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Acta Crystallogr Sect E Struct Rep Online. 2009 February 1; 65(Pt 2): o380.
Published online 2009 January 23. doi:  10.1107/S1600536809002396
PMCID: PMC2968409

3-Fluoro­benzoic acid–4-acetyl­pyridine (1/1) at 100 K

Abstract

In the title compound, C7H5FO2·C7H7NO, a moderate-strength hydrogen bond is formed between the carboxyl group of one mol­ecule and the pyridine N atom of the other. The benzoic acid mol­ecule is observed to be disordered over two positions with the second orientation only 4% occupied. This disorder is also reflected in the presence of diffuse scattering in the diffraction pattern.

Related literature

For the structure of pure m-fluoro­benzoic acid, see: Taga et al. (1985 [triangle]). For standard bond-length data, see: Allen et al. (1992 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o380-scheme1.jpg

Experimental

Crystal data

  • C7H5FO2·C7H7NO
  • M r = 261.25
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o380-efi1.jpg
  • a = 10.0498 (11) Å
  • b = 10.5779 (8) Å
  • c = 11.5045 (8) Å
  • β = 92.026 (4)°
  • V = 1222.23 (18) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 100 (2) K
  • 0.3 × 0.25 × 0.2 mm

Data collection

  • Rigaku R-AXIS RAPID IP image-plate diffractometer
  • Absorption correction: none
  • 15130 measured reflections
  • 2787 independent reflections
  • 1888 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.099
  • S = 1.05
  • 2787 reflections
  • 220 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: CrystalClear (Rigaku, 2008 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809002396/lh2755sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809002396/lh2755Isup2.hkl

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

Acknowledgments

The authors thank Rigaku for the loan of the diffrac­tom­eter.

supplementary crystallographic information

Comment

The structure of a molecular complex of 3-fluorobenzoic acid with 4-acetylpyridine (C7H5O2F C7H7NO) at 100 K is reported (Fig. 1). The molecular geometry of the 4-acetylpyridine is generally unremarkable. However the F atom in the 3-fluorobenzoic acid molecule is seen to be disordered over two positions in a 96:4% ratio. The majority component is found to lie on the same side of the molecule as the carbonyl C═O and this is consistent with the reported crystal structure of the pure material (Taga et al., 1985). The minority component was identified using a Fourier difference map which shows a peak height of greater than 1 electron bonded to C6, at a distance longer than characteristic for a C—H bond. The inclusion of a disorder model even at the 4% level improves the model significantly. Diffuse scattering was also observed in the diffraction images supporting the presence of disorder in this material. The minor component F atom was modelled isotropically and with constraints on the C—F distance. The thermal ellipsoids of both the carboxylic acid group and the methyl-keto group are slightly larger than those of their corresponding aromatic rings, indicating the possible presence of a small amount of libration in these groups.

A moderate strength hydrogen bond [O···N = 2.6428 (14) Å] is formed between the carboxylic acid group and the pyridine N atom. There is no indication of disorder of the carboxylic H atom at this temperature although the H atom isotropic thermal parameter is large as is often observed in the presence of a hydrogen bond. The two molecules lie almost exactly co-planar with each other.

These dimers are packed in an offset planar arrangement, as shown in Figs. 2 and 3. All the molecules are approximately co-planar with the (103) plane. The reason that this offset occurs may be due to the optimization of two close contacts from the methyl group. These contacts comprise a C—H···O interaction between the methyl group of the 4-acetylpyridine and the C═O of the carboxylic acid between planes, which induces an attractive tilt upwards in the acetylpyridine towards this acid molecule. Equally, the C—H···F interaction within the plane causes an attractive tilt in the adjacent molecule, giving rise to this offset packing arrangement.

Experimental

Crystals of the title material were grown by slow evaporation of solvent from a 1:1 solution of the two component molecules in ethanol.

Refinement

All non-H atoms were refined anisotropically except that of the disordered F atom where the minor component was left isotropic. The C—F distances for the minor and major components were constrained to be similar. All H atoms were identified in the difference map, and were allowed to refine isotropically with the exception of the disordered positions where they were fixed geometrically and refined as riding groups. The proportion of disorder was obtained by identifying the value which gave the lowest R-factor.

