3-Fluoro-N-(p-tol­yl)benzamide

Saeed, A.; Khera, R.A.; Gotoh, K.; Ishida, H.

doi:10.1107/S160053680803225X

organic compounds

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Volume 64| Part 11| November 2008| Page o2098

doi:10.1107/S160053680803225X

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3-Fluoro-N-(p-tolyl)benzamide

Aamer Saeed,^a ^* Rasheed Ahmad Khera,^a Kazuma Gotoh ^b and Hiroyuki Ishida ^b

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and ^bDepartment of Chemistry, Faculty of Science, Okayama University, Okayama 700-8530, Japan
^*Correspondence e-mail: aamersaeed@yahoo.com

(Received 17 September 2008; accepted 7 October 2008; online 11 October 2008)

In the crystal structure of the title compound, C₁₄H₁₂FNO, the amide –NHCO– mean plane makes dihedral angles of 28.6 (2) and 37.5 (2)° with the mean planes through the fluorobenzene and methylbenzene units, respectively. The dihedral angle between the two benzene ring mean planes is 65.69 (10)°. In the crystal structure, molecules are linked through N—H⋯O hydrogen bonds and stack along the b axis.

Related literature

For related structures, see: Chopra & Row (2005 ); Saeed et al. (2008 ).

Experimental

Crystal data

C₁₄H₁₂FNO
M_r = 229.25
Monoclinic, C 2/c
a = 27.645 (3) Å
b = 5.2618 (6) Å
c = 15.892 (2) Å
β = 93.519 (3)°
V = 2307.3 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 223 (1) K
0.40 × 0.35 × 0.18 mm

Data collection

Rigaku R-AXIS RAPIDII diffractometer
Absorption correction: numerical (ABSCOR; Higashi, 1999 ) T_min = 0.968, T_max = 0.983
13860 measured reflections
3357 independent reflections
1779 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.073
wR(F²) = 0.240
S = 1.01
3357 reflections
158 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.77 (2)	2.35 (2)	3.087 (3)	161 (2)
Symmetry code: (i) x, y-1, z.

Data collection: PROCESS-AUTO (Rigaku/MSC, 2004 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: CrystalStructure and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680803225X/su2064sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680803225X/su2064Isup2.hkl

checkCIF report

Comment top

The background to this study has been described in our earlier paper on 4-chloro-N-(2-chlorophenyl)-benzamide (Saeed et al., 2008).

In the crystal structure of the title compound the two benzene rings are considerably twisted with respect to one another, with a dihedral angle of 65.69 (10)°. The amide –NHCO– mean plane makes dihedral angles of 28.6 (2) and 37.5 (2)° with the best mean planes through the fluorobenzene and methylbenzene units, respectively. In the crystal the molecules are linked through N—H···O hydrogen bonds and stack up the b axis.

No C—H···F hydrogen bonds were observed here, in contrast to the situation in 4-fluoro-N-(2-fluorophenyl)-benzamide (Chopra & Row, 2005).

Related literature top

For related structures, see: Chopra & Row (2005); Saeed et al. (2008).

Experimental top

4-Fluorobenzoyl chloride (5.4 mmol) in CHCl₃ was treated with 4-methylaniline (21.6 mmol) under a nitrogen atmosphere at reflux for 4 h. Upon cooling the reaction mixture was diluted with CHCl₃ and washed consecutively with aq 1 M HCl and saturated aq NaHCO₃. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Crystallization of the residue in CHCl₃ afforded the title compound (84%) as white needles: Anal. calcd. for C₁₄H₁₂FNO: C 73.35, H 5.28, N 6.11%; found: C 73.30, H 5.32, N 6.09%.

Computing details top

Data collection: PROCESS-AUTO (Rigaku/MSC, 2004); cell refinement: PROCESS-AUTO (Rigaku/MSC, 2004); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004) and PLATON (Spek, 2003).

Figures top

	Fig. 1. A view of the molecular structure of the title compound. The displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. A view along the b axis of the crystal packing of the title compound.

