2-(3-Nitro­phen­yl)-4-oxo-4-phenyl­butane­nitrile

Yang, J.; Zhou, H.; Li, Z.

doi:10.1107/S1600536811021052

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1610

doi:10.1107/S1600536811021052

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2-(3-Nitrophenyl)-4-oxo-4-phenylbutanenitrile

Jingya Yang,^a ^* Hongyan Zhou ^b and Zheng Li ^a

^aKey Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education, Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, People's Republic of China, and ^bCollege of Science, Gansu Agricultural University, Lanzhou 730070, People's Republic of China
^*Correspondence e-mail: yangjy@nwnu.edu.cn

(Received 5 May 2011; accepted 1 June 2011; online 11 June 2011)

The structure of the title compound, C₁₆H₁₂N₂O₃, contains two aromatic rings bridged by a C₃ chain. The dihedral angle between the rings is 67.6 (1)°. No classical hydrogen bonds are not found in the crystal structure.

Related literature

For the synthesis of the title compound, see: Yang et al. (2009 ); Yang, Shen & Chen (2010 ). For a related structure, see: Yang, Wu & Chen (2010 ). For nitrile-containing pharmaceuticals, see: Fleming et al. (2010 ).

Experimental

Crystal data

C₁₆H₁₂N₂O₃
M_r = 280.28
Orthorhombic, P b c a
a = 10.105 (9) Å
b = 8.485 (8) Å
c = 31.37 (3) Å
V = 2690 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.28 × 0.25 × 0.24 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.973, T_max = 0.977
11482 measured reflections
2470 independent reflections
1541 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.122
S = 1.03
2470 reflections
191 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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: 10.1107/S1600536811021052/bh2356sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811021052/bh2356Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811021052/bh2356Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536811021052/bh2356Isup4.cml

checkCIF report

Comment top

Nitriles are important synthetic intermediates in organic synthesis, because of their easy preparations and versatile transformations (e.g. Yang, Wu & Chen, 2010). Furthermore, nitriles usually exhibit important biological and pharmacological activity. For example, many nitrile-containing pharmaceuticals are widely used in clinical treatments (Fleming et al., 2010).

Here we report on the crystal structure of the title compound, C₁₆H₁₂N₂O₃ (Fig. 1). In the structure, two aromatic rings are planar (the mean deviation from plane of the benzene ring carrying C1 is 0.0025 Å and the corresponding value of the phenyl ring carrying C10 is 0.0043 Å), but they make a large dihedral angle of 67.6 (1)°, which may be caused by the carbon chain of the bridging section that can rotate freely. From the packing diagram (Fig. 2), it can be seen that the molecules of the title compound, which display a similar V-shaped conformation, are interlayed along the a axis to form a crab-like motif and these crab-like motifs are repeatedly arranged to generate the final crystal structure.

Related literature top

For the synthesis of the title compound, see: Yang et al. (2009); Yang, Shen & Chen (2010). For a related structure, see: Yang, Wu & Chen (2010). For nitrile-containing pharmaceuticals, see: Fleming et al. (2010).

Experimental top

After Cs₂CO₃ (0.5 mg, 0.0015 mmol), (E)-3-(3-nitrophenyl)-1-phenylprop-2-en-1-one (76.0 mg, 0.3 mmol), and dioxane (0.5 ml) were charged into a dry Schlenk tube equipped with cold finger under argon, Me₃SiCN (57 ml, 0.45 mmol) and H₂O (22 ml, 1.2 mmol) were added. The reaction mixture was refluxed until the reaction was complete (monitored by TLC). Then, H₂O (2 ml) was added at r.t. and the resulting mixture was extracted with EtOAc (5 ml). The extract was washed with H₂O (2 ml), brine (3 ml), dried (Na₂SO₄), and concentrated. The crude product was purified by flash column chromatography on silica gel (PE–EtOAc, 10:1) to afford pure title compound as a yellowish solid (75.7 mg, 90% yield), as previously reported (Yang et al., 2009; Yang, Shen & Chen, 2010). Colorless single crystals of the title compound suitable for X-ray structure determination were obtained by vapour diffusion of petroleum ether into its ethyl acetate solution at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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. Thermal ellipsoid plot of the title compound at the 30% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Packing diagram of the title compound; all hydrogen atoms bonded to carbon are omitted for clarity.

