2-(4-Chloro­phen­yl)-4-oxo-4-phenyl­butane­nitrile

Ma, B.; Zhou, H.; Yang, J.

doi:10.1107/S1600536814002335

organic compounds

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ISSN: 2056-9890

Volume 70| Part 3| March 2014| Page o259

doi:10.1107/S1600536814002335

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2-(4-Chlorophenyl)-4-oxo-4-phenylbutanenitrile

Ben Ma,^a Hongyan Zhou ^b and Jingya Yang ^a ^*

^aCollege 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 13 January 2014; accepted 31 January 2014; online 8 February 2014)

The title molecule, C₁₆H₁₂ClNO, has a V-shaped conformation and the dihedral angle between the planes of the phenyl and benzene rings of 64.6 (1)°. No directional intermolecular interactions could be identified in the crystal.

CCDC reference: 984546

Related literature

For hydrocyanation reactions used for the synthesis of related nitrile derivatives, see: Li et al. (2012 ); Lin et al. (2012 ); Yang, Shen & Chen (2010 ); Yang, Wu & Chen (2010 ). For related structures, see: Yang et al. (2011 ); Abdel-Aziz et al. (2012a , 2012b ). For nitrile-containing pharmaceuticals, see: Fleming et al. (2010 ).

Experimental

Crystal data

C₁₆H₁₂ClNO
M_r = 269.72
Orthorhombic, P b c n
a = 31.247 (13) Å
b = 9.1889 (10) Å
c = 9.3719 (12) Å
V = 2690.9 (12) Å³
Z = 8
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 293 K
0.44 × 0.39 × 0.37 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Eos) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ) T_min = 0.584, T_max = 1.000
6683 measured reflections
2642 independent reflections
1605 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.145
S = 1.08
2642 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 984546

Crystal structure: contains datablocks I, exp_1126_4. DOI: 10.1107/S1600536814002335/bh2493sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814002335/bh2493Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814002335/bh2493Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536814002335/bh2493Isup4.cml

checkCIF report

Comment top

Nitriles usually exhibit important biological and pharmacological activity. For instance, many nitrile-containing pharmaceuticals are widely used in clinical treatments (Fleming et al., 2010). In addition, nitrile derivatives are essential synthetic intermediates in organic synthesis because of their easy achievements and versatile transformations (e.g. Li et al., 2012; Lin et al., 2012; Yang, Shen & Chen, 2010; Yang, Wu & Chen, 2010). The title compound exhibits a V-shaped configuration (Fig. 1), previously observed in related structures (Yang et al., 2011; Abdel-Aziz et al., 2012a, 2012b). One molecule interpenetrates with other symmetry-related molecules in the crystal, to generate a two-dimensional roof-like crystal structure (Fig. 2). Finally, the roof-like structures pack to be the stable crystal structure.

Related literature top

For hydrocyanation reactions used for the synthesis of related nitrile derivatives, see: Li et al. (2012); Lin et al. (2012); Yang, Shen & Chen (2010); Yang, Wu & Chen (2010). For related structures, see: Yang et al. (2011); Abdel-Aziz et al. (2012a, 2012b). For nitrile-containing pharmaceuticals, see: Fleming et al. (2010).

Experimental top

The synthesis follows that previously published (Yang, Shen & Chen, 2010). After Cs₂CO₃ (0.5 mg, 0.0015 mmol), (E)-3-(4-chlorophenyl)-1-phenylprop-2-en-1-one (72.8 mg, 0.3 mmol), and dioxane (0.5 ml) were charged into a dry Schlenk tube equipped with cold finger, 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 (as monitored by TLC). Then, H₂O (2 ml) was added at room temperature 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, 15:1) to afford the pure title compound as a white solid (71.2 mg, 88% yield). Colorless single crystals of the title compound suitable for X-ray structure determination were obtained by vapor diffusion of petroleum ether into an ethyl acetate solution, at room temperature.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

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.

2-(4-Chlorophenyl)-4-oxo-4-phenylbutanenitrile top

Crystal data top

C₁₆H₁₂ClNO	D_x = 1.332 Mg m⁻³
M_r = 269.72	Melting point: 383 K
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 1186 reflections
a = 31.247 (13) Å	θ = 3.7–22.6°
b = 9.1889 (10) Å	µ = 0.27 mm⁻¹
c = 9.3719 (12) Å	T = 293 K
V = 2690.9 (12) Å³	Block, colourless
Z = 8	0.44 × 0.39 × 0.37 mm
F(000) = 1120

Data collection top

Agilent SuperNova (Dual, Cu at zero, Eos) diffractometer	2642 independent reflections
Radiation source: MoKa	1605 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.044
Detector resolution: 16.0733 pixels mm^-1	θ_max = 26.0°, θ_min = 3.2°
ω scans	h = −20→38
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −11→10
T_min = 0.584, T_max = 1.000	l = −11→11
6683 measured reflections

