Crystal structure of 4′-bromo-2,3,5,6-tetra­fluoro­biphenyl-4-carbo­nitrile

Ricarda Heckel; Jürg Hulliger; Anke Schwarzer; Edwin Weber

doi:10.1107/S2056989015007847

. 2015 Apr 25;71(Pt 5):o347–o348. doi: 10.1107/S2056989015007847

Crystal structure of 4′-bromo-2,3,5,6-tetrafluorobiphenyl-4-carbonitrile

Ricarda Heckel ^a, Jürg Hulliger ^b, Anke Schwarzer ^a,^*, Edwin Weber ^a

PMCID: PMC4420037 PMID: 25995941

Abstract

The title compound, C₁₃H₄BrF₄N, synthesized from 1,4′-bromoiodobenzene and 4-bromo-2,3,5,6-tetrafluorobenzonitrile in a coupling reaction was found to crystallize in the orthorhombic space group P2₁2₁2₁. The two phenyl rings are rotated with respect to each other by 40.6 (6)°. The molecules interact via aryl–perfluoroaryl stacking [3.796 (2) and 3.773 (2) Å], resulting in intermolecular chains along the a-axis direction. C—H⋯F contacts of about 2.45 Å connect these chains. In contrast to the structure of the parent compound 4′-bromobiphenyl-4-carbonitrile, CN⋯Br contacts that could have given rise to a linear arrangement of the biphenyl molecules desirable for non-linear optical (NLO) materials are not observed in the packing. Instead, several Br⋯F [3.2405 (17) and 3.2777 (18) Å] and F⋯F [2.894 (2) Å] contacts of side-on type II form an intermolecular network of zigzag chains. The crystal studied was refined as an inversion twin.

Keywords: crystal structure, biphenyl, tetrafluoro substitution, bromo–cyano substitution, π–π^F stacking, halogen interactions

Related literature

For crystal structures of 4-cyano-4′-halogene substituted biphenyls, see: Gleason et al. (1991 ▸) for fluorine, Kronebusch et al. (1976 ▸) for bromine, Britton & Gleason (1991 ▸) for iodine. For halogen interactions in molecular crystal structures, see: Ramasubbu et al. (1986 ▸), Awwadi et al. (2006 ▸), Brammer et al. (2001 ▸) and Metrangolo et al. (2008 ▸). For interactions of halogens with cyano groups, see: Desiraju & Harlow (1989 ▸), Süss et al. (2005 ▸) and Mukherjee et al. (2014 ▸). For fluorine involved into these interactions, see: Schwarzer et al. (2010 ▸), Merz & Vasylyeva (2010 ▸), Schwarzer & Weber (2008 ▸) and Reichenbächer et al. (2005 ▸).

Experimental

Crystal data

C₁₃H₄BrF₄N
M _r = 330.08
Orthorhombic,
a = 7.3560 (15) Å
b = 12.107 (2) Å
c = 12.723 (3) Å
V = 1133.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 3.66 mm⁻¹
T = 93 K
0.49 × 0.13 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012) T _min = 0.486, T _max = 0.718
18347 measured reflections
3234 independent reflections
2930 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.052
S = 0.99
3234 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.31 e Å⁻³
Absolute structure: refined as an inversion twin.
Absolute structure parameter: 0.011 (9)

Data collection: SMART (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2015 ▸); molecular graphics: XP (Sheldrick, 2008 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸), publCIF (Westrip, 2010 ▸) and SHELXLE (Hübschle et al., 2011 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989015007847/im2464sup1.cif

e-71-0o347-sup1.cif^{(544.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015007847/im2464Isup2.hkl

e-71-0o347-Isup2.hkl^{(177.6KB, hkl)}

Click here for additional data file.^{(2KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015007847/im2464Isup3.cml

Click here for additional data file.^{(1,000.8KB, tif)}

. DOI: 10.1107/S2056989015007847/im2464fig1.tif

The molecular structure of the title molecule including atom labelling. Displacement ellipsoids drawn at the 50% probability level.

Click here for additional data file.^{(1.9MB, tif)}

. DOI: 10.1107/S2056989015007847/im2464fig2.tif

The crystal packing of the title compound showing the stacking interactions along [100].

CCDC reference: 1060721

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C9H9F2	0.95	2.47	2.882(4)	106
C13H13F3	0.95	2.45	2.865(3)	107

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supplementary crystallographic information

S1. Synthesis and crystallization

Under inert conditions, 1-bromo-4-iodobenzene (22.6 g, 80 mmol) in THF (90 mL) was added dropwise to magnesium shaving (1.8 g, 75 mmol. The reaction mixture was refluxed for 90 min. After cooling to room temperature, CuBr (25.8 g, 180 mmol) was added and the mixture was stirred for 1 h at this temperature. Then 15 ml of 1,4-dioxane was added and the mixture was stirred for an hour followed by dropwise addition of a solution of 4-bromo-2,3,5,6-tetrafluorobenzonitrile (6.4 g, 25 mmol) in toluene (50 ml). After refluxing for 2 d, the mixture was cooled to room temperature, filtered over Celite and freed from solvents removed under reduced pressure. The residue was dissolved in toluene and washed with 3M HCl followed by aqueous NaOH solution. The organic phases were collected, dried over Na₂SO₄ and evaporated. The raw product was purified by column chromatography (SiO₂; eluent: CH₂Cl₂/n-hexane, 2/1 v/v to yield 1.00 g (12 %) of the title compound. Single crystals suitable for X-ray diffraction were obtained from acetone solution at room temperature. Data for (I): M.p. 133-134 °C. ¹H NMR(400 MHz; acetone-d₆): δ_H = 7.57 (d, ³J_HH = 8.9, 2H, H-9, H-13), 7.82 (d, ³J_HH = 8.9, 2H, H-10, H12) ppm. ¹³C NMR (100 MHz; acetone-d₆): δ_C = 94.30 (d, ²J_CF = 17.4, C-2), 108.62 (t, ³J_CF = -3.7, C-1), 125.52, 126.32 (s, C-8, C11), 127.04 (t, ²J_CF = 17.4, C-5), 133.05 (t, ⁴J_CF = 2.5, C-9), 133.32 (s, C-10), 143.39, 146.69 (d, ¹J_CF = -147.2, C-4), 147.01, 150.43 (d, ¹J_CF = -265.5, C-3) ppm. ¹⁹F NMR(376 MHz; acetone-d₆): δ_F = -136.15 (F-1, d, ³J_FF = 9.3 ), -142.53 (F-2, d, ³J_FF = 9.3) ppm. GC—MS (m/z) 329 [M]⁺, 250 [M—Br]⁺, 231 [-F]⁺, 200 [-CF]⁺, 125, 99, 74, 50.

S2. Refinement details

The C-bound H atoms were positioned geometrically and allowed to ride on their parent atoms: C–H = 0.95 Å for aryl H atoms, with [U_iso(H) = 1.2U_eq(C)].