Crystal structure of [1,1′-biphen­yl]-2,2′-dicarbo­nitrile

Abstract

The complete mol­ecule of the title compound, C₁₄H₈N₂, is generated by a twofold rotation axis located at the midpoint of the biphenyl C—C bond. The dihedral angle between the symmetry-related phenyl rings is 46.16 (3)°. In the crystal, mol­ecules are linked by slipped parallel π–π inter­actions [centroid–centroid distance = 3.9451 (7) Å, normal distance = 3.6293 (5) Å, slippage 1.547 Å], forming columns along the b-axis direction.

Related literature  

The title compound has been used as a reactant for phthalocyanine synthesis (Shimizu et al., 2011 ▸, 2014 ▸). Related crystal structures were reported by Furukawa et al. (2008 ▸) and Paek et al. (1989 ▸). For synthetic details, see: Wu et al. (2007 ▸).

Experimental  

Crystal data  

• C₁₄H₈N₂

• M _r = 204.22

• Monoclinic,

• a = 15.7839 (9) Å

• b = 3.9451 (2) Å

• c = 16.6079 (9) Å

• β = 101.630 (3)°

• V = 1012.93 (9) ų

• Z = 4

• Mo Kα radiation

• μ = 0.08 mm⁻¹

• T = 173 K

• 0.43 × 0.12 × 0.06 mm

Data collection  

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T _min = 0.966, T _max = 0.995

• 4708 measured reflections

• 1157 independent reflections

• 988 reflections with I > 2σ(I)

• R _int = 0.030

Refinement  

• R[F ² > 2σ(F ²)] = 0.042

• wR(F ²) = 0.116

• S = 1.09

• 1157 reflections

• 73 parameters

• H-atom parameters constrained

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2010 ▸); software used to prepare material for publication: SHELXTL.

Supplementary Material

CCDC reference: 1401615

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

supplementary crystallographic information

S1. Experimental

The title compound was prepared by Suzuki coupling reaction of 2-bromobenzonitrile and 2-cyanophenyl boronic acid in acetonitrile (Wu et al., 2007). Slow evaporation of a solution in acetone/ethyl acetate gave single crystals suitable for X-ray analysis.

S2. Refinement

All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.95 Å, U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius. Symmetry-related atoms (not labelled) are generated by symmetry code x+1, y, -z+1/2.

Fig. 2.

Crystal packing viewed along the b axis. The intermolecular π–π interactions between the phenyl ring systems [Cg1···Cg1i, 3.9451 (7) Å; Cg1 is the centroid of the C2···C7 ring; symmetry code (i): x, y - 1, z] are shown as dashed lines. They link molecules into columns along [010].

Crystal data

C14H8N2	F(000) = 424
Mr = 204.22	Dx = 1.339 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.7839 (9) Å	Cell parameters from 1375 reflections
b = 3.9451 (2) Å	θ = 3.3–27.5°
c = 16.6079 (9) Å	µ = 0.08 mm−1
β = 101.630 (3)°	T = 173 K
V = 1012.93 (9) Å3	Block, colourless
Z = 4	0.43 × 0.12 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer	1157 independent reflections
Radiation source: fine-focus sealed tube	988 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 27.6°, θmin = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −20→20
Tmin = 0.966, Tmax = 0.995	k = −5→1
4708 measured reflections	l = −21→19

Refinement

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0584P)2 + 0.5212P] where P = (Fo2 + 2Fc2)/3
1157 reflections	(Δ/σ)max < 0.001
73 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

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 F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.58879 (7)	0.3650 (3)	0.08819 (7)	0.0323 (3)
C1	0.53155 (8)	0.2522 (3)	0.11172 (7)	0.0233 (3)
C2	0.45640 (7)	0.1152 (3)	0.13725 (7)	0.0206 (3)
C3	0.37963 (8)	0.1099 (3)	0.07828 (7)	0.0244 (3)
H3	0.3791	0.1894	0.0242	0.029*
C4	0.30457 (8)	−0.0108 (3)	0.09854 (8)	0.0273 (3)
H4	0.2522	−0.0139	0.0586	0.033*
C5	0.30609 (8)	−0.1274 (3)	0.17741 (8)	0.0257 (3)
H5	0.2545	−0.2117	0.1914	0.031*
C6	0.38225 (8)	−0.1224 (3)	0.23640 (7)	0.0231 (3)
H6	0.3819	−0.2037	0.2902	0.028*
C7	0.45930 (7)	−0.0004 (3)	0.21832 (7)	0.0196 (3)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0275 (6)	0.0450 (7)	0.0253 (6)	−0.0066 (5)	0.0075 (4)	0.0013 (5)
C1	0.0244 (6)	0.0277 (7)	0.0176 (6)	−0.0017 (5)	0.0034 (4)	−0.0014 (5)
C2	0.0208 (6)	0.0225 (6)	0.0194 (6)	−0.0003 (4)	0.0059 (4)	−0.0015 (4)
C3	0.0258 (6)	0.0290 (7)	0.0180 (6)	−0.0002 (5)	0.0037 (5)	0.0003 (4)
C4	0.0214 (6)	0.0331 (7)	0.0255 (7)	−0.0011 (5)	0.0000 (5)	−0.0016 (5)
C5	0.0206 (6)	0.0286 (6)	0.0286 (7)	−0.0028 (5)	0.0069 (5)	−0.0006 (5)
C6	0.0245 (6)	0.0239 (6)	0.0216 (6)	−0.0017 (5)	0.0068 (5)	0.0020 (4)
C7	0.0205 (6)	0.0187 (6)	0.0199 (6)	0.0012 (4)	0.0044 (5)	−0.0013 (4)

Geometric parameters (Å, º)

N1—C1	1.1443 (16)	C4—H4	0.9500
C1—C2	1.4427 (16)	C5—C6	1.3893 (17)
C2—C3	1.3963 (16)	C5—H5	0.9500
C2—C7	1.4135 (16)	C6—C7	1.3957 (16)
C3—C4	1.3800 (17)	C6—H6	0.9500
C3—H3	0.9500	C7—C7i	1.488 (2)
C4—C5	1.3839 (18)
N1—C1—C2	176.92 (12)	C4—C5—C6	120.68 (11)
C3—C2—C7	121.34 (11)	C4—C5—H5	119.7
C3—C2—C1	116.62 (10)	C6—C5—H5	119.7
C7—C2—C1	122.02 (10)	C5—C6—C7	121.38 (11)
C4—C3—C2	120.04 (11)	C5—C6—H6	119.3
C4—C3—H3	120.0	C7—C6—H6	119.3
C2—C3—H3	120.0	C6—C7—C2	116.99 (11)
C3—C4—C5	119.57 (11)	C6—C7—C7i	120.90 (12)
C3—C4—H4	120.2	C2—C7—C7i	122.09 (12)
C5—C4—H4	120.2
C7—C2—C3—C4	−0.18 (18)	C5—C6—C7—C7i	−179.21 (9)
C1—C2—C3—C4	−178.65 (11)	C3—C2—C7—C6	0.51 (17)
C2—C3—C4—C5	−0.26 (19)	C1—C2—C7—C6	178.91 (11)
C3—C4—C5—C6	0.34 (19)	C3—C2—C7—C7i	179.27 (9)
C4—C5—C6—C7	0.02 (19)	C1—C2—C7—C7i	−2.34 (15)
C5—C6—C7—C2	−0.44 (17)

Symmetry code: (i) −x+1, y, −z+1/2.