2-(3-Nitrophenyl)-4-oxo-4-phenylbutanenitrile top

Crystal data top

C₁₆H₁₂N₂O₃	F(000) = 1168
M_r = 280.28	D_x = 1.384 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1926 reflections
a = 10.105 (9) Å	θ = 2.6–24.8°
b = 8.485 (8) Å	µ = 0.10 mm⁻¹
c = 31.37 (3) Å	T = 296 K
V = 2690 (4) Å³	Block, colourless
Z = 8	0.28 × 0.25 × 0.24 mm

Data collection top

Bruker APEXII CCD diffractometer	2470 independent reflections
Radiation source: fine-focus sealed tube	1541 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→9
T_min = 0.973, T_max = 0.977	k = −10→10
11482 measured reflections	l = −36→38

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.122	w = 1/[σ²(F_o²) + (0.0432P)² + 0.5508P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2470 reflections	Δρ_max = 0.14 e Å⁻³
191 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.0057 (9)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₆H₁₂N₂O₃	V = 2690 (4) Å³
M_r = 280.28	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.105 (9) Å	µ = 0.10 mm⁻¹
b = 8.485 (8) Å	T = 296 K
c = 31.37 (3) Å	0.28 × 0.25 × 0.24 mm

Data collection top

Bruker APEXII CCD diffractometer	2470 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1541 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.977	R_int = 0.064
11482 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 1.03	Δρ_max = 0.14 e Å⁻³
2470 reflections	Δρ_min = −0.21 e Å⁻³
191 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.9659 (2)	0.7730 (3)	0.76158 (8)	0.0531 (7)
H1	1.0233	0.8327	0.7449	0.064*
C2	0.9790 (3)	0.7738 (3)	0.80556 (8)	0.0600 (7)
H2	1.0458	0.8331	0.8182	0.072*
C3	0.8944 (3)	0.6881 (3)	0.83050 (8)	0.0611 (8)
H3	0.9030	0.6898	0.8600	0.073*
C4	0.7968 (3)	0.5993 (3)	0.81171 (8)	0.0612 (8)
H4	0.7392	0.5406	0.8286	0.073*
C5	0.7838 (2)	0.5969 (3)	0.76813 (8)	0.0529 (7)
H5	0.7177	0.5359	0.7558	0.063*
C6	0.8680 (2)	0.6842 (2)	0.74222 (7)	0.0431 (6)
C7	0.8505 (3)	0.6785 (3)	0.69527 (7)	0.0462 (6)
C8	0.9342 (2)	0.7828 (3)	0.66743 (7)	0.0472 (6)
H8A	1.0267	0.7642	0.6740	0.057*
H8B	0.9148	0.8919	0.6741	0.057*
C9	0.9127 (2)	0.7566 (3)	0.61978 (7)	0.0470 (6)
H9	0.8180	0.7682	0.6139	0.056*
C10	0.9863 (2)	0.8761 (2)	0.59265 (6)	0.0411 (6)
C11	1.1213 (3)	0.8670 (3)	0.58598 (7)	0.0505 (6)
