2-[4-(Azido­meth­yl)phen­yl]benzonitrile

Peng, B.

doi:10.1107/S1600536812029261

organic compounds

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Volume 68| Part 7| July 2012| Page o2297

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2-[4-(Azidomethyl)phenyl]benzonitrile

Bo Peng ^a ^*

^aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Nanjing 210048, People's Republic of China
^*Correspondence e-mail: pengbnjcc@126.com

(Received 20 June 2012; accepted 27 June 2012; online 30 June 2012)

The title compound, C₁₄H₁₀N₄, was obtained by a reaction of 4′-(bromomethyl)biphenyl-2-carbonitrile and sodium azide. The dihedral angle between the benzene rings is 46.41 (7)°. Weak intermolecular C—H⋯π interactions occur in the crystal.

Related literature

For background literature, see: Haertling (1999 ); Homes et al. (2001 ).

Experimental

Crystal data

C₁₄H₁₀N₄
M_r = 234.26
Triclinic, $[P \overline 1]$
a = 8.0763 (16) Å
b = 8.2183 (16) Å
c = 10.116 (2) Å
α = 76.22 (3)°
β = 69.36 (3)°
γ = 85.94 (3)°
V = 610.2 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
6204 measured reflections
2748 independent reflections
1559 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.146
S = 1.02
2748 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C7–C12 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14B⋯Cgⁱ	0.97	2.75	3.642 (3)	154
Symmetry code: (i) -x+1, -y+1, -z.

Data collection: CrystalClear (Rigaku, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812029261/xu5575sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812029261/xu5575Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812029261/xu5575Isup3.cml

checkCIF report

Comment top

At present, much attention in ferroelectric material field is focused on developing ferroelectric pure organic or inorganic compounds (Haertling et al. 1999; Homes et al. 2001). In order to find more dielectric ferroelectric materials, we investigate the physical properties of the title compound(Fig. 1). The dielectric constant of the title compound as a function of temperature indicates that the permittivity is basically temperature-independent (dielectric constant equaling to 3.5 to 4.8), suggesting that this compound should be not a real ferroelectrics or there may be no distinct phase transition occurred within the measured temperature range. Similarly, below the melting point (373 K) of the compound, the dielectric constant as a function of temperature also goes smoothly, and there is no dielectric anomaly observed (dielectric constant equaling to 3.5 to 4.8).Herein, we report the synthesis and crystal structure of the title compound, 2-[4-(azidomethyl)phenyl]benzonitrile.

Molecules of the title compound have normal geometric parameters. The bond lengths and angles are within their normal ranges. All benzene rings are planar and the azide group is linear.The dihedral angle between the benzene rings in the molecule is 46.41 (7). Dipole–dipole and van der Waals interactions are effective in the molecular packing.

Related literature top

For background literature, see: Haertling (1999); Homes et al. (2001).

Experimental top

To a stirred solution of 4'-(bromomethyl)biphenyl-2-carbonitrile (5.42 g, 0.02 mol) in 30 mL of methanol, sodium azide (1.3 g, 0.02 mol) was added at the room temperature. The temperature was raised to 50°C in half an hour gradually and the mixture was stirred at this temperature for 12 h. The precipitate was filtered and washed with a small amount of water. The title compound was isolated using column chromatography (Petroleum ether: ethyl acetate-4:1). Single crystals suitable for X-ray diffraction analysis were obtained

Structure description top

For background literature, see: Haertling (1999); Homes et al. (2001).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Perspective structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

2-[4-(Azidomethyl)phenyl]benzonitrile top

Crystal data top

C₁₄H₁₀N₄	Z = 2
M_r = 234.26	F(000) = 244
Triclinic, P1	D_x = 1.275 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0763 (16) Å	Cell parameters from 2748 reflections
b = 8.2183 (16) Å	θ = 2.6–27.4°
c = 10.116 (2) Å	µ = 0.08 mm⁻¹
α = 76.22 (3)°	T = 293 K
β = 69.36 (3)°	Prism, colorless
γ = 85.94 (3)°	0.20 × 0.20 × 0.20 mm
V = 610.2 (2) Å³

Data collection top

Rigaku Mercury2 diffractometer	1559 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.035
Graphite monochromator	θ_max = 27.4°, θ_min = 3.5°
Detector resolution: 13.6612 pixels mm^-1	h = −10→10
CCD_Profile_fitting scans	k = −10→10
6204 measured reflections	l = −13→13
2748 independent 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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0613P)² + 0.0517P] where P = (F_o² + 2F_c²)/3
2748 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₄H₁₀N₄	γ = 85.94 (3)°
M_r = 234.26	V = 610.2 (2) Å³
Triclinic, P1	Z = 2
a = 8.0763 (16) Å	Mo Kα radiation
b = 8.2183 (16) Å	µ = 0.08 mm⁻¹
c = 10.116 (2) Å	T = 293 K
α = 76.22 (3)°	0.20 × 0.20 × 0.20 mm
β = 69.36 (3)°

