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

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.

1. 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).

2. Experimental

2.1. Crystal data

• C₁₃H₄BrF₄N

• M_r = 330.08

• Orthorhombic, P 2₁ 2₁ 2₁

• a = 7.3560 (15) Å

• b = 12.107 (2) Å

• c = 12.723 (3) Å

• V = 1133.1 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 3.66 mm⁻¹

• T = 93 K

• 0.49 × 0.13 × 0.10 mm

2.2. 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

2.3. Refinement

• R[F² > 2σ(F²)] = 0.028

• wR(F²) = 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)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯F2	0.95	2.47	2.882 (4)	106
C13—H13⋯F3	0.95	2.45	2.865 (3)	107

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).

Supporting 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)].

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).

Structure description

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).

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.

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)].

Computing details

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures

	Fig. 1. The molecular structure of the title molecule including atom labelling. Displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The crystal packing of the title compound showing the stacking interactions along [100].

4'-Bromo-2,3,5,6-tetrafluorobiphenyl-4-carbonitrile

Crystal data

C13H4BrF4N	Dx = 1.935 Mg m^−3
Mr = 330.08	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 4750 reflections
a = 7.3560 (15) Å	θ = 3.2–28.4°
b = 12.107 (2) Å	µ = 3.66 mm^−1
c = 12.723 (3) Å	T = 93 K
V = 1133.1 (4) Å^3	Splitter, colorless
Z = 4	0.49 × 0.13 × 0.10 mm
F(000) = 640

Data collection

Bruker SMART CCD area-detector diffractometer	2930 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.053
phi and ω scans	θmax = 29.8°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −10→10
Tmin = 0.486, Tmax = 0.718	k = −16→16
18347 measured reflections	l = −17→17
3234 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.028	w = 1/[σ^2(Fo^2) + (0.0144P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.052	(Δ/σ)max = 0.001
S = 0.99	Δρmax = 0.46 e Å^−3
3234 reflections	Δρmin = −0.31 e Å^−3
173 parameters	Absolute structure: Refined as an inversion twin.
0 restraints	Absolute structure parameter: 0.011 (9)

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. Refined as a 2-component inversion twin.

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

	x	y	z	Uiso*/Ueq
Br1	0.89811 (4)	0.35795 (3)	0.37922 (2)	0.01853 (8)
F1	0.7744 (2)	1.00596 (16)	0.75920 (12)	0.0196 (4)
F2	0.7639 (2)	0.79698 (15)	0.69387 (12)	0.0179 (4)
F3	1.0359 (2)	0.90632 (14)	0.37137 (13)	0.0163 (4)
F4	1.0323 (2)	1.11450 (14)	0.43493 (13)	0.0196 (4)
N1	0.9005 (4)	1.2681 (2)	0.66563 (19)	0.0208 (6)
C1	0.9026 (4)	1.1790 (2)	0.6343 (2)	0.0161 (6)
C2	0.9029 (5)	1.0664 (2)	0.5984 (2)	0.0153 (6)
C3	0.8371 (4)	0.9812 (3)	0.6627 (2)	0.0154 (7)
C4	0.8354 (4)	0.8729 (3)	0.6295 (2)	0.0147 (6)
C5	0.9004 (4)	0.8418 (2)	0.5296 (2)	0.0131 (6)
C6	0.9650 (4)	0.9283 (3)	0.4667 (2)	0.0129 (6)
C7	0.9665 (4)	1.0369 (3)	0.4992 (2)	0.0144 (6)
C8	0.8998 (5)	0.7249 (2)	0.4938 (2)	0.0133 (6)
C9	0.9476 (4)	0.6389 (3)	0.5620 (2)	0.0145 (6)
H9	0.9807	0.6555	0.6324	0.017*
C10	0.9474 (4)	0.5302 (3)	0.5286 (2)	0.0161 (7)
H10	0.9795	0.4725	0.5756	0.019*
C11	0.8997 (5)	0.5065 (2)	0.4254 (2)	0.0148 (6)
C12	0.8517 (4)	0.5894 (3)	0.3554 (2)	0.0153 (7)
H12	0.8191	0.5720	0.2851	0.018*
C13	0.8520 (4)	0.6986 (3)	0.3898 (2)	0.0142 (6)
H13	0.8196	0.7560	0.3424	0.017*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.02368 (15)	0.01300 (14)	0.01890 (13)	−0.00129 (14)	0.00259 (14)	−0.00242 (13)
F1	0.0229 (10)	0.0218 (10)	0.0141 (8)	0.0003 (8)	0.0031 (7)	−0.0022 (7)
F2	0.0213 (10)	0.0185 (10)	0.0138 (8)	−0.0028 (8)	0.0029 (7)	0.0034 (7)
F3	0.0201 (9)	0.0163 (9)	0.0125 (7)	0.0014 (7)	0.0034 (7)	−0.0004 (8)
F4	0.0265 (10)	0.0143 (10)	0.0179 (8)	−0.0015 (7)	0.0042 (7)	0.0030 (7)
N1	0.0216 (14)	0.0193 (15)	0.0215 (12)	0.0015 (14)	0.0011 (13)	−0.0013 (11)
C1	0.0153 (14)	0.0200 (15)	0.0130 (13)	−0.0011 (13)	0.0005 (14)	0.0010 (11)
C2	0.0156 (13)	0.0137 (14)	0.0165 (13)	0.0012 (14)	−0.0020 (13)	−0.0026 (11)
C3	0.0133 (15)	0.0204 (18)	0.0125 (13)	0.0020 (13)	−0.0003 (11)	−0.0034 (12)
C4	0.0121 (13)	0.0149 (16)	0.0169 (13)	−0.0017 (11)	−0.0013 (12)	0.0049 (14)
C5	0.0112 (12)	0.0144 (15)	0.0136 (11)	0.0014 (14)	−0.0040 (12)	−0.0006 (11)
C6	0.0110 (14)	0.0162 (16)	0.0116 (13)	0.0024 (12)	−0.0007 (11)	−0.0012 (12)
C7	0.0136 (14)	0.0138 (16)	0.0160 (14)	0.0003 (12)	−0.0008 (11)	0.0035 (12)
C8	0.0101 (13)	0.0134 (15)	0.0164 (12)	−0.0001 (13)	0.0009 (13)	−0.0013 (11)
C9	0.0117 (14)	0.0187 (16)	0.0133 (12)	−0.0030 (13)	−0.0021 (10)	−0.0017 (14)
C10	0.0155 (17)	0.0149 (16)	0.0178 (14)	0.0010 (12)	0.0008 (12)	0.0033 (13)
C11	0.0125 (13)	0.0136 (15)	0.0183 (13)	−0.0029 (14)	0.0017 (14)	−0.0048 (11)
C12	0.0147 (16)	0.0191 (17)	0.0120 (14)	−0.0006 (12)	0.0002 (10)	−0.0025 (12)
C13	0.0136 (15)	0.0151 (15)	0.0137 (13)	0.0018 (11)	−0.0005 (11)	0.0045 (12)

