2,5 Di­phenylpentane­nitrile

organic papers

o1668

Structure Reports Online

ISSN 1600-5368

2,5-Diphenylpentanenitrile

Jie Li, Chun-Bao Li* and Qi-Yun Shao

Department of Chemistry, Tianjin University, Tianjin 300072, People's Republic of China

Correspondence e-mail: [email protected]

Key indicators Single-crystal X-ray study T= 293 K

Mean(C±C) = 0.003 AÊ Rfactor = 0.056 wRfactor = 0.143

Data-to-parameter ratio = 17.4

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2003 International Union of Crystallography Printed in Great Britain ± all rights reserved

This paper reports a new synthesis of the title compound, C17H17N, and its crystal structure. In the molecule, the two

phenyl rings are approximately parallel. The cyano group is almost perpendicular to the two phenyl rings.

Comment

Freerksen et al. (1983) repeated the Watt procedure (Watt, 1974), obtaining the title compound, (I), in 56% yield. Masuko

et al.(1985) synthesized (I) in 94% yield, starting from benzyl nitrile and phenylpropyl chloride. Similarly, Hinoet al.(1988) prepared the compound using benzyl nitrile and 3-bromo-propylbenzene. In these syntheses, expensive starting mater-ials were used. We report our synthesis of this compoundviaa Friedel±Crafts reaction. The starting material, 5-chloro-2-phenylvaleronitrile was synthesized by reaction of benzyl nitrile and 1-bromo-3-chloropropane in the presence of NaOH and the phase-transfer catalyst benzyltrimethyl-ammonium bromide. (I) was produced in 90% yield by re¯uxing a mixture of benzene, AlCl3and

5-chloro-2-phenyl-valeronitrile.

The molecular structure is illustrated in Fig. 1. The two phenyl rings are approximately parallel, forming a dihedral angle of 7.9 (5)_{. The angle N1ÐC5ÐC1 is 178.6 (2),}

indi-cating that atom C5 issphybridized. The angles between N1Ð C5ÐC1 and the two phenyl rings are 86.9 (5) and 92.7 (5)_,

respectively, indicating that the cyano group is perpendicular

Received 26 August 2003 Accepted 11 September 2003 Online 7 October 2003

Figure 1

to the phenyl ring planes. Atoms, C1, C2, C3 and C4 are almost coplanar. The C5ÐN1 distance is 1.137 (3) AÊ, similar to the CÐN bond length 1.134 (2) AÊ in bis(2-methylbenzyl cyanide) tetracyanobenzene (Hosomiet al., 1997).

Experimental

5-Chloro-2-phenylvaleronitrile (4.3 g, 22.3 mmol) and benzene (20.0 ml) were heated in a 50 ml round-bottom ¯ask, catalysed by AlCl3(4.0 g, 29.9 mmol). The reaction mixture was re¯uxed for 6 h,

then poured into iced water and acidi®ed with dilute HCl. The organic layer was separated and washed with water, dried and concentrated. Evaporation of the solvent and crystallization of the residue from toluene yielded (I), 4.733 g, 90%, m.p. 351±353 K (literature m.p. 349±351 K). Crystals were obtained by slow evaporation of a toluene solution. IR (KBr) 2235 (ms) cmÿ1_. 1_H

NMR (400 CDCl3)3.75±3.78 (1H, m), 7.13±7.38 (10H, m) p.p.m.

Crystal data

C17H17N

Mr= 235.32

Orthorhombic,Pbca a= 8.356 (3) AÊ

b= 17.406 (5) AÊ

c= 19.052 (6) AÊ

V= 2771.0 (15) AÊ3

Z= 8

Dx= 1.128 Mg mÿ3

MoKradiation Cell parameters from 897

re¯ections

= 2.6±22.7

= 0.07 mmÿ1

T= 293 (2) K Block, colorless 0.300.250.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer

'and!scans

Absorption correction: none 14985 measured re¯ections 2843 independent re¯ections

1751 re¯ections withI> 2(I)

Rint= 0.065

max= 26.4

h=ÿ6!10

k=ÿ21!21

l=ÿ23!23

Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.056}

wR(F2_{) = 0.143}

S= 1.04 2843 re¯ections 163 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0511P)2

+ 0.5892P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001 max= 0.12 e AÊÿ3 min=ÿ0.19 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,_).

C1ÐC5 1.472 (3)

C1ÐC6 1.519 (2) C1ÐC2 1.544 (2)

C5ÐC1ÐC6 111.74 (15)

C12ÐC4ÐC3 112.25 (15)

C7ÐC6ÐC1 122.37 (16)

C11ÐC6ÐC1 119.22 (15)

C17ÐC12ÐC4 120.62 (18)

C13ÐC12ÐC4 121.70 (18)

C5ÐC1ÐC2ÐC3 ÿ61.9 (2)

C5ÐC1ÐC6ÐC7 ÿ31.9 (2) C3ÐC4ÐC12ÐC17C3ÐC4ÐC12ÐC13 ÿ78.3 (2)99.5 (2)

Data collection:SMART(Bruker, 1997); cell re®nement:SMART; data reduction: SAINT (Bruker, 1997) and SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication:SHELXTL.