Figures

Fig. 1.
The title complex with displacement ellipsoids drawn at the 50% probability level. The minor disordered component is represented by F1a and H2a. The intermolecular hydrogen bond is indicated by a dashed line.
Fig. 2.
Packing figure viewed along the b axis. The tilted layer structure can be clearly seen and close intermolecular C—H···F and C—H···O distances are represented by dotted lines.
Fig. 3.
Packing view to illustrate the offset from planarity of the various units. This figure shows exactly the same molecules as in Fig. 2, but rotated by 90°.

Crystal data

C7H5FO2·C7H7NOF(000) = 544
Mr = 261.25Dx = 1.42 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 10265 reflections
a = 10.0498 (11) Åθ = 3–28°
b = 10.5779 (8) ŵ = 0.11 mm1
c = 11.5045 (8) ÅT = 100 K
β = 92.026 (4)°Block, colourless
V = 1222.23 (18) Å30.3 × 0.25 × 0.2 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP image-plate diffractometerRint = 0.031
ω scansθmax = 27.5°, θmin = 3.3°
15130 measured reflectionsh = −13→13
2787 independent reflectionsk = −13→11
1888 reflections with I > 2σ(I)l = −13→14

Refinement

Refinement on F21 restraint
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.035w = 1/[σ2(Fo2) + (0.0573P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.099(Δ/σ)max = 0.001
S = 1.05Δρmax = 0.23 e Å3
2787 reflectionsΔρmin = −0.21 e Å3
220 parameters