3-Fluoro-N-(p-tolyl)benzamide top

Crystal data top

C₁₄H₁₂FNO	F(000) = 960.00
M_r = 229.25	D_x = 1.320 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -C 2yc	Cell parameters from 7127 reflections
a = 27.645 (3) Å	θ = 3.0–30.0°
b = 5.2618 (6) Å	µ = 0.09 mm⁻¹
c = 15.892 (2) Å	T = 223 K
β = 93.519 (3)°	Block, colorless
V = 2307.3 (5) Å³	0.40 × 0.35 × 0.18 mm
Z = 8

Data collection top

Rigaku R-AXIS RAPIDII diffractometer	1779 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.055
ω scans	θ_max = 30.0°
Absorption correction: numerical (ABSCOR; Higashi, 1999)	h = −38→38
T_min = 0.968, T_max = 0.983	k = −6→7
13860 measured reflections	l = −22→22
3357 independent reflections

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)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.240	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.1335P)²] where P = (F_o² + 2F_c²)/3
3357 reflections	(Δ/σ)_max = 0.001
158 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₄H₁₂FNO	V = 2307.3 (5) Å³
M_r = 229.25	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 27.645 (3) Å	µ = 0.09 mm⁻¹
b = 5.2618 (6) Å	T = 223 K
c = 15.892 (2) Å	0.40 × 0.35 × 0.18 mm
β = 93.519 (3)°

Data collection top

Rigaku R-AXIS RAPIDII diffractometer	3357 independent reflections
Absorption correction: numerical (ABSCOR; Higashi, 1999)	1779 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.983	R_int = 0.055
13860 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.073	0 restraints
wR(F²) = 0.240	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.32 e Å⁻³
3357 reflections	Δρ_min = −0.21 e Å⁻³
158 parameters

