Crystal structure of 4'-bromo-2,3,5,6-tetra-fluoro-biphenyl-4-carbo-nitrile.

The title compound, C13H4BrF4N, synthesized from 1,4'-bromo-iodo-benzene and 4-bromo-2,3,5,6-tetra-fluoro-benzo-nitrile in a coupling reaction was found to crystallize in the ortho-rhom-bic space group P212121. The two phenyl rings are rotated with respect to each other by 40.6 (6)°. The mol-ecules inter-act via aryl-perfluoroaryl stacking [3.796 (2) and 3.773 (2) Å], resulting in inter-molecular 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'-bromo-biphenyl-4-carbo-nitrile, CN⋯Br contacts that could have given rise to a linear arrangement of the biphenyl mol-ecules 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 inter-molecular network of zigzag chains. The crystal studied was refined as an inversion twin.

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 = 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

Δρmax = 0.46 e Å−3

Δρmin = −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 ▸).

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

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

Click here for additional data file.

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

Click here for additional data file.

. 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.

. 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

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) Å3	Splitter, colorless
Z = 4	0.49 × 0.13 × 0.10 mm
F(000) = 640

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 on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.028	w = 1/[σ2(Fo2) + (0.0144P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 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)

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.

	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*

	U11	U22	U33	U12	U13	U23
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)

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)

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

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