Refinement top

Refinement on F²	0 constraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F² > 2σ(F²)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0418P)² + 0.4921P] where P = (F_o² + 2F_c²)/3
2642 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₆H₁₂ClNO	V = 2690.9 (12) Å³
M_r = 269.72	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 31.247 (13) Å	µ = 0.27 mm⁻¹
b = 9.1889 (10) Å	T = 293 K
c = 9.3719 (12) Å	0.44 × 0.39 × 0.37 mm

Data collection top

Agilent SuperNova (Dual, Cu at zero, Eos) diffractometer	2642 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	1605 reflections with I > 2σ(I)
T_min = 0.584, T_max = 1.000	R_int = 0.044
6683 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.08	Δρ_max = 0.14 e Å⁻³
2642 reflections	Δρ_min = −0.23 e Å⁻³
172 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.49185 (3)	0.22108 (11)	0.94462 (10)	0.0911 (4)
O1	0.31808 (7)	0.4639 (2)	1.6227 (2)	0.0802 (7)
N1	0.39810 (8)	0.1944 (3)	1.6798 (3)	0.0696 (7)
C1	0.41798 (9)	0.1701 (3)	1.2875 (3)	0.0602 (8)
H1	0.4064	0.0933	1.3392	0.072*
C2	0.44356 (9)	0.1413 (3)	1.1702 (3)	0.0655 (8)
H2	0.4492	0.0457	1.1436	0.079*
C3	0.46042 (8)	0.2544 (4)	1.0936 (3)	0.0632 (8)
C4	0.45302 (9)	0.3961 (4)	1.1351 (3)	0.0705 (9)
H4	0.4652	0.4728	1.0846	0.085*
C5	0.42749 (9)	0.4235 (3)	1.2521 (3)	0.0655 (8)
H5	0.4224	0.5192	1.2796	0.079*
C6	0.40944 (8)	0.3116 (3)	1.3289 (3)	0.0528 (7)
C7	0.37986 (8)	0.3464 (3)	1.4528 (3)	0.0541 (7)
H7	0.3839	0.4493	1.4768	0.065*
C8	0.33248 (8)	0.3254 (3)	1.4156 (3)	0.0561 (7)
H8A	0.3269	0.3682	1.3228	0.067*
H8B	0.3263	0.2221	1.4094	0.067*
C9	0.30306 (10)	0.3939 (3)	1.5247 (3)	0.0579 (7)
C10	0.25590 (9)	0.3757 (3)	1.5110 (3)	0.0541 (7)
C11	0.22948 (10)	0.4530 (3)	1.6019 (3)	0.0699 (9)
H11	0.2415	0.5151	1.6692	0.084*
C12	0.18561 (11)	0.4396 (4)	1.5944 (4)	0.0797 (10)
H12	0.1683	0.4923	1.6563	0.096*
C13	0.16764 (11)	0.3486 (4)	1.4955 (4)	0.0809 (10)
H13	0.1380	0.3393	1.4904	0.097*
C14	0.19339 (11)	0.2709 (4)	1.4037 (4)	0.0770 (9)
H14	0.1812	0.2091	1.3364	0.092*
C15	0.23731 (10)	0.2848 (3)	1.4116 (3)	0.0643 (8)
H15	0.2546	0.2323	1.3493	0.077*
C16	0.39056 (9)	0.2607 (3)	1.5808 (3)	0.0559 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0720 (5)	0.1253 (8)	0.0759 (6)	0.0063 (5)	0.0188 (5)	−0.0007 (5)
O1	0.0793 (14)	0.0887 (16)	0.0725 (14)	0.0126 (12)	−0.0085 (12)	−0.0260 (12)
N1	0.0627 (15)	0.0749 (18)	0.0712 (18)	0.0033 (13)	−0.0059 (14)	0.0092 (14)
C1	0.0579 (16)	0.0528 (17)	0.070 (2)	−0.0036 (14)	0.0068 (16)	0.0033 (14)
C2	0.0604 (17)	0.0644 (18)	0.072 (2)	0.0008 (16)	0.0029 (17)	−0.0078 (16)
C3	0.0445 (15)	0.085 (2)	0.0606 (19)	0.0018 (15)	−0.0017 (15)	0.0050 (16)
C4	0.0598 (17)	0.072 (2)	0.080 (2)	−0.0025 (16)	0.0099 (17)	0.0201 (17)
C5	0.0653 (17)	0.0531 (17)	0.078 (2)	0.0058 (15)	0.0081 (17)	0.0083 (15)
C6	0.0490 (14)	0.0547 (16)	0.0548 (17)	−0.0010 (13)	−0.0030 (14)	0.0053 (13)
C7	0.0593 (15)	0.0486 (15)	0.0545 (17)	0.0003 (13)	−0.0022 (15)	0.0026 (13)
C8	0.0568 (15)	0.0628 (18)	0.0488 (16)	0.0107 (14)	−0.0024 (14)	0.0000 (13)
C9	0.0695 (18)	0.0541 (16)	0.0502 (17)	0.0128 (15)	−0.0010 (15)	0.0031 (14)
C10	0.0630 (16)	0.0529 (16)	0.0465 (15)	0.0143 (14)	0.0030 (14)	0.0079 (13)
C11	0.077 (2)	0.068 (2)	0.065 (2)	0.0228 (17)	0.0037 (17)	−0.0005 (15)
C12	0.078 (2)	0.088 (3)	0.073 (2)	0.028 (2)	0.0169 (19)	0.0067 (19)
C13	0.0607 (18)	0.098 (3)	0.084 (2)	0.014 (2)	0.0059 (19)	0.020 (2)
C14	0.069 (2)	0.095 (3)	0.068 (2)	−0.0010 (19)	−0.0033 (18)	−0.0019 (18)
C15	0.0646 (18)	0.075 (2)	0.0536 (18)	0.0085 (16)	0.0027 (16)	−0.0027 (15)
C16	0.0499 (15)	0.0567 (17)	0.061 (2)	−0.0012 (13)	−0.0040 (15)	−0.0023 (15)

