2-Chloro-4-fluoro-N-phenyl­benzamide

Tan, Z.; Bing, Y.; Fang, S.; Kai, Z.; Yan, Y.

doi:10.1107/S1600536809024787

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1757

doi:10.1107/S1600536809024787

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2-Chloro-4-fluoro-N-phenylbenzamide

Zhengde Tan,^a ^* Yi Bing,^a Shen Fang,^a Zhao Kai ^b and Yang Yan ^a

^aCollege of Chemistry and Chemical Engineering, Hunan Institute of Engineering, Xiangtan 411104, People's Republic of China, and ^bGuangxi Institute of Standards and Technology, Nanning 530022, People's Republic of China
^*Correspondence e-mail: tzd0517@163.com

(Received 7 June 2009; accepted 27 June 2009; online 4 July 2009)

In the title compound, C₁₃H₉ClFNO, the dihedral angle between the two aromatic rings is 13.6 (2)°. In the crystal, the molecules are linked by intermolecular N—H⋯O hydrogen bonds into chains extending along the c-axis direction.

Related literature

For the chemical and pharmacological properties of amides, see: Arrizabalaga et al. (1984 ); Šladowska et al. (1999 ).

Experimental

Crystal data

C₁₃H₉ClFNO
M_r = 249.66
Monoclinic, C c
a = 22.262 (3) Å
b = 5.6452 (6) Å
c = 9.6743 (12) Å
β = 105.832 (2)°
V = 1169.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 298 K
0.45 × 0.40 × 0.27 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.869, T_max = 0.919
2887 measured reflections
1671 independent reflections
1470 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.079
S = 1.04
1671 reflections
154 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.12 e Å⁻³
Absolute structure: Flack, (1983 ), 637 Friedel pairs
Flack parameter: 0.04 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.04	2.857 (3)	159
Symmetry code: (i) $[x, -y+1, z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809024787/si2182sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024787/si2182Isup2.hkl

checkCIF report

Comment top

The chemical and pharmacological properties of acid amides have been investigated extensively, owing to their chelating ability with metal ions and to their potentially beneficial chemical and biological activties (Arrizabalaga et al., 1984; Šladowska et al., 1999). As part of our studies on the synthesis and characterization of related compounds, we report here the synthesis and crystal structure of 2-chloro-4-fluoro-N-phenylbenzamide. The C=O bond length is 1.224 (3) Å, indicating that the molecule is in the keto form (Fig. 1). In the crystal structure, the molecules are linked by intermolecular N—H···O hydrogen bonds into chains, which extend along the c direction (Table 1 and Fig. 2)

Related literature top

For the chemical and pharmacological properties of acid amides, see: Arrizabalaga et al. (1984); Šladowska et al. (1999).

Experimental top

A solution of 2-chloro-4-fluorobenzoyl chloride (10 mmol) in 50 ml toluene was added to a solution of aniline (10 mmol) in 10 ml toluene. The reaction mixture was refluxed for 1 h with stirring then the resulting white precipitate was obtained by filtration, washed several times with ethanol and dried in vacuo (yield 90%). Elemental analysis calculated: C, 62.54; H, 3.63; N, 5.61; found: C, 62.51; H, 3.62; N, 5.59. Crystals were obtained by slow evaporation of a solution in methanol after one week.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Crystal packing of the title compound, showing the hydrogen bonds as dashed lines.

2-Chloro-4-fluoro-N-phenylbenzamide top

Crystal data top

C₁₃H₉ClFNO	F(000) = 512
M_r = 249.66	D_x = 1.418 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 22.262 (3) Å	Cell parameters from 1638 reflections
b = 5.6452 (6) Å	θ = 2.9–27.0°
c = 9.6743 (12) Å	µ = 0.32 mm⁻¹
β = 105.832 (2)°	T = 298 K
V = 1169.7 (2) Å³	Block, colorless
Z = 4	0.45 × 0.40 × 0.27 mm

Data collection top

Bruker SMART CCD diffractometer	1671 independent reflections
Radiation source: fine-focus sealed tube	1470 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→26
T_min = 0.869, T_max = 0.919	k = −6→5
2887 measured reflections	l = −11→11

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)] = 0.032	H-atom parameters constrained
wR(F²) = 0.079	w = 1/[σ²(F_o²) + (0.0432P)² + 0.1416P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1671 reflections	Δρ_max = 0.21 e Å⁻³
154 parameters	Δρ_min = −0.12 e Å⁻³
2 restraints	Absolute structure: Flack, (1983), 637 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (7)

Crystal data top

C₁₃H₉ClFNO	V = 1169.7 (2) Å³
M_r = 249.66	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 22.262 (3) Å	µ = 0.32 mm⁻¹
b = 5.6452 (6) Å	T = 298 K
c = 9.6743 (12) Å	0.45 × 0.40 × 0.27 mm
β = 105.832 (2)°