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
F1	0.69906 (5)	0.5995 (3)	0.23465 (10)	0.0965 (5)
O1	0.52251 (5)	0.6096 (3)	0.14071 (11)	0.0781 (5)
N1	0.50521 (6)	0.1882 (4)	0.12722 (11)	0.0639 (5)
C1	0.58887 (6)	0.3226 (4)	0.14164 (11)	0.0594 (5)
C2	0.62009 (7)	0.4878 (4)	0.18591 (12)	0.0656 (5)
H2	0.6081	0.6327	0.2122	0.079*
C3	0.66868 (8)	0.4361 (4)	0.19066 (14)	0.0703 (5)
C4	0.68819 (7)	0.2292 (5)	0.15293 (14)	0.0745 (6)
H4	0.7217	0.1984	0.1576	0.089*
C5	0.65712 (7)	0.0677 (4)	0.10794 (14)	0.0732 (6)
H5	0.6697	−0.0741	0.0807	0.088*
C6	0.60772 (7)	0.1105 (4)	0.10214 (12)	0.0657 (5)
H6	0.5869	−0.0026	0.0718	0.079*
C7	0.53603 (7)	0.3860 (4)	0.13667 (11)	0.0608 (5)
C8	0.45358 (7)	0.2026 (4)	0.11934 (11)	0.0599 (5)
C9	0.42706 (7)	0.0146 (4)	0.15561 (13)	0.0675 (5)
H9	0.4431	−0.1164	0.1865	0.081*
C10	0.37703 (7)	0.0181 (4)	0.14673 (13)	0.0729 (6)
H10	0.3594	−0.1125	0.1712	0.087*
C11	0.35222 (7)	0.2093 (4)	0.10264 (11)	0.0675 (5)
C12	0.37940 (7)	0.3956 (4)	0.06655 (13)	0.0705 (6)
H12	0.3634	0.5269	0.0359	0.085*
C13	0.42967 (8)	0.3940 (4)	0.07434 (13)	0.0704 (5)
H13	0.4474	0.5228	0.0491	0.085*
C14	0.29774 (8)	0.2111 (6)	0.09397 (16)	0.0916 (8)
H14A	0.2850	0.2043	0.1495	0.137*
H14B	0.2864	0.0647	0.0613	0.137*
H14C	0.2867	0.3655	0.0655	0.137*
H1	0.5158 (7)	0.055 (4)	0.1353 (12)	0.058 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0752 (8)	0.0995 (10)	0.1131 (11)	−0.0114 (7)	−0.0082 (7)	−0.0173 (8)
O1	0.0711 (9)	0.0616 (9)	0.1023 (12)	0.0027 (7)	0.0107 (7)	−0.0059 (7)
N1	0.0633 (9)	0.0566 (9)	0.0719 (10)	0.0009 (9)	0.0063 (7)	0.0030 (8)
C1	0.0655 (11)	0.0619 (10)	0.0518 (9)	−0.0016 (8)	0.0112 (7)	0.0049 (7)
C2	0.0692 (12)	0.0646 (11)	0.0636 (11)	−0.0002 (10)	0.0087 (8)	−0.0013 (9)
C3	0.0681 (12)	0.0758 (13)	0.0669 (11)	−0.0049 (10)	0.0035 (9)	0.0027 (9)
C4	0.0648 (11)	0.0822 (14)	0.0779 (13)	0.0043 (11)	0.0148 (9)	0.0089 (11)
C5	0.0746 (13)	0.0759 (13)	0.0709 (12)	0.0088 (11)	0.0190 (9)	−0.0006 (10)
C6	0.0705 (11)	0.0665 (11)	0.0610 (10)	0.0004 (9)	0.0127 (8)	−0.0028 (8)
C7	0.0625 (10)	0.0636 (11)	0.0570 (10)	0.0008 (9)	0.0088 (8)	−0.0002 (8)
C8	0.0605 (10)	0.0645 (10)	0.0551 (9)	−0.0013 (8)	0.0076 (7)	−0.0050 (8)
C9	0.0657 (11)	0.0717 (12)	0.0659 (11)	0.0011 (9)	0.0100 (8)	0.0067 (9)
C10	0.0717 (12)	0.0787 (13)	0.0694 (12)	−0.0049 (11)	0.0141 (9)	0.0063 (10)
C11	0.0635 (11)	0.0852 (14)	0.0540 (10)	0.0019 (10)	0.0058 (8)	−0.0085 (9)
C12	0.0712 (12)	0.0729 (13)	0.0663 (12)	0.0063 (10)	−0.0044 (9)	0.0028 (9)
C13	0.0763 (12)	0.0725 (12)	0.0626 (11)	−0.0045 (10)	0.0041 (9)	0.0088 (9)
C14	0.0683 (13)	0.126 (2)	0.0807 (15)	0.0047 (14)	0.0050 (11)	−0.0041 (14)

Geometric parameters (Å, º) top

F1—C3	1.364 (2)	C6—H6	0.9400
O1—C7	1.238 (2)	C8—C9	1.378 (3)
N1—C7	1.347 (3)	C8—C13	1.380 (3)
N1—C8	1.427 (2)	C9—C10	1.382 (3)
N1—H1	0.77 (2)	C9—H9	0.9400
C1—C2	1.386 (3)	C10—C11	1.384 (3)
C1—C6	1.397 (3)	C10—H10	0.9400
C1—C7	1.496 (3)	C11—C12	1.381 (3)
C2—C3	1.368 (3)	C11—C14	1.504 (3)
C2—H2	0.9400	C12—C13	1.388 (3)
C3—C4	1.370 (3)	C12—H12	0.9400
C4—C5	1.377 (3)	C13—H13	0.9400
C4—H4	0.9400	C14—H14A	0.9700
C5—C6	1.382 (3)	C14—H14B	0.9700
C5—H5	0.9400	C14—H14C	0.9700