H11	1.1692	0.7857	0.5985	0.061*
C12	1.1858 (3)	0.9763 (3)	0.56111 (8)	0.0555 (7)
H12	1.2767	0.9683	0.5570	0.067*
C13	1.1164 (3)	1.0971 (3)	0.54237 (7)	0.0512 (7)
H13	1.1588	1.1705	0.5251	0.061*
C14	0.9831 (3)	1.1064 (2)	0.54980 (6)	0.0408 (6)
C15	0.9168 (2)	0.9985 (2)	0.57425 (6)	0.0425 (6)
H15	0.8260	1.0075	0.5784	0.051*
C16	0.9514 (3)	0.5952 (3)	0.60812 (7)	0.0543 (7)
N1	0.9820 (3)	0.4705 (3)	0.60021 (7)	0.0789 (8)
N2	0.9061 (3)	1.2315 (2)	0.52900 (6)	0.0551 (6)
O1	0.77009 (19)	0.5898 (2)	0.67920 (5)	0.0685 (6)
O2	0.7895 (2)	1.2441 (2)	0.53819 (6)	0.0762 (6)
O3	0.9621 (2)	1.3169 (2)	0.50346 (6)	0.0822 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0547 (19)	0.0492 (15)	0.0554 (16)	−0.0029 (13)	0.0082 (13)	−0.0014 (11)
C2	0.063 (2)	0.0625 (17)	0.0547 (16)	0.0048 (15)	−0.0027 (14)	−0.0084 (13)
C3	0.075 (2)	0.0583 (16)	0.0504 (15)	0.0120 (16)	0.0040 (15)	0.0060 (13)
C4	0.068 (2)	0.0549 (16)	0.0612 (17)	0.0003 (15)	0.0160 (15)	0.0127 (13)
C5	0.0537 (18)	0.0455 (14)	0.0595 (16)	−0.0052 (13)	0.0064 (13)	0.0021 (11)
C6	0.0445 (15)	0.0328 (11)	0.0520 (14)	0.0030 (11)	0.0029 (12)	−0.0005 (10)
C7	0.0465 (17)	0.0381 (12)	0.0539 (14)	0.0004 (12)	0.0034 (12)	−0.0021 (11)
C8	0.0552 (17)	0.0396 (13)	0.0469 (13)	−0.0003 (12)	0.0044 (12)	−0.0019 (10)
C9	0.0488 (16)	0.0423 (13)	0.0498 (14)	0.0000 (12)	−0.0024 (12)	0.0033 (11)
C10	0.0458 (16)	0.0380 (13)	0.0396 (12)	0.0008 (12)	−0.0016 (11)	−0.0032 (9)
C11	0.0514 (18)	0.0459 (14)	0.0541 (14)	0.0061 (13)	−0.0062 (13)	−0.0009 (11)
C12	0.0466 (17)	0.0611 (17)	0.0588 (15)	−0.0019 (14)	0.0072 (13)	−0.0091 (13)
C13	0.065 (2)	0.0471 (15)	0.0418 (13)	−0.0128 (14)	0.0069 (13)	−0.0057 (11)
C14	0.0525 (18)	0.0373 (13)	0.0327 (11)	−0.0009 (12)	−0.0002 (11)	−0.0023 (9)
C15	0.0462 (15)	0.0418 (13)	0.0395 (12)	0.0016 (12)	0.0023 (11)	−0.0047 (10)
C16	0.076 (2)	0.0431 (14)	0.0434 (13)	−0.0050 (14)	0.0011 (13)	0.0012 (11)
N1	0.130 (2)	0.0490 (14)	0.0580 (13)	0.0020 (15)	0.0080 (14)	−0.0041 (11)
N2	0.0806 (19)	0.0456 (13)	0.0390 (11)	0.0003 (13)	−0.0050 (12)	0.0016 (9)
O1	0.0680 (14)	0.0775 (13)	0.0598 (11)	−0.0274 (11)	0.0011 (10)	−0.0029 (10)
O2	0.0735 (16)	0.0810 (14)	0.0740 (13)	0.0222 (12)	−0.0015 (12)	0.0186 (10)
O3	0.1196 (19)	0.0640 (12)	0.0631 (12)	−0.0041 (12)	0.0080 (12)	0.0230 (10)

