⁻¹
T = 100 K
0.33 × 0.29 × 0.15 mm

Data collection

Bruker SMART APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.869, T_max = 0.937
14562 measured reflections
3971 independent reflections
3173 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.143
S = 1.09
3971 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 1.32 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.90	2.00	2.8996 (12)	174
C1—H1A⋯O1	0.95	2.20	2.8222 (14)	122
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681201416X/hb6705sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681201416X/hb6705Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681201416X/hb6705Isup3.cml

checkCIF report

Comment top

To complement earlier studies of acetamides (Khan et al., 2010; Tahir & Shad, 2011), we report herein the crystal structure of the title compound.

In the title compound (Fig. 1), an S(6) ring motif (Bernstein et al., 1995) is formed via intramolecular C1—H1A···O1 hydrogen bond (Table 1). Bond lengths and angles are within the normal ranges and are comparable with the related structure (Rosli et al., 2007).

In the crystal (Fig. 2), N1—H1···O1 hydrogen bonds (Table 1) link the molecules to form chains along the c axis.

Related literature top

For background to acetamides, see: Khan et al. (2010); Tahir & Shad (2011). For hydrogen-bond motifs, see: Bernstein et al. (1995). For a related structure, see: Rosli et al. (2007). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

3-Chloro-4-fluoro aniline (0.145 g, 1 mmol) was dissolved in acetic acid (20 mL) and refluxed for 4 h. The solution was then cooled and poured into 100 ml of ice-cold water with stirring. The precipitate obtained was filtered, washed with water and dried. Orange blocks were grown from DMF solution by the slow evaporation method. M. P.: 384 K.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids. Dashed line indicates the intramolecular hydrogen bond.
	Fig. 2. The crystal packing of the title compound, viewed along the a axis, showing the chains along the c axis. H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity.

N-(3-Chloro-4-fluorophenyl)acetamide top

Crystal data top

C₈H₇ClFNO	F(000) = 384
M_r = 187.60	D_x = 1.571 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5541 reflections
a = 7.6776 (4) Å	θ = 3.0–36.8°
b = 12.7671 (7) Å	µ = 0.44 mm⁻¹
c = 9.8130 (4) Å	T = 100 K
β = 124.432 (3)°	Block, orange
V = 793.35 (7) Å³	0.33 × 0.29 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEXII DUO CCD diffractometer	3971 independent reflections
Radiation source: fine-focus sealed tube	3173 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ϕ and ω scans	θ_max = 36.9°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −12→12
T_min = 0.869, T_max = 0.937	k = −21→17
14562 measured reflections	l = −14→16

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0844P)² + 0.1402P] where P = (F_o² + 2F_c²)/3
3971 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 1.32 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

C₈H₇ClFNO	V = 793.35 (7) Å³
M_r = 187.60	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.6776 (4) Å	µ = 0.44 mm⁻¹
b = 12.7671 (7) Å	T = 100 K
c = 9.8130 (4) Å	0.33 × 0.29 × 0.15 mm
β = 124.432 (3)°

Data collection top

Bruker SMART APEXII DUO CCD diffractometer	3971 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3173 reflections with I > 2σ(I)
T_min = 0.869, T_max = 0.937	R_int = 0.035
14562 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.09	Δρ_max = 1.32 e Å⁻³
3971 reflections	Δρ_min = −0.50 e Å⁻³
110 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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	0.32215 (5)	−0.12199 (2)	0.38846 (3)	0.02251 (9)
F1	0.31780 (12)	−0.24025 (5)	0.13350 (9)	0.02207 (16)
O1	0.18905 (15)	0.24972 (7)	0.21236 (10)	0.02070 (17)
N1	0.20506 (15)	0.18521 (7)	0.00234 (11)	0.01588 (16)
H1	0.1979	0.2007	−0.0902	0.019*
C1	0.27231 (17)	0.03769 (8)	0.18824 (12)	0.01625 (18)
H1A	0.2766	0.0831	0.2668	0.019*
C2	0.29704 (17)	−0.06971 (8)	0.21576 (13)	0.01634 (18)
C3	0.29615 (17)	−0.13592 (8)	0.10379 (13)	0.01655 (18)
C4	0.27098 (18)	−0.09670 (9)	−0.03746 (13)	0.01834 (19)
H4A	0.2733	−0.1423	−0.1129	0.022*
C5	0.24229 (17)	0.01024 (9)	−0.06795 (13)	0.01731 (19)
H5A	0.2233	0.0377	−0.1655	0.021*
C6	0.24111 (16)	0.07801 (8)	0.04398 (12)	0.01421 (17)
C7	0.17661 (17)	0.26277 (8)	0.08257 (13)	0.01566 (18)
C8	0.1266 (2)	0.36891 (9)	0.00122 (14)	0.0196 (2)
H8A	0.2467	0.4160	0.0687	0.029*
H8B	0.0013	0.3977	−0.0091	0.029*
H8C	0.0992	0.3619	−0.1088	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.03690 (18)	0.01515 (13)	0.02113 (14)	0.00050 (9)	0.01980 (13)	0.00337 (8)
F1	0.0318 (4)	0.0111 (3)	0.0247 (3)	0.0014 (2)	0.0167 (3)	0.0004 (2)
O1	0.0340 (4)	0.0164 (4)	0.0183 (3)	0.0011 (3)	0.0188 (3)	−0.0001 (3)
N1	0.0246 (4)	0.0120 (3)	0.0155 (3)	−0.0003 (3)	0.0140 (3)	0.0001 (3)
C1	0.0230 (5)	0.0126 (4)	0.0160 (4)	−0.0006 (3)	0.0128 (4)	−0.0006 (3)
C2	0.0214 (4)	0.0136 (4)	0.0162 (4)	−0.0009 (3)	0.0120 (3)	0.0003 (3)
C3	0.0204 (4)	0.0116 (4)	0.0183 (4)	0.0000 (3)	0.0114 (4)	−0.0005 (3)
C4	0.0243 (5)	0.0152 (4)	0.0180 (4)	0.0002 (3)	0.0134 (4)	−0.0029 (3)
C5	0.0238 (5)	0.0153 (4)	0.0165 (4)	−0.0002 (3)	0.0136 (4)	−0.0011 (3)
C6	0.0183 (4)	0.0122 (4)	0.0148 (4)	−0.0007 (3)	0.0109 (3)	−0.0003 (3)
C7	0.0201 (4)	0.0134 (4)	0.0159 (4)	−0.0007 (3)	0.0116 (3)	−0.0003 (3)
C8	0.0281 (5)	0.0136 (4)	0.0211 (5)	0.0011 (3)	0.0163 (4)	0.0019 (3)

