1,2,3-Trifluoro­benzene

Kirchner, M.T.; Bläser, D.; Boese, R.; Thakur, T.S.; Desiraju, G.R.

doi:10.1107/S1600536809038975

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2670

https://doi.org/10.1107/S1600536809038975

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1,2,3-Trifluorobenzene

Michael T. Kirchner,^a Dieter Bläser,^a Roland Boese,^a ^* Tejender S. Thakur ^b and Gautam R. Desiraju ^b ^*

^aInstitut für Anorganische Chemie der Universität, 45117 Essen, Germany, and ^bIndian Institute of Science, Bangalore 560 012, India
^*Correspondence e-mail: roland.boese@uni-due.de, gautam_desiraju@yahoo.com

(Received 12 August 2009; accepted 25 September 2009; online 7 October 2009)

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 ); Bats et al. (2000 ); Choudhury et al. (2004 ); D'Oria & Novoa (2008 ); Dunitz & Taylor (1997 ); Howard et al. (1996 ); Müller et al. (2007 ); O'Hagan (2008 ); Reichenbacher et al. (2005 ); Weiss et al. (1997 ). For related crystal structures of several polyfluorinated benzenes, see: Thalladi et al. (1998 ). For crystallization techniques, see: Boese & Nussbaumer (1994 ).

Experimental

Crystal data

C₆H₃F₃
M_r = 132.08
Monoclinic, C 2/c
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 ) 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[F² > 2σ(F²)] = 0.061
wR(F²) = 0.226
S = 1.04
634 reflections
44 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯F2ⁱ	1.10	2.77	3.560 (3)	129
C3—H3⋯F1ⁱⁱ	1.10	2.59	3.528 (4)	144
C4—H4⋯F2ⁱⁱⁱ	1.00	2.60	3.440 (4)	142
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); 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 ) and GIMP2 (The GIMP team, 2008 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809038975/lh2880Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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).

Structure description top

Computing details top

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

Figures top

	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).

1,2,3-Trifluorobenzene top

Crystal data top

C₆H₃F₃	F(000) = 264
M_r = 132.08	D_x = 1.569 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 376 reflections
a = 7.4238 (19) Å	θ = 3.8–22.7°
b = 11.590 (3) Å	µ = 0.16 mm⁻¹
c = 7.0473 (17) Å	T = 233 K
β = 112.783 (4)°	Cylindric, colourless
V = 559.1 (2) Å³	0.30 × 0.30 × 0.30 mm
Z = 4

Data collection top

Siemens SMART three-axis goniometer with an APEXII area-detector system diffractometer	634 independent reflections
Radiation source: fine-focus sealed tube	413 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
Detector resolution: 512 pixels mm^-1	θ_max = 28.2°, θ_min = 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
T_min = 0.820, T_max = 0.953	l = −9→4
1074 measured 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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.226	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.1501P)² + 0.039P], where P = (F_o² + 2F_c²)/3
634 reflections	(Δ/σ)_max = 0.017
44 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₆H₃F₃	V = 559.1 (2) Å³
M_r = 132.08	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 7.4238 (19) Å	µ = 0.16 mm⁻¹
b = 11.590 (3) Å	T = 233 K
c = 7.0473 (17) Å	0.30 × 0.30 × 0.30 mm
β = 112.783 (4)°

Data collection top

Siemens SMART three-axis goniometer with an APEXII area-detector system diffractometer	634 independent reflections
Absorption correction: multi-scan (SADABS; Bruker; 2004)	413 reflections with I > 2σ(I)
T_min = 0.820, T_max = 0.953	R_int = 0.013
1074 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.226	H-atom parameters constrained
S = 1.04	Δρ_max = 0.20 e Å⁻³
634 reflections	Δρ_min = −0.18 e Å⁻³
44 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 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) top

	x	y	z	U_iso*/U_eq
F1	1.0000	0.30558 (17)	0.2500	0.1156 (10)
F2	0.6666 (2)	0.4183 (2)	0.1576 (3)	0.1354 (10)
C1	1.0000	0.4213 (3)	0.2500	0.0769 (9)
C2	0.8308 (3)	0.4803 (2)	0.2036 (3)	0.0824 (8)
C3	0.8265 (4)	0.5973 (3)	0.2023 (3)	0.0942 (9)
H3	0.6833	0.6388	0.1585	0.113*
C4	1.0000	0.6558 (3)	0.2500	0.1006 (13)
H4	1.0000	0.7422	0.2500	0.121*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.161 (2)	0.0623 (13)	0.1249 (16)	0.000	0.0563 (14)	0.000
F2	0.0959 (12)	0.157 (2)	0.1484 (16)	−0.0341 (10)	0.0415 (10)	0.0067 (12)
C1	0.1030 (19)	0.0573 (16)	0.0725 (15)	0.000	0.0364 (13)	0.000
C2	0.0830 (14)	0.0890 (17)	0.0770 (13)	−0.0101 (9)	0.0327 (10)	0.0013 (9)
C3	0.1073 (17)	0.0935 (18)	0.0858 (15)	0.0277 (12)	0.0419 (12)	0.0094 (10)
C4	0.163 (4)	0.0605 (17)	0.0848 (19)	0.000	0.056 (2)	0.000

Geometric parameters (Å, º) top

F1—C1	1.341 (4)	C3—C4	1.377 (3)
F2—C2	1.342 (3)	C3—H3	1.0973
C1—C2	1.354 (3)	C4—H4	1.0018
C2—C3	1.357 (4)

F1—C1—C2	120.30 (15)	C2—C3—H3	117.3
C2ⁱ—C1—C2	119.4 (3)	C4—C3—H3	124.4
F2—C2—C3	121.1 (2)	C3—C4—C3ⁱ	121.0 (3)
F2—C2—C1	117.3 (3)	C3—C4—H4	119.5
C3—C2—C1	121.5 (2)	C3ⁱ—C4—H4	119.5
C2—C3—C4	118.3 (2)

Symmetry code: (i) −x+2, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···F2ⁱⁱ	1.10	2.77	3.560 (3)	129
C3—H3···F1ⁱⁱⁱ	1.10	2.59	3.528 (4)	144
C4—H4···F2^iv	1.00	2.60	3.440 (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.

Experimental details

Crystal data
Chemical formula	C₆H₃F₃
M_r	132.08
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	233
a, b, c (Å)	7.4238 (19), 11.590 (3), 7.0473 (17)
β (°)	112.783 (4)
V (Å³)	559.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.30 × 0.30 × 0.30

Data collection
Diffractometer	Siemens SMART three-axis goniometer with an APEXII area-detector system
Absorption correction	Multi-scan (SADABS; Bruker; 2004)
T_min, T_max	0.820, 0.953
No. of measured, independent and observed [I > 2σ(I)] reflections	1074, 634, 413
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.226, 1.04
No. of reflections	634
No. of parameters	44
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.18

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2008) and GIMP2 (The GIMP team, 2008), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···F2ⁱ	1.10	2.77	3.560 (3)	129
C3—H3···F1ⁱⁱ	1.10	2.59	3.528 (4)	144
C4—H4···F2ⁱⁱⁱ	1.00	2.60	3.440 (4)	142

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

Acknowledgements

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.

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