References

Bruker (1997).SMART, SAINTandSHELXTL.Versions 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Freerksen, R. W., Selikson, S. J. & Wroble, R. R. (1983).J. Org. Chem.48, 4087±4096.

Hino, K., Nagai, Y. & Uno, H. (1988).Chem. Pharm. Bull.36, 2386±2400. Hosomi, H., Ohba, S., Ito, Y. & Nakabayashi, H. (1997).Acta Cryst.C53,

IUC9700031.

Masuko, F., Ohita, Katsura, T. & Itami (1985). US Patent NO. 4 536 599. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of

GoÈttingen, Germany.

supporting information

sup-1 Acta Cryst. (2003). E59, o1668–o1669

supporting information

Acta Cryst. (2003). E59, o1668–o1669 [https://doi.org/10.1107/S1600536803020178]

2,5-Diphenylpentanenitrile

Jie Li, Chun-Bao Li and Qi-Yun Shao

2-Phenylbenzenepentanenitrile

Crystal data C17H17N Mr = 235.32

Orthorhombic, Pbca Hall symbol: -P 2ac 2ab a = 8.356 (3) Å

b = 17.406 (5) Å c = 19.052 (6) Å V = 2771.0 (15) Å3 Z = 8

F(000) = 1008 Dx = 1.128 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 897 reflections θ = 2.6–22.7°

µ = 0.07 mm−1 T = 293 K Plate, colorless 0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART CCD area detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

14985 measured reflections 2843 independent reflections

1751 reflections with I > 2σ(I) Rint = 0.065

θmax = 26.4°, θmin = 2.1° h = −6→10

k = −21→21 l = −23→23

Refinement Refinement on F2 Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.056} wR(F2_{) = 0.143} S = 1.04 2843 reflections 163 parameters

0 restraints

H-atom parameters constrained w = 1/[σ2_(Fo2_{) + (0.0511P)}2 _{+ 0.5892P]}

where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001

Δρmax = 0.12 e Å−3 Δρmin = −0.19 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

C1 0.1351 (2) 0.94690 (10) 0.67673 (9) 0.0513 (4)

H1 0.2366 0.9249 0.6606 0.062*

C2 0.0044 (2) 0.92497 (10) 0.62301 (10) 0.0542 (5)

H2A −0.0978 0.9442 0.6396 0.065*

H2B 0.0278 0.9502 0.5788 0.065*

C3 −0.0102 (2) 0.83919 (10) 0.61017 (10) 0.0563 (5)

H3A 0.0923 0.8195 0.5944 0.068*

H3B −0.0365 0.8138 0.6540 0.068*

C4 −0.1368 (2) 0.81992 (10) 0.55605 (11) 0.0654 (5)

H4A −0.2384 0.8416 0.5708 0.078*

H4B −0.1079 0.8432 0.5116 0.078*

C5 0.0974 (3) 0.91317 (12) 0.74562 (12) 0.0696 (6) C6 0.15559 (19) 1.03350 (10) 0.68115 (8) 0.0471 (4) C7 0.0718 (2) 1.07785 (12) 0.72834 (10) 0.0648 (6)

H7 0.0062 1.0544 0.7614 0.078*

C8 0.0846 (3) 1.15723 (13) 0.72684 (12) 0.0739 (6)

H8 0.0263 1.1867 0.7585 0.089*

C9 0.1819 (3) 1.19238 (11) 0.67936 (10) 0.0681 (6)

H9 0.1901 1.2457 0.6786 0.082*

C10 0.2674 (3) 1.14887 (11) 0.63281 (10) 0.0663 (6)

H10 0.3346 1.1726 0.6005 0.080*

C11 0.2546 (2) 1.07007 (10) 0.63364 (9) 0.0569 (5)

H11 0.3133 1.0410 0.6018 0.068*

C12 −0.1560 (2) 0.73446 (10) 0.54602 (9) 0.0521 (5) C13 −0.0854 (2) 0.69639 (12) 0.49059 (10) 0.0605 (5)

H13 −0.0292 0.7244 0.4571 0.073*

C14 −0.0963 (2) 0.61770 (12) 0.48377 (11) 0.0681 (6)

H14 −0.0466 0.5931 0.4463 0.082*

C15 −0.1803 (3) 0.57589 (12) 0.53204 (12) 0.0766 (7)

H15 −0.1880 0.5228 0.5277 0.092*

C16 −0.2531 (3) 0.61298 (12) 0.58688 (12) 0.0809 (7)

H16 −0.3111 0.5849 0.6197 0.097*

C17 −0.2409 (3) 0.69130 (12) 0.59370 (10) 0.0681 (6)