Geometric parameters (Å, º) top

C1—C6	1.384 (3)	C9—C16	1.470 (4)
C1—C2	1.386 (4)	C9—C10	1.518 (3)
C1—H1	0.9300	C9—H9	0.9800
C2—C3	1.368 (4)	C10—C15	1.380 (3)
C2—H2	0.9300	C10—C11	1.381 (3)
C3—C4	1.374 (4)	C11—C12	1.376 (3)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.374 (4)	C12—C13	1.374 (3)
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.390 (3)	C13—C14	1.369 (4)
C5—H5	0.9300	C13—H13	0.9300
C6—C7	1.484 (3)	C14—C15	1.370 (3)
C7—O1	1.217 (3)	C14—N2	1.469 (3)
C7—C8	1.504 (3)	C15—H15	0.9300
C8—C9	1.527 (3)	C16—N1	1.130 (3)
C8—H8A	0.9700	N2—O2	1.218 (3)
C8—H8B	0.9700	N2—O3	1.219 (3)

C6—C1—C2	120.5 (2)	C16—C9—C8	109.97 (19)
C6—C1—H1	119.7	C10—C9—C8	112.46 (19)
C2—C1—H1	119.7	C16—C9—H9	107.9
C3—C2—C1	120.4 (3)	C10—C9—H9	107.9
C3—C2—H2	119.8	C8—C9—H9	107.9
C1—C2—H2	119.8	C15—C10—C11	118.8 (2)
C2—C3—C4	119.7 (3)	C15—C10—C9	119.2 (2)
C2—C3—H3	120.2	C11—C10—C9	122.1 (2)
C4—C3—H3	120.2	C12—C11—C10	121.0 (2)
C3—C4—C5	120.2 (3)	C12—C11—H11	119.5
C3—C4—H4	119.9	C10—C11—H11	119.5
C5—C4—H4	119.9	C13—C12—C11	120.3 (3)
C4—C5—C6	121.1 (2)	C13—C12—H12	119.9
C4—C5—H5	119.5	C11—C12—H12	119.9
C6—C5—H5	119.5	C14—C13—C12	118.2 (2)
C1—C6—C5	118.1 (2)	C14—C13—H13	120.9
C1—C6—C7	122.6 (2)	C12—C13—H13	120.9
C5—C6—C7	119.3 (2)	C13—C14—C15	122.5 (2)
O1—C7—C6	120.7 (2)	C13—C14—N2	119.1 (2)
O1—C7—C8	119.9 (2)	C15—C14—N2	118.2 (2)
C6—C7—C8	119.3 (2)	C14—C15—C10	119.2 (2)
C7—C8—C9	113.8 (2)	C14—C15—H15	120.4
C7—C8—H8A	108.8	C10—C15—H15	120.4
C9—C8—H8A	108.8	N1—C16—C9	178.2 (3)
C7—C8—H8B	108.8	O2—N2—O3	123.5 (2)
C9—C8—H8B	108.8	O2—N2—C14	118.1 (2)
H8A—C8—H8B	107.7	O3—N2—C14	118.4 (3)
C16—C9—C10	110.6 (2)

C6—C1—C2—C3	−0.7 (4)	C8—C9—C10—C15	−103.3 (2)
C1—C2—C3—C4	0.7 (4)	C16—C9—C10—C11	−47.2 (3)
C2—C3—C4—C5	−0.2 (4)	C8—C9—C10—C11	76.2 (3)
C3—C4—C5—C6	−0.4 (4)	C15—C10—C11—C12	−0.7 (3)
C2—C1—C6—C5	0.2 (3)	C9—C10—C11—C12	179.7 (2)
C2—C1—C6—C7	−179.5 (2)	C10—C11—C12—C13	0.0 (4)
C4—C5—C6—C1	0.4 (4)	C11—C12—C13—C14	1.1 (3)
C4—C5—C6—C7	−179.9 (2)	C12—C13—C14—C15	−1.5 (3)
C1—C6—C7—O1	174.3 (2)	C12—C13—C14—N2	−178.05 (19)
C5—C6—C7—O1	−5.4 (3)	C13—C14—C15—C10	0.7 (3)
C1—C6—C7—C8	−5.2 (3)	N2—C14—C15—C10	177.34 (18)
C5—C6—C7—C8	175.1 (2)	C11—C10—C15—C14	0.4 (3)
O1—C7—C8—C9	−3.5 (3)	C9—C10—C15—C14	179.96 (19)
C6—C7—C8—C9	176.0 (2)	C13—C14—N2—O2	−175.3 (2)
C7—C8—C9—C16	−62.9 (3)	C15—C14—N2—O2	8.0 (3)
C7—C8—C9—C10	173.33 (19)	C13—C14—N2—O3	4.9 (3)
C16—C9—C10—C15	133.2 (2)	C15—C14—N2—O3	−171.9 (2)

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂N₂O₃
M_r	280.28
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	10.105 (9), 8.485 (8), 31.37 (3)
V (Å³)	2690 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.28 × 0.25 × 0.24

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.973, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	11482, 2470, 1541
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.122, 1.03
No. of reflections	2470
No. of parameters	191
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.21

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the National Natural Science Foundation of China (grant No. 20772096) for financial support and Dr Yong-Liang Shao from the Center of Testing and Analysis, Lanzhou University, for the structure determination.

References

Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fleming, F. F., Yao, L., Ravikumar, P. C., Funk, L. & Shook, B. C. (2010). J. Med. Chem. 53, 7902–7917. Web of Science CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, J., Shen, Y. & Chen, F.-X. (2010). Synthesis, pp. 1325–1333. CAS Google Scholar
Yang, J., Wang, Y., Wu, S. & Chen, F.-X. (2009). Synlett, pp. 3365–3367. Google Scholar
Yang, J., Wu, S. & Chen, F.-X. (2010). Synlett, pp. 2725–2728. Google Scholar