Geometric parameters (Å, º)

Br1—C11	1.892 (3)	C5—C8	1.487 (4)
F1—C3	1.346 (3)	C6—C7	1.379 (4)
F2—C4	1.339 (3)	C8—C9	1.400 (4)
F3—C6	1.347 (3)	C8—C13	1.406 (4)
F4—C7	1.336 (3)	C9—C10	1.383 (4)
N1—C1	1.150 (4)	C9—H9	0.9500
C1—C2	1.438 (4)	C10—C11	1.389 (4)
C2—C7	1.393 (4)	C10—H10	0.9500
C2—C3	1.402 (4)	C11—C12	1.388 (4)
C3—C4	1.377 (4)	C12—C13	1.392 (4)
C4—C5	1.409 (4)	C12—H12	0.9500
C5—C6	1.401 (4)	C13—H13	0.9500
N1—C1—C2	178.1 (3)	C9—C8—C13	118.6 (3)
C7—C2—C3	117.1 (3)	C9—C8—C5	121.2 (2)
C7—C2—C1	122.1 (3)	C13—C8—C5	120.3 (3)
C3—C2—C1	120.8 (2)	C10—C9—C8	121.1 (3)
F1—C3—C4	119.3 (3)	C10—C9—H9	119.4
F1—C3—C2	119.1 (3)	C8—C9—H9	119.4
C4—C3—C2	121.6 (3)	C9—C10—C11	119.2 (3)
F2—C4—C3	118.0 (3)	C9—C10—H10	120.4
F2—C4—C5	120.1 (3)	C11—C10—H10	120.4
C3—C4—C5	121.9 (3)	C12—C11—C10	121.4 (3)
C6—C5—C4	115.5 (3)	C12—C11—Br1	119.1 (2)
C6—C5—C8	122.5 (2)	C10—C11—Br1	119.5 (2)
C4—C5—C8	122.0 (3)	C11—C12—C13	119.0 (3)
F3—C6—C7	117.1 (3)	C11—C12—H12	120.5
F3—C6—C5	119.8 (3)	C13—C12—H12	120.5
C7—C6—C5	123.0 (3)	C12—C13—C8	120.7 (3)
F4—C7—C6	119.3 (3)	C12—C13—H13	119.6
F4—C7—C2	119.8 (3)	C8—C13—H13	119.6
C6—C7—C2	120.9 (3)
C7—C2—C3—F1	179.9 (3)	C5—C6—C7—C2	0.2 (5)
C1—C2—C3—F1	−0.5 (4)	C3—C2—C7—F4	−179.4 (3)
C7—C2—C3—C4	0.1 (5)	C1—C2—C7—F4	1.0 (5)
C1—C2—C3—C4	179.7 (3)	C3—C2—C7—C6	−0.3 (4)
F1—C3—C4—F2	2.6 (4)	C1—C2—C7—C6	−179.9 (3)
C2—C3—C4—F2	−177.5 (3)	C6—C5—C8—C9	139.2 (3)
F1—C3—C4—C5	−179.5 (3)	C4—C5—C8—C9	−40.8 (4)
C2—C3—C4—C5	0.3 (5)	C6—C5—C8—C13	−40.4 (5)
F2—C4—C5—C6	177.3 (3)	C4—C5—C8—C13	139.6 (3)
C3—C4—C5—C6	−0.5 (4)	C13—C8—C9—C10	−0.3 (4)
F2—C4—C5—C8	−2.6 (4)	C5—C8—C9—C10	−179.9 (3)
C3—C4—C5—C8	179.6 (3)	C8—C9—C10—C11	0.3 (4)
C4—C5—C6—F3	177.6 (2)	C9—C10—C11—C12	−0.2 (5)
C8—C5—C6—F3	−2.4 (4)	C9—C10—C11—Br1	−179.8 (2)
C4—C5—C6—C7	0.2 (4)	C10—C11—C12—C13	0.1 (5)
C8—C5—C6—C7	−179.8 (3)	Br1—C11—C12—C13	179.7 (2)
F3—C6—C7—F4	1.8 (4)	C11—C12—C13—C8	−0.1 (4)
C5—C6—C7—F4	179.3 (3)	C9—C8—C13—C12	0.2 (4)
F3—C6—C7—C2	−177.3 (3)	C5—C8—C13—C12	179.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···F2	0.95	2.47	2.882 (4)	106
C13—H13···F3	0.95	2.45	2.865 (3)	107