H17 −0.2910 0.7156 0.6312 0.082*

N1 0.0651 (3) 0.88699 (13) 0.79845 (11) 0.1081 (8)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

supporting information

sup-3 Acta Cryst. (2003). E59, o1668–o1669

C7 0.0670 (13) 0.0658 (13) 0.0616 (12) −0.0135 (10) 0.0161 (10) −0.0092 (10) C8 0.0763 (14) 0.0674 (14) 0.0779 (15) −0.0043 (11) 0.0121 (12) −0.0251 (11) C9 0.0819 (14) 0.0498 (11) 0.0725 (13) −0.0097 (10) −0.0096 (12) −0.0073 (10) C10 0.0813 (14) 0.0597 (13) 0.0579 (12) −0.0197 (11) 0.0041 (10) 0.0012 (10) C11 0.0627 (11) 0.0576 (12) 0.0504 (10) −0.0071 (9) 0.0074 (9) −0.0070 (8) C12 0.0524 (10) 0.0470 (10) 0.0569 (11) −0.0027 (8) −0.0124 (9) −0.0006 (8) C13 0.0582 (11) 0.0675 (13) 0.0559 (11) −0.0081 (10) −0.0044 (9) 0.0030 (10) C14 0.0708 (13) 0.0667 (13) 0.0668 (13) 0.0032 (11) −0.0051 (11) −0.0189 (11) C15 0.0972 (17) 0.0483 (12) 0.0842 (16) −0.0107 (11) −0.0128 (13) −0.0086 (11) C16 0.1023 (17) 0.0629 (14) 0.0776 (15) −0.0290 (12) 0.0094 (13) 0.0007 (11) C17 0.0754 (13) 0.0648 (13) 0.0641 (12) −0.0112 (11) 0.0072 (11) −0.0100 (10) N1 0.145 (2) 0.1040 (17) 0.0750 (14) −0.0220 (14) −0.0059 (14) 0.0297 (13)

Geometric parameters (Å, º)

C1—C5 1.472 (3) C8—C9 1.361 (3)

C1—C6 1.519 (2) C8—H8 0.9300

C1—C2 1.544 (2) C9—C10 1.368 (3)

C1—H1 0.9800 C9—H9 0.9300

C2—C3 1.518 (2) C10—C11 1.376 (2)

C2—H2A 0.9700 C10—H10 0.9300

C2—H2B 0.9700 C11—H11 0.9300

C3—C4 1.515 (2) C12—C17 1.376 (3)

C3—H3A 0.9700 C12—C13 1.379 (3)

C3—H3B 0.9700 C13—C14 1.379 (3)

C4—C12 1.508 (2) C13—H13 0.9300

C4—H4A 0.9700 C14—C15 1.367 (3)

C4—H4B 0.9700 C14—H14 0.9300

C5—N1 1.137 (3) C15—C16 1.371 (3)

C6—C7 1.376 (2) C15—H15 0.9300

C6—C11 1.382 (2) C16—C17 1.373 (3)

C7—C8 1.386 (3) C16—H16 0.9300

C7—H7 0.9300 C17—H17 0.9300

C5—C1—C6 111.74 (15) C9—C8—C7 120.51 (19)

C5—C1—C2 109.94 (15) C9—C8—H8 119.7

C6—C1—C2 111.21 (14) C7—C8—H8 119.7

C5—C1—H1 107.9 C8—C9—C10 119.61 (19)

C6—C1—H1 107.9 C8—C9—H9 120.2

C2—C1—H1 107.9 C10—C9—H9 120.2

C3—C2—C1 114.01 (14) C9—C10—C11 120.24 (19)

C3—C2—H2A 108.8 C9—C10—H10 119.9

C1—C2—H2A 108.7 C11—C10—H10 119.9

C3—C2—H2B 108.7 C10—C11—C6 120.90 (18)

C1—C2—H2B 108.8 C10—C11—H11 119.5

H2A—C2—H2B 107.6 C6—C11—H11 119.5

C4—C3—C2 112.56 (14) C17—C12—C13 117.64 (17)

C2—C3—H3A 109.1 C13—C12—C4 121.70 (18) C4—C3—H3B 109.1 C14—C13—C12 121.39 (19)

C2—C3—H3B 109.1 C14—C13—H13 119.3

H3A—C3—H3B 107.8 C12—C13—H13 119.3

C12—C4—C3 112.25 (15) C15—C14—C13 120.0 (2)

C12—C4—H4A 109.2 C15—C14—H14 120.0

C3—C4—H4A 109.2 C13—C14—H14 120.0

C12—C4—H4B 109.2 C14—C15—C16 119.3 (2)

C3—C4—H4B 109.2 C14—C15—H15 120.3

H4A—C4—H4B 107.9 C16—C15—H15 120.3

N1—C5—C1 178.6 (2) C15—C16—C17 120.5 (2) C7—C6—C11 118.30 (17) C15—C16—H16 119.8 C7—C6—C1 122.37 (16) C17—C16—H16 119.8 C11—C6—C1 119.22 (15) C16—C17—C12 121.2 (2) C6—C7—C8 120.44 (18) C16—C17—H17 119.4

C6—C7—H7 119.8 C12—C17—H17 119.4

C8—C7—H7 119.8