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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2670.
Published online 2009 October 7. doi:  10.1107/S1600536809038975
PMCID: PMC2971369

1,2,3-Trifluoro­benzene

Abstract

In the title compound, C6H3F3, weak electrostatic and dispersive forces between C(δ+)—F(δ−) and H(δ+)—C(δ−) groups are at the borderline of the hydrogen-bond phenomenon and are poorly directional and further deformed in the presence of π–π stacking inter­actions. The mol­ecule lies on a twofold rotation axis. In the crystal structure, one-dimensional tapes are formed via two anti­dromic C—H(...)F hydrogen bonds. These tapes are, in turn, connected into corrugated two-dimensional sheets by bifurcated C—H(...)F hydrogen bonds. Packing in the third dimension is furnished by π–π stacking inter­actions with a centroid–centroid distance of 3.6362 (14) Å.

Related literature

For C—H(...)F inter­actions, see: Althoff et al. (2006 [triangle]); Bats et al. (2000 [triangle]); Choudhury et al. (2004 [triangle]); D’Oria & Novoa (2008 [triangle]); Dunitz & Taylor (1997 [triangle]); Howard et al. (1996 [triangle]); Müller et al. (2007 [triangle]); O’Hagan (2008 [triangle]); Reichenbacher et al. (2005 [triangle]); Weiss et al. (1997 [triangle]). For related crystal structures of several polyfluorinated benzenes, see: Thalladi et al. (1998 [triangle]). For crystallization techniques, see: Boese & Nussbaumer (1994 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2670-scheme1.jpg

Experimental

Crystal data

  • C6H3F3
  • M r = 132.08
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2670-efi2.jpg
  • a = 7.4238 (19) Å
  • b = 11.590 (3) Å
  • c = 7.0473 (17) Å
  • β = 112.783 (4)°
  • V = 559.1 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.16 mm−1
  • T = 233 K
  • 0.30 × 0.30 × 0.30 mm

Data collection

  • Siemens SMART three-axis goniometer with an APEXII area-detector system diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker; 2004 [triangle]) T min = 0.820, T max = 0.953
  • 1074 measured reflections
  • 634 independent reflections
  • 413 reflections with I > 2σ(I)
  • R int = 0.013

Refinement

  • R[F 2 > 2σ(F 2)] = 0.061
  • wR(F 2) = 0.226
  • S = 1.04
  • 634 reflections
  • 44 parameters
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: Mercury (Macrae et al., 2008 [triangle]) and GIMP2 (The GIMP team, 2008 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809038975/lh2880sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809038975/lh2880Isup2.hkl

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

Acknowledgments

MTK and RB thank the DFG FOR-618. GRD thanks the DST for the award of a J.C. Bose fellowship. TST thanks the UGC for an SRF.

supplementary crystallographic information

Comment

Despite the high electronegativity difference between carbon and fluorine, the C–F bond acts as a poor hydrogen bond acceptor due to the hardness of the F-atom (Dunitz & Taylor, 1997; O'Hagan, 2008). The resultant weak C–H···F–C interactions (Howard et al., 1996; Reichenbacher et al., 2005) arise mainly due to electrostatic and dispersive forces between the C(δ+)–F(δ-) and the H(δ+)–C(δ-) fragments. These interactions, at the borderline of the hydrogen bond phenomenon, are also poorly directional and are deformed by other dominant interactions (Weiss, et al., 1997; D'Oria & Novoa, 2008; Müller et al., 2007). In the absence of other interactions these weak interactions can play a role in the overall crystal packing of the molecule (Bats et al. 2000; Choudhury et al. 2004; Althoff et al. 2006). In activated systems such as polyfluorobenzenes, C–H···F–C interactions may be of significance, and in connection there are some reports of the crystal structures of several polyfluorinated benzene compunds (Thalladi et al., 1998). As a continuation of this work, we report here the crystal structure 1,2,3-trifluorobenzene (1). The comparison crystal structures of 1,2- and 1,4-difluorobenzene and 1,3,5-trifluorobenzene have been reported in this earlier work.