Data collection top

Bruker SMART CCD diffractometer	1671 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1470 reflections with I > 2σ(I)
T_min = 0.869, T_max = 0.919	R_int = 0.023
2887 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.079	Δρ_max = 0.21 e Å⁻³
S = 1.04	Δρ_min = −0.12 e Å⁻³
1671 reflections	Absolute structure: Flack, (1983), 637 Friedel pairs
154 parameters	Absolute structure parameter: 0.04 (7)
2 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
Cl1	0.25827 (4)	0.57325 (11)	0.03581 (7)	0.0567 (2)
F1	0.19086 (10)	−0.1122 (4)	0.2865 (2)	0.0839 (7)
N1	0.42846 (11)	0.5122 (4)	0.3097 (2)	0.0439 (5)
H1	0.4200	0.4944	0.3907	0.053*
O1	0.39721 (10)	0.4168 (4)	0.0742 (2)	0.0619 (6)
C1	0.38996 (13)	0.4115 (4)	0.1951 (3)	0.0407 (6)
C2	0.33604 (12)	0.2803 (4)	0.2241 (2)	0.0362 (6)
C3	0.27498 (13)	0.3337 (4)	0.1537 (3)	0.0392 (6)
C4	0.22559 (14)	0.2060 (5)	0.1747 (3)	0.0479 (7)
H4	0.1845	0.2458	0.1281	0.057*
C5	0.23956 (15)	0.0173 (6)	0.2675 (3)	0.0538 (8)
C6	0.29854 (16)	−0.0470 (5)	0.3395 (3)	0.0513 (8)
H6	0.3061	−0.1772	0.4008	0.062*
C7	0.34669 (13)	0.0887 (5)	0.3182 (3)	0.0457 (7)
H7	0.3875	0.0510	0.3681	0.055*
C8	0.48249 (13)	0.6470 (5)	0.3095 (3)	0.0428 (7)
C9	0.47880 (18)	0.8278 (6)	0.2111 (4)	0.0632 (8)
H9	0.4415	0.8593	0.1422	0.076*
C10	0.5315 (2)	0.9607 (7)	0.2168 (5)	0.0802 (12)
H10	0.5296	1.0810	0.1501	0.096*
C11	0.5862 (2)	0.9185 (6)	0.3187 (5)	0.0805 (12)
H11	0.6212	1.0107	0.3220	0.097*
C12	0.58956 (18)	0.7403 (7)	0.4161 (5)	0.0810 (10)
H12	0.6269	0.7102	0.4855	0.097*
C13	0.53723 (17)	0.6047 (6)	0.4110 (4)	0.0637 (9)
H13	0.5395	0.4838	0.4775	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0651 (5)	0.0510 (4)	0.0528 (5)	0.0117 (4)	0.0138 (3)	0.0092 (4)
F1	0.0792 (15)	0.0871 (14)	0.0939 (17)	−0.0334 (11)	0.0379 (13)	0.0012 (12)
N1	0.0456 (13)	0.0597 (13)	0.0304 (13)	−0.0075 (11)	0.0170 (10)	−0.0029 (10)
O1	0.0661 (15)	0.0934 (16)	0.0314 (11)	−0.0216 (11)	0.0221 (10)	−0.0078 (10)
C1	0.0450 (15)	0.0521 (15)	0.0278 (15)	0.0011 (13)	0.0145 (12)	0.0014 (12)
C2	0.0434 (15)	0.0422 (14)	0.0235 (13)	−0.0018 (12)	0.0101 (11)	−0.0035 (10)
C3	0.0473 (16)	0.0376 (13)	0.0340 (15)	0.0002 (11)	0.0133 (13)	−0.0045 (11)
C4	0.0416 (16)	0.0548 (16)	0.0473 (17)	−0.0005 (13)	0.0122 (13)	−0.0097 (14)
C5	0.060 (2)	0.0530 (17)	0.056 (2)	−0.0156 (18)	0.0290 (18)	−0.0052 (14)
C6	0.070 (2)	0.0450 (17)	0.0436 (18)	−0.0034 (14)	0.0226 (16)	0.0029 (13)
C7	0.0496 (18)	0.0528 (16)	0.0337 (15)	0.0032 (13)	0.0097 (14)	−0.0016 (13)
C8	0.0431 (18)	0.0492 (15)	0.0410 (16)	−0.0041 (13)	0.0199 (14)	−0.0049 (12)
C9	0.065 (2)	0.0698 (19)	0.057 (2)	−0.0049 (17)	0.0210 (17)	0.0119 (17)
C10	0.088 (3)	0.072 (2)	0.090 (3)	−0.018 (2)	0.042 (3)	0.014 (2)
C11	0.062 (3)	0.084 (3)	0.102 (3)	−0.021 (2)	0.034 (3)	−0.005 (2)
C12	0.048 (2)	0.088 (3)	0.103 (3)	−0.0086 (18)	0.0121 (18)	0.002 (2)
C13	0.056 (2)	0.071 (2)	0.062 (2)	−0.0065 (17)	0.0130 (17)	0.0067 (16)