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<1)
F10.86852 (8)0.91451 (8)0.42397 (7)0.0336 (2)0.96
C20.80192 (13)0.81276 (12)0.46507 (11)0.0243 (3)0.96
C2A0.80192 (13)0.81276 (12)0.46507 (11)0.0243 (3)0.04
H2A0.84810.88200.43730.029*0.04
C30.67564 (13)0.83201 (12)0.50485 (11)0.0220 (3)
H30.6362 (14)0.9146 (14)0.5003 (11)0.024 (4)*
C40.60718 (12)0.72721 (12)0.54569 (10)0.0203 (3)
C50.66565 (13)0.60822 (12)0.54596 (10)0.0229 (3)
H50.6176 (15)0.5344 (14)0.5736 (12)0.029 (4)*
C60.79390 (13)0.59376 (13)0.50555 (11)0.0251 (3)0.96
H60.83340.51420.50630.030*0.96
C6A0.79390 (13)0.59376 (13)0.50555 (11)0.0251 (3)0.04
F1A0.8666 (19)0.4867 (15)0.5104 (17)0.033 (4)*0.04
C70.86291 (14)0.69651 (13)0.46440 (11)0.0256 (3)
H70.9528 (16)0.6854 (14)0.4351 (12)0.027 (4)*
C80.46965 (13)0.74749 (11)0.58875 (10)0.0211 (3)
O90.41636 (10)0.64448 (9)0.63191 (8)0.0299 (2)
H90.325 (2)0.6594 (19)0.6527 (17)0.068 (6)*
O100.41357 (9)0.84903 (9)0.58340 (8)0.0287 (2)
N110.16961 (11)0.68081 (10)0.69676 (9)0.0235 (3)
C120.09586 (13)0.58338 (13)0.73125 (11)0.0235 (3)
H120.1365 (15)0.4988 (14)0.7270 (11)0.026 (4)*
C130.11730 (14)0.79700 (13)0.70272 (11)0.0254 (3)
H130.1748 (15)0.8649 (15)0.6758 (12)0.030 (4)*
C14−0.00901 (13)0.81965 (13)0.74237 (11)0.0240 (3)
H14−0.0396 (15)0.9059 (16)0.7441 (13)0.033 (4)*
C15−0.03229 (13)0.59762 (12)0.77072 (10)0.0213 (3)
H15−0.0813 (14)0.5233 (14)0.7917 (12)0.026 (4)*
C16−0.08659 (12)0.71782 (12)0.77594 (10)0.0208 (3)
C17−0.22611 (13)0.74106 (12)0.81607 (10)0.0222 (3)
O18−0.26975 (10)0.84818 (9)0.81733 (9)0.0327 (3)
C19−0.30654 (14)0.63097 (14)0.85455 (13)0.0282 (3)
H19A−0.399 (2)0.6527 (17)0.8522 (15)0.049 (5)*
H19B−0.2946 (17)0.5564 (17)0.8057 (14)0.045 (5)*
H19C−0.2765 (17)0.6106 (17)0.9328 (15)0.050 (5)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
F10.0277 (5)0.0260 (5)0.0480 (5)−0.0030 (3)0.0144 (4)0.0045 (4)
C20.0239 (7)0.0238 (7)0.0255 (7)−0.0041 (5)0.0044 (5)0.0021 (5)
C2A0.0239 (7)0.0238 (7)0.0255 (7)−0.0041 (5)0.0044 (5)0.0021 (5)
C30.0236 (7)0.0210 (7)0.0215 (6)0.0006 (5)0.0014 (5)−0.0009 (5)
C40.0203 (6)0.0220 (7)0.0186 (6)−0.0006 (5)0.0003 (5)−0.0013 (5)
C50.0258 (7)0.0223 (7)0.0207 (6)−0.0009 (5)0.0013 (5)0.0016 (5)
C60.0265 (7)0.0232 (7)0.0257 (6)0.0045 (5)0.0031 (5)−0.0007 (5)
C6A0.0265 (7)0.0232 (7)0.0257 (6)0.0045 (5)0.0031 (5)−0.0007 (5)
C70.0215 (7)0.0299 (7)0.0255 (7)0.0032 (5)0.0047 (5)0.0010 (5)
C80.0203 (6)0.0209 (7)0.0221 (6)−0.0018 (5)0.0008 (5)−0.0012 (5)
O90.0223 (5)0.0251 (5)0.0428 (6)−0.0002 (4)0.0101 (4)0.0039 (4)
O100.0251 (5)0.0224 (5)0.0391 (5)0.0015 (4)0.0081 (4)0.0013 (4)
N110.0207 (5)0.0241 (6)0.0259 (6)−0.0014 (4)0.0029 (4)0.0015 (4)
C120.0235 (7)0.0224 (7)0.0247 (7)0.0011 (5)0.0029 (5)−0.0003 (5)
C130.0254 (7)0.0230 (7)0.0278 (7)−0.0033 (6)0.0015 (5)0.0021 (5)
C140.0256 (7)0.0189 (7)0.0275 (7)0.0002 (5)−0.0006 (5)−0.0003 (5)
C150.0220 (6)0.0189 (7)0.0231 (6)−0.0010 (5)0.0018 (5)0.0009 (5)
C160.0197 (6)0.0227 (7)0.0199 (6)0.0000 (5)−0.0018 (5)−0.0021 (5)
C170.0211 (7)0.0225 (7)0.0228 (6)0.0018 (5)−0.0013 (5)−0.0037 (5)
O180.0270 (5)0.0236 (5)0.0477 (6)0.0054 (4)0.0055 (4)−0.0027 (4)
C190.0205 (7)0.0279 (8)0.0364 (8)0.0003 (6)0.0048 (6)−0.0001 (6)

Geometric parameters (Å, °)

