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Acta Crystallogr Sect E Struct Rep Online. 2009 January 1; 65(Pt 1): o201.
Published online 2008 December 24. doi:  10.1107/S1600536808043122
PMCID: PMC2968107

2-Fluoro-N-o-tolyl­benzamide

Abstract

In the title compound, C14H12FNO, the ortho-F atom and corresponding H atom on the fluoro­benzene ring are disordered over two positions with occupancies of 0.856 (4) and 0.144 (4). The amide unit is planar with a maximum deviation of 0.0057 (16) Å and the amide plane makes dihedral angles of 38.27 (11)° with the fluoro­benzene ring plane and 37.53 (10)° with the tolyl ring. The two benzene rings are inclined at an angle of 4.17 (15)°. In the crystal structure, chains form along b through N—H(...)O hydrogen bonds augmented by C—H(...)π inter­actions. Additional inter­molecular C—H(...)O and C—H(...)F hydrogen bonds further stabilize the structure, forming layers in the ac plane.

Related literature

For related structures, see: Chopra & Guru Row (2008 [triangle]); Donnelly et al. (2008 [triangle]); Hou et al. (2004 [triangle]); Saeed et al. (2008 [triangle]). For reference structural data, see: Allen et al. (1987 [triangle]).

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Object name is e-65-0o201-scheme1.jpg

Experimental

Crystal data

  • C14H12FNO
  • M r = 229.25
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o201-efi1.jpg
  • a = 10.749 (4) Å
  • b = 4.8245 (17) Å
  • c = 21.580 (7) Å
  • β = 93.820 (19)°
  • V = 1116.6 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 93 (2) K
  • 0.25 × 0.15 × 0.05 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2006 [triangle]) T min = 0.779, T max = 0.995
  • 7896 measured reflections
  • 1228 independent reflections
  • 925 reflections with I > 2σ(I)
  • R int = 0.067
  • θmax = 21.3°

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.108
  • S = 1.06
  • 1228 reflections
  • 169 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker 2006 [triangle]); cell refinement: APEX2 and SAINT (Bruker 2006 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]) and TITAN2000 (Hunter & Simpson, 1999 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 [triangle]), PLATON (Spek, 2003 [triangle]) and publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I. DOI: 10.1107/S1600536808043122/hb2882sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808043122/hb2882Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the University of Otago for purchase of the diffractometer.

supplementary crystallographic information

Comment

As part of our ongoing work on the structure of benzanilides and related compounds (Saeed et al., 2008), we report here the structure of the title 2-fluorobenzamide derivative, (I), Fig 1. The C2—C1—O1—N1—C8 unit is almost planar with a maximum deviation of 0.0057 (16)Å for N1. This plane makes dihedral angles of 38.27 (11) ° with the fluorobenzene ring plane and 37.53 (10)° with the tolyl ring. The two benzene rings are inclined at an angle of 4.17 (15)° giving the molecule a stepped structure. Bond distances in the molecule are not unusual (Allen et al., 1987) and agree well with those reported previously (see for example Chopra & Guru Row, 2008; Donnelly et al., 2008; Hou et al., 2004, Saeed et al., 2008).

In the crystal structure, chains form along b through N—H···O hydrogen bonds augmented by C—H···π interactions involving the methyl group and the tolyl rings (Table 1, Fig. 2). Additional intermolecular C—H···O and C—H···F hydrogen bonds further stabilize the structure forming layers in the ac plane, that stack down the b axis (Fig. 3).