Data collection top

Rigaku Mercury2 diffractometer	1559 reflections with I > 2σ(I)
6204 measured reflections	R_int = 0.035
2748 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 1.02	Δρ_max = 0.14 e Å⁻³
2748 reflections	Δρ_min = −0.21 e Å⁻³
163 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 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 (Å²) top

	x	y	z	U_iso*/U_eq
C7	0.0733 (2)	0.6414 (2)	0.1795 (2)	0.0441 (5)
C1	−0.0353 (2)	0.7492 (2)	0.2778 (2)	0.0444 (5)
C9	0.2358 (3)	0.3876 (2)	0.1389 (2)	0.0519 (5)
H9A	0.2727	0.2827	0.1769	0.062*
C11	0.2308 (3)	0.6036 (3)	−0.0645 (2)	0.0565 (5)
H11A	0.2629	0.6449	−0.1643	0.068*
C8	0.1297 (2)	0.4830 (2)	0.2324 (2)	0.0482 (5)
H8A	0.0957	0.4404	0.3321	0.058*
C3	−0.2866 (3)	0.7958 (2)	0.4875 (2)	0.0545 (5)
H3A	−0.3858	0.7539	0.5675	0.065*
C12	0.1262 (3)	0.7001 (2)	0.0292 (2)	0.0538 (5)
H12A	0.0908	0.8055	−0.0091	0.065*
C6	0.0093 (3)	0.9192 (2)	0.2491 (2)	0.0579 (6)
H6A	0.1082	0.9631	0.1695	0.070*
C2	−0.1865 (2)	0.6899 (2)	0.3994 (2)	0.0446 (5)
C14	0.4070 (3)	0.3449 (3)	−0.1131 (2)	0.0662 (6)
H14A	0.4233	0.4016	−0.2127	0.079*
H14B	0.5220	0.3337	−0.1020	0.079*
C10	0.2877 (2)	0.4470 (2)	−0.0112 (2)	0.0499 (5)
C13	−0.2470 (3)	0.5166 (3)	0.4378 (2)	0.0555 (5)
C5	−0.0900 (3)	1.0228 (3)	0.3361 (2)	0.0655 (6)
H5A	−0.0571	1.1349	0.3142	0.079*
C4	−0.2381 (3)	0.9620 (2)	0.4556 (2)	0.0612 (6)
H4A	−0.3041	1.0327	0.5137	0.073*
N1	−0.2994 (3)	0.3814 (2)	0.4726 (2)	0.0849 (7)
N3	0.4183 (2)	0.0789 (2)	−0.14723 (19)	0.0640 (5)
N2	0.3271 (3)	0.1777 (2)	−0.0802 (2)	0.0799 (6)
N4	0.4870 (3)	−0.0238 (3)	−0.2027 (3)	0.1025 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C7	0.0391 (10)	0.0458 (11)	0.0475 (11)	0.0000 (8)	−0.0138 (9)	−0.0123 (9)
C1	0.0476 (11)	0.0399 (10)	0.0465 (11)	0.0041 (9)	−0.0176 (9)	−0.0100 (9)
C9	0.0494 (11)	0.0464 (11)	0.0566 (13)	0.0062 (9)	−0.0146 (10)	−0.0128 (10)
C11	0.0573 (12)	0.0613 (13)	0.0447 (11)	−0.0030 (11)	−0.0098 (10)	−0.0113 (10)
C8	0.0487 (11)	0.0478 (11)	0.0465 (11)	0.0024 (9)	−0.0139 (10)	−0.0123 (9)
C3	0.0575 (12)	0.0490 (12)	0.0486 (12)	0.0016 (10)	−0.0079 (10)	−0.0120 (10)
C12	0.0551 (12)	0.0487 (11)	0.0511 (12)	0.0022 (10)	−0.0140 (10)	−0.0062 (10)
C6	0.0596 (13)	0.0462 (11)	0.0567 (13)	−0.0065 (10)	−0.0073 (11)	−0.0084 (10)
C2	0.0479 (11)	0.0382 (10)	0.0467 (11)	0.0005 (9)	−0.0140 (9)	−0.0114 (9)
C14	0.0547 (13)	0.0708 (15)	0.0653 (15)	−0.0037 (12)	−0.0034 (11)	−0.0266 (12)
C10	0.0395 (10)	0.0560 (12)	0.0525 (12)	−0.0037 (9)	−0.0080 (9)	−0.0202 (10)
C13	0.0507 (12)	0.0486 (12)	0.0593 (13)	0.0009 (10)	−0.0055 (10)	−0.0185 (11)
C5	0.0763 (16)	0.0402 (11)	0.0744 (16)	−0.0047 (11)	−0.0167 (13)	−0.0153 (11)
C4	0.0704 (14)	0.0466 (12)	0.0632 (14)	0.0088 (11)	−0.0148 (12)	−0.0212 (11)
N1	0.0769 (14)	0.0530 (12)	0.1028 (17)	−0.0111 (11)	0.0031 (12)	−0.0261 (12)
N3	0.0634 (12)	0.0643 (12)	0.0597 (12)	0.0051 (10)	−0.0131 (10)	−0.0197 (10)
N2	0.0686 (12)	0.0743 (13)	0.0863 (14)	−0.0054 (11)	0.0052 (11)	−0.0461 (12)
N4	0.1053 (18)	0.0736 (15)	0.1081 (19)	0.0189 (14)	−0.0048 (15)	−0.0375 (14)