Geometric parameters (Å, º) top

Cl1—C3	1.743 (3)	C6—H6	0.9300
F1—C5	1.361 (4)	C7—H7	0.9300
N1—C1	1.330 (4)	C8—C13	1.362 (5)
N1—C8	1.424 (3)	C8—C9	1.382 (4)
N1—H1	0.8600	C9—C10	1.381 (5)
O1—C1	1.224 (3)	C9—H9	0.9300
C1—C2	1.500 (4)	C10—C11	1.363 (6)
C2—C3	1.377 (4)	C10—H10	0.9300
C2—C7	1.392 (4)	C11—C12	1.366 (6)
C3—C4	1.375 (4)	C11—H11	0.9300
C4—C5	1.373 (4)	C12—C13	1.383 (5)
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.357 (5)	C13—H13	0.9300
C6—C7	1.378 (4)

C1—N1—C8	125.4 (2)	C6—C7—C2	122.0 (3)
C1—N1—H1	117.3	C6—C7—H7	119.0
C8—N1—H1	117.3	C2—C7—H7	119.0
O1—C1—N1	124.3 (3)	C13—C8—C9	120.0 (3)
O1—C1—C2	120.8 (2)	C13—C8—N1	119.7 (3)
N1—C1—C2	114.9 (2)	C9—C8—N1	120.3 (3)
C3—C2—C7	117.5 (2)	C10—C9—C8	118.9 (3)
C3—C2—C1	122.1 (2)	C10—C9—H9	120.5
C7—C2—C1	120.2 (2)	C8—C9—H9	120.5
C4—C3—C2	122.2 (2)	C11—C10—C9	121.1 (3)
C4—C3—Cl1	117.8 (2)	C11—C10—H10	119.5
C2—C3—Cl1	119.92 (19)	C9—C10—H10	119.5
C5—C4—C3	117.1 (3)	C10—C11—C12	119.8 (3)
C5—C4—H4	121.5	C10—C11—H11	120.1
C3—C4—H4	121.5	C12—C11—H11	120.1
C6—C5—F1	118.8 (3)	C11—C12—C13	119.8 (4)
C6—C5—C4	123.9 (3)	C11—C12—H12	120.1
F1—C5—C4	117.3 (3)	C13—C12—H12	120.1
C5—C6—C7	117.2 (3)	C8—C13—C12	120.5 (3)
C5—C6—H6	121.4	C8—C13—H13	119.7
C7—C6—H6	121.4	C12—C13—H13	119.7

C8—N1—C1—O1	2.1 (4)	C4—C5—C6—C7	0.7 (4)
C8—N1—C1—C2	−179.5 (2)	C5—C6—C7—C2	−1.6 (4)
O1—C1—C2—C3	−58.5 (3)	C3—C2—C7—C6	1.1 (4)
N1—C1—C2—C3	123.1 (3)	C1—C2—C7—C6	−175.2 (2)
O1—C1—C2—C7	117.5 (3)	C1—N1—C8—C13	−133.3 (3)
N1—C1—C2—C7	−60.9 (3)	C1—N1—C8—C9	49.8 (4)
C7—C2—C3—C4	0.5 (4)	C13—C8—C9—C10	0.9 (5)
C1—C2—C3—C4	176.6 (2)	N1—C8—C9—C10	177.8 (3)
C7—C2—C3—Cl1	179.33 (19)	C8—C9—C10—C11	−1.0 (6)
C1—C2—C3—Cl1	−4.5 (3)	C9—C10—C11—C12	0.8 (6)
C2—C3—C4—C5	−1.4 (4)	C10—C11—C12—C13	−0.4 (6)
Cl1—C3—C4—C5	179.8 (2)	C9—C8—C13—C12	−0.5 (5)
C3—C4—C5—C6	0.7 (4)	N1—C8—C13—C12	−177.4 (3)
C3—C4—C5—F1	−178.8 (2)	C11—C12—C13—C8	0.2 (6)
F1—C5—C6—C7	−179.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.04	2.857 (3)	159

Symmetry code: (i) x, −y+1, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₉ClFNO
M_r	249.66
Crystal system, space group	Monoclinic, Cc
Temperature (K)	298
a, b, c (Å)	22.262 (3), 5.6452 (6), 9.6743 (12)
β (°)	105.832 (2)
V (Å³)	1169.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.45 × 0.40 × 0.27

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.869, 0.919
No. of measured, independent and observed [I > 2σ(I)] reflections	2887, 1671, 1470
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.079, 1.04
No. of reflections	1671
No. of parameters	154
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.12
Absolute structure	Flack, (1983), 637 Friedel pairs
Absolute structure parameter	0.04 (7)

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), 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
N1—H1···O1ⁱ	0.86	2.04	2.857 (3)	158.9

Symmetry code: (i) x, −y+1, z+1/2.

Acknowledgements

The authors thank the Science Foundation of Hunan Institute of Engineering, China for support.

References

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Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
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Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Šladowska, H., Sieklucka-Dziuba, M., Rajtar, G., Sodowski, M. & Kleinrok, Z. (1999). Farmaco, 54, 773–779. Web of Science PubMed Google Scholar