Geometric parameters (Å, º) top

Cl1—C2	1.7278 (11)	C3—C4	1.3807 (15)
F1—C3	1.3535 (12)	C4—C5	1.3884 (15)
O1—C7	1.2335 (13)	C4—H4A	0.9500
N1—C7	1.3573 (14)	C5—C6	1.4023 (14)
N1—C6	1.4102 (14)	C5—H5A	0.9500
N1—H1	0.9003	C7—C8	1.5081 (15)
C1—C2	1.3896 (15)	C8—H8A	0.9800
C1—C6	1.3938 (14)	C8—H8B	0.9800
C1—H1A	0.9500	C8—H8C	0.9800
C2—C3	1.3832 (15)

C7—N1—C6	127.56 (9)	C4—C5—C6	120.56 (10)
C7—N1—H1	119.1	C4—C5—H5A	119.7
C6—N1—H1	113.3	C6—C5—H5A	119.7
C2—C1—C6	119.21 (9)	C1—C6—C5	119.61 (10)
C2—C1—H1A	120.4	C1—C6—N1	123.06 (9)
C6—C1—H1A	120.4	C5—C6—N1	117.32 (9)
C3—C2—C1	120.66 (10)	O1—C7—N1	123.81 (10)
C3—C2—Cl1	119.39 (8)	O1—C7—C8	121.05 (10)
C1—C2—Cl1	119.93 (8)	N1—C7—C8	115.14 (9)
F1—C3—C4	120.24 (9)	C7—C8—H8A	109.5
F1—C3—C2	119.04 (10)	C7—C8—H8B	109.5
C4—C3—C2	120.71 (10)	H8A—C8—H8B	109.5
C3—C4—C5	119.22 (10)	C7—C8—H8C	109.5
C3—C4—H4A	120.4	H8A—C8—H8C	109.5
C5—C4—H4A	120.4	H8B—C8—H8C	109.5

C6—C1—C2—C3	1.61 (16)	C2—C1—C6—C5	−2.14 (16)
C6—C1—C2—Cl1	−176.64 (8)	C2—C1—C6—N1	177.04 (10)
C1—C2—C3—F1	−179.12 (10)	C4—C5—C6—C1	1.00 (16)
Cl1—C2—C3—F1	−0.85 (14)	C4—C5—C6—N1	−178.22 (10)
C1—C2—C3—C4	0.09 (16)	C7—N1—C6—C1	−6.20 (17)
Cl1—C2—C3—C4	178.35 (9)	C7—N1—C6—C5	172.99 (10)
F1—C3—C4—C5	177.95 (10)	C6—N1—C7—O1	3.71 (18)
C2—C3—C4—C5	−1.24 (17)	C6—N1—C7—C8	−176.05 (10)
C3—C4—C5—C6	0.69 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.90	2.00	2.8996 (12)	174
C1—H1A···O1	0.95	2.20	2.8222 (14)	122

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₈H₇ClFNO
M_r	187.60
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.6776 (4), 12.7671 (7), 9.8130 (4)
β (°)	124.432 (3)
V (Å³)	793.35 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.44
Crystal size (mm)	0.33 × 0.29 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII DUO CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.869, 0.937
No. of measured, independent and observed [I > 2σ(I)] reflections	14562, 3971, 3173
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.845

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.143, 1.09
No. of reflections	3971
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.32, −0.50

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.90	2.00	2.8996 (12)	174
C1—H1A···O1	0.95	2.20	2.8222 (14)	122

Symmetry code: (i) x, −y+1/2, z−1/2.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: C-7581-2009.

Acknowledgements

HKF and WSL thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). WSL also thanks the Malaysian Government and USM for the award of the post of Research Officer under the Research University Grant (1001/PFIZIK/811160). BN thanks the UGC SAP for financial assistance for the purchase of chemicals. DNS thanks Mangalore University for research facilities.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Khan, F. N., Roopan, S. M., Malathi, N., Hathwar, V. R. & Akkurt, M. (2010). Acta Cryst. E66, o2043–o2044. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rosli, M. M., Karthikeyan, M. S., Fun, H.-K., Razak, I. A. & Patil, P. S. (2007). Acta Cryst. E63, o67–o68. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tahir, M. N. & Shad, H. A. (2011). Acta Cryst. E67, o443. Web of Science CSD CrossRef IUCr Journals Google Scholar