Geometric parameters (Å, º) top

C7—C8	1.395 (2)	C12—H12A	0.9300
C7—C12	1.397 (3)	C6—C5	1.381 (3)
C7—C1	1.496 (2)	C6—H6A	0.9300
C1—C6	1.403 (2)	C2—C13	1.456 (3)
C1—C2	1.408 (3)	C14—N2	1.474 (3)
C9—C8	1.389 (2)	C14—C10	1.514 (3)
C9—C10	1.395 (3)	C14—H14A	0.9700
C9—H9A	0.9300	C14—H14B	0.9700
C11—C10	1.386 (3)	C13—N1	1.146 (2)
C11—C12	1.393 (3)	C5—C4	1.385 (3)
C11—H11A	0.9300	C5—H5A	0.9300
C8—H8A	0.9300	C4—H4A	0.9300
C3—C4	1.378 (3)	N3—N4	1.128 (2)
C3—C2	1.403 (2)	N3—N2	1.220 (2)
C3—H3A	0.9300

C8—C7—C12	117.61 (17)	C1—C6—H6A	119.2
C8—C7—C1	122.25 (17)	C3—C2—C1	121.39 (17)
C12—C7—C1	120.11 (17)	C3—C2—C13	117.21 (17)
C6—C1—C2	116.68 (17)	C1—C2—C13	121.39 (16)
C6—C1—C7	120.17 (17)	N2—C14—C10	109.67 (17)
C2—C1—C7	123.13 (16)	N2—C14—H14A	109.7
C8—C9—C10	120.86 (18)	C10—C14—H14A	109.7
C8—C9—H9A	119.6	N2—C14—H14B	109.7
C10—C9—H9A	119.6	C10—C14—H14B	109.7
C10—C11—C12	120.88 (19)	H14A—C14—H14B	108.2
C10—C11—H11A	119.6	C11—C10—C9	118.27 (17)
C12—C11—H11A	119.6	C11—C10—C14	120.86 (19)
C9—C8—C7	121.18 (18)	C9—C10—C14	120.84 (19)
C9—C8—H8A	119.4	N1—C13—C2	177.4 (2)
C7—C8—H8A	119.4	C6—C5—C4	120.90 (19)
C4—C3—C2	120.07 (19)	C6—C5—H5A	119.6
C4—C3—H3A	120.0	C4—C5—H5A	119.6
C2—C3—H3A	120.0	C3—C4—C5	119.36 (19)
C11—C12—C7	121.20 (19)	C3—C4—H4A	120.3
C11—C12—H12A	119.4	C5—C4—H4A	120.3
C7—C12—H12A	119.4	N4—N3—N2	172.5 (2)
C5—C6—C1	121.59 (19)	N3—N2—C14	115.65 (18)
C5—C6—H6A	119.2

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C7–C12 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14B···Cgⁱ	0.97	2.75	3.642 (3)	154

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀N₄
M_r	234.26
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.0763 (16), 8.2183 (16), 10.116 (2)
α, β, γ (°)	76.22 (3), 69.36 (3), 85.94 (3)
V (Å³)	610.2 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku Mercury2
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6204, 2748, 1559
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.146, 1.02
No. of reflections	2748
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.21

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C7–C12 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14B···Cgⁱ	0.97	2.7484	3.642 (3)	154

Symmetry code: (i) −x+1, −y+1, −z.

References

Haertling, G. H. (1999). J. Am. Ceram. Soc. 82, 797–810. CrossRef CAS Google Scholar
Homes, C. C., Vogt, T., Shapiro, S. M., Wakimoto, S. & Ramirez, A. P. (2001). Science, 293, 673–676. Web of Science CrossRef PubMed CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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https://doi.org/10.1107/S1600536812029261

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