Experimental

2-Fluorobenzoyl chloride (5.4 mmol) in CHCl3 was treated with 2-methylaniline (21.6 mmol) under a nitrogen atmosphere at reflux for 3 h. Upon cooling, the reaction mixture was diluted with CHCl3 and washed consecutively with 1 M aqueous HCl and saturated aq NaHCO3. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. Crystallization of the residue from CHCl3 afforded (I) as colourless needles in an81% yield: Anal. calcd. for C14H12FNO: C 73.35, H 5.28, N 6.11%; found: C 73.30, H 5.32, N 6.09%

Refinement

The H atom bound to N1 was located in a difference electron density map and refined freely with an isotropic displacement parameter. All other H-atoms were refined using a riding model with C—H = 0.95 Å, Uiso= 1.2Ueq (C) for aromatic and 0.98 Å, Uiso = 1.5Ueq (C) for methyl H atoms. The ortho-F atom and corresponding H atom on the fluorobenzene ring are disordered over two positions with occupancies 0.856 (4) and 0.144 (4). Crystals were very small and weakly diffracting, with no significant data obtained beyond θ = 21°

Figures

Fig. 1.
The molecular structure of (I) with displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level. For clarity atoms of the minor disorder component have been omitted.
Fig. 2.
Chains formed along a by N—H···O hydrogen bonds (dashed lines) and C—H···π interactions (dotted lines). Spheres represent the centroids of C8···C13 benzene ...
Fig. 3.
Crystal packing of (I) viewed down the b axis with hydrogen bonds drawn as dashed lines.

Crystal data

C14H12FNOF(000) = 480
Mr = 229.25Dx = 1.364 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1374 reflections
a = 10.749 (4) Åθ = 3.3–21.2°
b = 4.8245 (17) ŵ = 0.10 mm1
c = 21.580 (7) ÅT = 93 K
β = 93.820 (19)°Rectangular plate, colourless
V = 1116.6 (7) Å30.25 × 0.15 × 0.05 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer1228 independent reflections
Radiation source: fine-focus sealed tube925 reflections with I > 2σ(I)
graphiteRint = 0.067
ω scansθmax = 21.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2006)h = −10→10
Tmin = 0.779, Tmax = 0.995k = −4→4
7896 measured reflectionsl = −22→22

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.06w = 1/[σ2(Fo2) + (0.0633P)2] where P = (Fo2 + 2Fc2)/3
1228 reflections(Δ/σ)max < 0.001
169 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = −0.21 e Å3

Special details

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)