C7—N1—C8	126.25 (17)	C9—C8—C13	119.37 (18)
C7—N1—H1	117.0 (15)	C9—C8—N1	118.68 (17)
C8—N1—H1	115.6 (15)	C13—C8—N1	121.91 (17)
C2—C1—C6	119.43 (17)	C8—C9—C10	120.14 (19)
C2—C1—C7	117.56 (17)	C8—C9—H9	119.9
C6—C1—C7	122.99 (17)	C10—C9—H9	119.9
C3—C2—C1	118.83 (19)	C9—C10—C11	121.58 (19)
C3—C2—H2	120.6	C9—C10—H10	119.2
C1—C2—H2	120.6	C11—C10—H10	119.2
F1—C3—C2	118.34 (19)	C12—C11—C10	117.44 (17)
F1—C3—C4	118.61 (19)	C12—C11—C14	121.6 (2)
C2—C3—C4	123.05 (19)	C10—C11—C14	120.9 (2)
C3—C4—C5	117.92 (19)	C11—C12—C13	121.75 (18)
C3—C4—H4	121.0	C11—C12—H12	119.1
C5—C4—H4	121.0	C13—C12—H12	119.1
C4—C5—C6	121.1 (2)	C8—C13—C12	119.71 (18)
C4—C5—H5	119.4	C8—C13—H13	120.1
C6—C5—H5	119.4	C12—C13—H13	120.1
C5—C6—C1	119.65 (19)	C11—C14—H14A	109.5
C5—C6—H6	120.2	C11—C14—H14B	109.5
C1—C6—H6	120.2	H14A—C14—H14B	109.5
O1—C7—N1	123.30 (18)	C11—C14—H14C	109.5
O1—C7—C1	120.43 (17)	H14A—C14—H14C	109.5
N1—C7—C1	116.27 (17)	H14B—C14—H14C	109.5

C6—C1—C2—C3	−0.9 (3)	C2—C1—C7—N1	−152.62 (17)
C7—C1—C2—C3	−179.24 (17)	C6—C1—C7—N1	29.1 (3)
C1—C2—C3—F1	−179.77 (18)	C7—N1—C8—C9	−144.0 (2)
C1—C2—C3—C4	0.6 (3)	C7—N1—C8—C13	38.1 (3)
F1—C3—C4—C5	−179.27 (19)	C13—C8—C9—C10	0.1 (3)
C2—C3—C4—C5	0.3 (3)	N1—C8—C9—C10	−177.82 (17)
C3—C4—C5—C6	−1.0 (3)	C8—C9—C10—C11	−0.8 (3)
C4—C5—C6—C1	0.8 (3)	C9—C10—C11—C12	0.9 (3)
C2—C1—C6—C5	0.2 (3)	C9—C10—C11—C14	−179.65 (19)
C7—C1—C6—C5	178.47 (18)	C10—C11—C12—C13	−0.5 (3)
C8—N1—C7—O1	0.9 (3)	C14—C11—C12—C13	−179.9 (2)
C8—N1—C7—C1	−178.66 (15)	C9—C8—C13—C12	0.3 (3)
C2—C1—C7—O1	27.8 (3)	N1—C8—C13—C12	178.19 (17)
C6—C1—C7—O1	−150.5 (2)	C11—C12—C13—C8	−0.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.77 (2)	2.35 (2)	3.087 (3)	161 (2)

Symmetry code: (i) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂FNO
M_r	229.25
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	223
a, b, c (Å)	27.645 (3), 5.2618 (6), 15.892 (2)
β (°)	93.519 (3)
V (Å³)	2307.3 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.40 × 0.35 × 0.18

Data collection
Diffractometer	Rigaku R-AXIS RAPIDII diffractometer
Absorption correction	Numerical (ABSCOR; Higashi, 1999)
T_min, T_max	0.968, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	13860, 3357, 1779
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.073, 0.240, 1.01
No. of reflections	3357
No. of parameters	158
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.21

Computer programs: PROCESS-AUTO (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), CrystalStructure (Rigaku/MSC, 2004) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.77 (2)	2.35 (2)	3.087 (3)	161 (2)

Symmetry code: (i) x, y−1, z.

References

Chopra, D. & Row, T. N. G. (2005). Cryst. Growth Des. 5, 1679–1681. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Higashi, T. (1999). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2004). CrystalStructure and PROCESS-AUTO. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Saeed, A., Khera, R. A., Gotoh, K. & Ishida, H. (2008). Acta Cryst. E64, o1934. 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. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2098

doi:10.1107/S160053680803225X

Open

access