Experimental

The crystals were prepared from commerical samples by zone melting in a quartz capillary at 235 K (1) according to the procedure outlined by (Boese & Nussbaumer, 1994).

Refinement

Treatment of hydrogen atoms: Riding model with the 1.2 fold isotropic displacement parameters of the equivalent Uij of the corresponding carbon atom.

Figures

Fig. 1.
Part of the crystal structure of 1 (a) 2D network of C–H···F–C interactions viewed along the c-axis (b) π–π stacking of molecules viewed along the c-axis.
Fig. 2.
The molecular structure of (1) with displacement ellipsoids drawn at the 50% probability level. The identically labelled atoms are related to each other by the symmetry operator (2-x, y, -z+1/2).

Crystal data

C6H3F3F(000) = 264
Mr = 132.08Dx = 1.569 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 376 reflections
a = 7.4238 (19) Åθ = 3.8–22.7°
b = 11.590 (3) ŵ = 0.16 mm1
c = 7.0473 (17) ÅT = 233 K
β = 112.783 (4)°Cylindric, colourless
V = 559.1 (2) Å30.30 × 0.30 × 0.30 mm
Z = 4

Data collection

Siemens SMART three-axis goniometer with an APEXII area-detector system diffractometer634 independent reflections
Radiation source: fine-focus sealed tube413 reflections with I > 2σ(I)
graphiteRint = 0.013
Detector resolution: 512 pixels mm-1θmax = 28.2°, θmin = 3.5°
in ω at 0.3° scan width one run with 740 frames, phi = 0°, chi = 0°h = −9→9
Absorption correction: multi-scan (SADABS; Bruker; 2004)k = −14→10
Tmin = 0.820, Tmax = 0.953l = −9→4
1074 measured reflections

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)] = 0.061Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.226H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.1501P)2 + 0.039P], where P = (Fo2 + 2Fc2)/3
634 reflections(Δ/σ)max = 0.017
44 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = −0.18 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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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*/Ueq
F11.00000.30558 (17)0.25000.1156 (10)
F20.6666 (2)0.4183 (2)0.1576 (3)0.1354 (10)
C11.00000.4213 (3)0.25000.0769 (9)
C20.8308 (3)0.4803 (2)0.2036 (3)0.0824 (8)
C30.8265 (4)0.5973 (3)0.2023 (3)0.0942 (9)
H30.68330.63880.15850.113*
C41.00000.6558 (3)0.25000.1006 (13)
H41.00000.74220.25000.121*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
F10.161 (2)0.0623 (13)0.1249 (16)0.0000.0563 (14)0.000
F20.0959 (12)0.157 (2)0.1484 (16)−0.0341 (10)0.0415 (10)0.0067 (12)
C10.1030 (19)0.0573 (16)0.0725 (15)0.0000.0364 (13)0.000
C20.0830 (14)0.0890 (17)0.0770 (13)−0.0101 (9)0.0327 (10)0.0013 (9)
C30.1073 (17)0.0935 (18)0.0858 (15)0.0277 (12)0.0419 (12)0.0094 (10)
C40.163 (4)0.0605 (17)0.0848 (19)0.0000.056 (2)0.000

Geometric parameters (Å, °)

F1—C11.341 (4)C3—C41.377 (3)
F2—C21.342 (3)C3—H31.0973
C1—C21.354 (3)C4—H41.0018
C2—C31.357 (4)
F1—C1—C2120.30 (15)C2—C3—H3117.3
C2i—C1—C2119.4 (3)C4—C3—H3124.4
F2—C2—C3121.1 (2)C3—C4—C3i121.0 (3)
F2—C2—C1117.3 (3)C3—C4—H4119.5
C3—C2—C1121.5 (2)C3i—C4—H4119.5
C2—C3—C4118.3 (2)

Symmetry codes: (i) −x+2, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C3—H3···F2ii1.102.773.560 (3)129
C3—H3···F1iii1.102.593.528 (4)144
C4—H4···F2iv1.002.603.440 (4)142

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH2880).

References

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