xyzUiso*/UeqOcc. (<1)
C10.5852 (2)1.1330 (5)0.13062 (12)0.0203 (7)
O10.57188 (16)1.3797 (3)0.11721 (8)0.0291 (6)
C20.5376 (2)1.0250 (4)0.18985 (11)0.0177 (7)
C70.4271 (2)1.1328 (5)0.20975 (13)0.0229 (7)
H70.38281.26770.18500.027*0.856 (4)
F10.71053 (15)0.7317 (3)0.21278 (8)0.0296 (7)0.856 (4)
C30.5996 (2)0.8335 (5)0.22854 (13)0.0242 (7)
H30.67570.75770.21620.029*0.144 (4)
F1'0.3678 (10)1.321 (2)0.1771 (6)0.046 (4)0.144 (4)
C40.5566 (3)0.7481 (5)0.28378 (13)0.0302 (7)
H40.60220.61790.30930.036*
C50.4450 (3)0.8563 (5)0.30152 (13)0.0284 (7)
H50.41260.79790.33930.034*
C60.3806 (2)1.0486 (5)0.26455 (12)0.0270 (7)
H60.30431.12280.27690.032*
N10.64105 (18)0.9476 (5)0.09499 (10)0.0197 (6)
HN10.639 (2)0.781 (5)0.1077 (12)0.028 (8)*
C80.6910 (2)1.0053 (4)0.03731 (11)0.0173 (7)
C90.8010 (2)0.8696 (4)0.02298 (12)0.0186 (7)
C140.8660 (2)0.6685 (5)0.06812 (12)0.0243 (7)
H14A0.88010.75740.10880.036*
H14B0.94630.61400.05280.036*
H14C0.81380.50370.07200.036*
C100.8481 (2)0.9264 (5)−0.03388 (12)0.0242 (7)
H100.92200.8353−0.04460.029*
C110.7908 (2)1.1116 (5)−0.07566 (12)0.0264 (7)
H110.82571.1480−0.11410.032*
C120.6822 (2)1.2436 (5)−0.06095 (13)0.0235 (7)
H120.64211.3704−0.08940.028*
C130.6326 (2)1.1905 (5)−0.00504 (12)0.0205 (7)
H130.55791.28070.00490.025*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0195 (15)0.0157 (16)0.0256 (18)−0.0019 (12)0.0003 (13)0.0007 (13)
O10.0434 (12)0.0128 (11)0.0326 (12)0.0013 (8)0.0142 (9)0.0032 (8)
C20.0229 (15)0.0104 (13)0.0197 (16)−0.0033 (12)0.0005 (13)−0.0007 (11)
C70.0246 (16)0.0188 (15)0.0253 (18)−0.0012 (13)0.0015 (14)−0.0003 (12)
F10.0306 (11)0.0303 (11)0.0279 (12)0.0111 (9)0.0007 (9)0.0041 (8)
C30.0245 (17)0.0213 (16)0.0268 (19)−0.0004 (12)0.0028 (14)−0.0024 (12)
F1'0.050 (8)0.044 (8)0.046 (9)0.018 (6)0.011 (6)0.015 (6)
C40.0394 (18)0.0271 (16)0.0236 (19)−0.0024 (14)−0.0015 (15)0.0038 (13)
C50.0409 (18)0.0276 (16)0.0170 (17)−0.0117 (14)0.0051 (14)0.0006 (12)
C60.0278 (16)0.0292 (16)0.0246 (18)−0.0018 (13)0.0060 (13)−0.0021 (13)
N10.0258 (13)0.0101 (13)0.0239 (15)0.0023 (11)0.0060 (11)0.0022 (11)
C80.0203 (15)0.0113 (14)0.0206 (17)−0.0051 (11)0.0028 (13)−0.0002 (11)
C90.0212 (15)0.0125 (14)0.0216 (17)−0.0031 (11)−0.0008 (13)−0.0027 (11)
C140.0244 (15)0.0227 (15)0.0259 (18)0.0031 (12)0.0022 (13)−0.0016 (12)
C100.0234 (15)0.0241 (15)0.0255 (18)0.0002 (13)0.0040 (13)−0.0049 (13)
C110.0305 (17)0.0291 (16)0.0199 (17)−0.0047 (13)0.0043 (14)−0.0017 (13)
C120.0295 (16)0.0188 (15)0.0216 (18)−0.0042 (13)−0.0033 (13)0.0034 (12)
C130.0173 (14)0.0163 (14)0.0278 (19)−0.0020 (11)−0.0007 (13)−0.0003 (12)

Geometric parameters (Å, °)