F1—C21.3611 (15)N11—C131.3394 (17)
C2—C71.3740 (19)C12—C151.3888 (18)
C2—C31.3794 (18)C12—H120.985 (15)
C3—C41.3949 (18)C13—C141.3848 (19)
C3—H30.960 (15)C13—H130.979 (16)
C4—C51.3890 (18)C14—C161.3923 (18)
C4—C81.5001 (18)C14—H140.963 (16)
C5—C61.3940 (18)C15—C161.3858 (18)
C5—H50.978 (15)C15—H150.963 (15)
C6—C71.3819 (19)C16—C171.5118 (17)
C6—H60.9300C17—O181.2153 (15)
C7—H70.982 (16)C17—C191.4935 (19)
C8—O101.2135 (15)C19—H19A0.955 (19)
C8—O91.3189 (15)C19—H19B0.978 (17)
O9—H90.97 (2)C19—H19C0.964 (18)
N11—C121.3378 (17)
F1—C2—C7118.74 (11)N11—C12—H12116.7 (9)
F1—C2—C3117.91 (12)C15—C12—H12120.4 (9)
C7—C2—C3123.35 (12)N11—C13—C14122.79 (12)
C2—C3—C4117.71 (12)N11—C13—H13114.8 (9)
C2—C3—H3119.9 (8)C14—C13—H13122.4 (9)
C4—C3—H3122.3 (8)C13—C14—C16119.10 (12)
C5—C4—C3120.48 (12)C13—C14—H14117.9 (9)
C5—C4—C8121.57 (11)C16—C14—H14123.0 (9)
C3—C4—C8117.95 (11)C16—C15—C12119.00 (12)
C4—C5—C6119.65 (12)C16—C15—H15122.1 (9)
C4—C5—H5120.7 (9)C12—C15—H15118.8 (9)
C6—C5—H5119.6 (9)C15—C16—C14118.20 (12)
C7—C6—C5120.60 (13)C15—C16—C17122.23 (11)
C7—C6—H6119.7C14—C16—C17119.57 (12)
C5—C6—H6119.7O18—C17—C19121.61 (12)
C2—C7—C6118.20 (12)O18—C17—C16119.62 (12)
C2—C7—H7121.6 (9)C19—C17—C16118.77 (11)
C6—C7—H7120.2 (9)C17—C19—H19A109.9 (11)
O10—C8—O9123.80 (12)C17—C19—H19B112.3 (10)
O10—C8—C4122.79 (11)H19A—C19—H19B108.4 (14)
O9—C8—C4113.41 (11)C17—C19—H19C107.2 (11)
C8—O9—H9111.0 (12)H19A—C19—H19C110.6 (14)
C12—N11—C13117.97 (11)H19B—C19—H19C108.4 (14)
N11—C12—C15122.91 (12)
F1—C2—C3—C4179.30 (11)C3—C4—C8—O9−176.16 (11)
C7—C2—C3—C4−0.3 (2)C13—N11—C12—C151.11 (19)
C2—C3—C4—C50.14 (18)C12—N11—C13—C14−0.25 (19)
C2—C3—C4—C8−179.83 (11)N11—C13—C14—C16−1.1 (2)
C3—C4—C5—C60.28 (18)N11—C12—C15—C16−0.61 (19)
C8—C4—C5—C6−179.75 (11)C12—C15—C16—C14−0.72 (18)
C4—C5—C6—C7−0.5 (2)C12—C15—C16—C17179.02 (11)
F1—C2—C7—C6−179.53 (11)C13—C14—C16—C151.51 (19)
C3—C2—C7—C60.1 (2)C13—C14—C16—C17−178.24 (11)
C5—C6—C7—C20.3 (2)C15—C16—C17—O18−178.87 (11)
C5—C4—C8—O10−175.77 (11)C14—C16—C17—O180.87 (18)
C3—C4—C8—O104.20 (19)C15—C16—C17—C191.77 (18)
C5—C4—C8—O93.87 (17)C14—C16—C17—C19−178.49 (12)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O9—H9···N110.97 (2)1.68 (2)2.6428 (14)176.3 (18)
C19—H19C···O10i0.96 (2)2.57 (2)3.385 (2)142.5 (14)
C13—H13···F1ii0.98 (2)2.63 (2)3.3870 (16)134.3 (12)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH2755).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1992). International Tables for Crystallography, Vol. C, pp. 685–706. Dordrecht: Kluwer Academic Publishers.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst.39, 453–457.
  • Rigaku (2008). CrystalClear incorporating D*TREK and FSPROCESS Rigaku, The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Taga, T., Yamamoto, N. & Osaki, K. (1985). Acta Cryst. C41, 153–154.

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