C1—O11.231 (3)N1—C81.416 (3)
C1—N11.347 (3)N1—HN10.85 (3)
C1—C21.501 (3)C8—C131.397 (3)
C2—C31.386 (3)C8—C91.404 (3)
C2—C71.390 (3)C9—C101.385 (4)
C7—F1'1.292 (10)C9—C141.512 (3)
C7—C61.375 (4)C14—H14A0.9800
C7—H70.9500C14—H14B0.9800
F1—C31.354 (3)C14—H14C0.9800
C3—C41.370 (4)C10—C111.384 (3)
C3—H30.9500C10—H100.9500
C4—C51.385 (4)C11—C121.385 (4)
C4—H40.9500C11—H110.9500
C5—C61.379 (4)C12—C131.375 (4)
C5—H50.9500C12—H120.9500
C6—H60.9500C13—H130.9500
O1—C1—N1123.9 (2)C13—C8—N1121.4 (2)
O1—C1—C2119.7 (2)C9—C8—N1118.4 (2)
N1—C1—C2116.5 (2)C13—C8—C14i76.61 (13)
C3—C2—C7116.7 (2)C9—C8—C14i90.97 (14)
C3—C2—C1124.5 (2)N1—C8—C14i103.13 (14)
C7—C2—C1118.6 (2)C10—C9—C8117.7 (2)
F1'—C7—C6118.8 (6)C10—C9—C14121.2 (2)
F1'—C7—C2119.7 (6)C8—C9—C14121.1 (2)
C6—C7—C2121.4 (2)C9—C14—H14A109.5
C6—C7—H7119.3C9—C14—H14B109.5
C2—C7—H7119.3H14A—C14—H14B109.5
F1—C3—C4117.6 (2)C9—C14—H14C109.5
F1—C3—C2119.1 (2)H14A—C14—H14C109.5
C4—C3—C2123.2 (2)H14B—C14—H14C109.5
C4—C3—H3118.4C11—C10—C9122.1 (2)
C2—C3—H3118.4C11—C10—H10118.9
C3—C4—C5118.4 (3)C9—C10—H10118.9
C3—C4—H4120.8C10—C11—C12119.5 (3)
C5—C4—H4120.8C10—C11—H11120.2
C6—C5—C4120.2 (3)C12—C11—H11120.2
C6—C5—H5119.9C13—C12—C11119.8 (2)
C4—C5—H5119.9C13—C12—H12120.1
C5—C6—C7120.0 (3)C11—C12—H12120.1
C5—C6—H6120.0C12—C13—C8120.6 (2)
C7—C6—H6120.0C12—C13—C14i88.08 (15)
C1—N1—C8125.5 (2)C8—C13—C14i81.74 (14)
C1—N1—HN1115.0 (18)C12—C13—H13119.7
C8—N1—HN1119.2 (18)C8—C13—H13119.7
C13—C8—C9120.2 (2)C14i—C13—H13100.3
O1—C1—C2—C3−140.1 (3)C1—N1—C8—C13−37.4 (3)
N1—C1—C2—C339.8 (3)C1—N1—C8—C9143.2 (2)
O1—C1—C2—C736.3 (3)C1—N1—C8—C14i44.8 (3)
N1—C1—C2—C7−143.8 (2)C13—C8—C9—C100.0 (3)
C3—C2—C7—F1'176.9 (6)N1—C8—C9—C10179.4 (2)
C1—C2—C7—F1'0.3 (7)C14i—C8—C9—C10−75.1 (2)
C3—C2—C7—C6−1.4 (3)C13—C8—C9—C14179.9 (2)
C1—C2—C7—C6−178.0 (2)N1—C8—C9—C14−0.6 (3)
C7—C2—C3—F1−176.9 (2)C14i—C8—C9—C14104.9 (2)
C1—C2—C3—F1−0.5 (3)C8—C9—C10—C110.6 (3)
C7—C2—C3—C40.5 (4)C14—C9—C10—C11−179.4 (2)
C1—C2—C3—C4176.9 (2)C9—C10—C11—C12−0.7 (4)
F1—C3—C4—C5178.2 (2)C10—C11—C12—C130.3 (4)
C2—C3—C4—C50.7 (4)C11—C12—C13—C80.3 (3)
C3—C4—C5—C6−1.0 (4)C11—C12—C13—C14i79.5 (2)
C4—C5—C6—C70.2 (4)C9—C8—C13—C12−0.4 (3)
F1'—C7—C6—C5−177.3 (6)N1—C8—C13—C12−179.8 (2)
C2—C7—C6—C51.0 (4)C14i—C8—C13—C1282.8 (2)
O1—C1—N1—C8−0.8 (4)C9—C8—C13—C14i−83.2 (2)
C2—C1—N1—C8179.30 (19)N1—C8—C13—C14i97.4 (2)

Symmetry codes: (i) x, y+1, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—HN1···O1ii0.85 (3)2.08 (3)2.887 (3)158 (2)
C6—H6···F1'iii0.952.603.219 (11)123
C12—H12···O1iv0.952.633.434 (3)143
C12—H12···F1'iv0.952.403.287 (11)154
C14—H14C···Cg1ii0.982.983.702 (3)131

Symmetry codes: (ii) x, y−1, z; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x+1, −y+3, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2882).

References

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  • Hunter, K. A. & Simpson, J. (1999). TITAN2000 University of Otago, New Zealand.
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  • Westrip, S. P. (2009). publCIF In preparation.

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