Geometric parameters (Å, º) top

Cl1—C3	1.734 (3)	C7—C16	1.474 (4)
O1—C9	1.216 (3)	C8—H8A	0.9700
N1—C16	1.134 (4)	C8—H8B	0.9700
C1—H1	0.9300	C8—C9	1.512 (4)
C1—C2	1.385 (4)	C9—C10	1.489 (4)
C1—C6	1.382 (4)	C10—C11	1.383 (4)
C2—H2	0.9300	C10—C15	1.379 (4)
C2—C3	1.369 (4)	C11—H11	0.9300
C3—C4	1.379 (4)	C11—C12	1.378 (4)
C4—H4	0.9300	C12—H12	0.9300
C4—C5	1.379 (4)	C12—C13	1.368 (5)
C5—H5	0.9300	C13—H13	0.9300
C5—C6	1.376 (4)	C13—C14	1.378 (4)
C6—C7	1.518 (4)	C14—H14	0.9300
C7—H7	0.9800	C14—C15	1.380 (5)
C7—C8	1.533 (4)	C15—H15	0.9300

C2—C1—H1	119.5	H8A—C8—H8B	107.9
C6—C1—H1	119.5	C9—C8—C7	112.4 (2)
C6—C1—C2	120.9 (3)	C9—C8—H8A	109.1
C1—C2—H2	120.2	C9—C8—H8B	109.1
C3—C2—C1	119.6 (3)	O1—C9—C8	119.8 (3)
C3—C2—H2	120.2	O1—C9—C10	120.4 (3)
C2—C3—Cl1	120.4 (3)	C10—C9—C8	119.8 (2)
C2—C3—C4	120.3 (3)	C11—C10—C9	118.7 (3)
C4—C3—Cl1	119.3 (2)	C15—C10—C9	122.9 (3)
C3—C4—H4	120.2	C15—C10—C11	118.4 (3)
C5—C4—C3	119.6 (3)	C10—C11—H11	119.5
C5—C4—H4	120.2	C12—C11—C10	121.1 (3)
C4—C5—H5	119.5	C12—C11—H11	119.5
C6—C5—C4	121.1 (3)	C11—C12—H12	120.1
C6—C5—H5	119.5	C13—C12—C11	119.8 (3)
C1—C6—C7	122.0 (2)	C13—C12—H12	120.1
C5—C6—C1	118.5 (3)	C12—C13—H13	120.0
C5—C6—C7	119.5 (3)	C12—C13—C14	120.0 (3)
C6—C7—H7	107.4	C14—C13—H13	120.0
C6—C7—C8	112.8 (2)	C13—C14—H14	120.0
C8—C7—H7	107.4	C13—C14—C15	119.9 (3)
C16—C7—C6	111.8 (2)	C15—C14—H14	120.0
C16—C7—H7	107.4	C10—C15—C14	120.8 (3)
C16—C7—C8	109.7 (2)	C10—C15—H15	119.6
C7—C8—H8A	109.1	C14—C15—H15	119.6
C7—C8—H8B	109.1	N1—C16—C7	178.9 (3)

Cl1—C3—C4—C5	179.0 (2)	C6—C1—C2—C3	−0.4 (4)
O1—C9—C10—C11	7.2 (4)	C6—C7—C8—C9	−166.1 (2)
O1—C9—C10—C15	−172.7 (3)	C7—C8—C9—O1	4.4 (4)
C1—C2—C3—Cl1	−179.0 (2)	C7—C8—C9—C10	−175.9 (2)
C1—C2—C3—C4	1.8 (4)	C8—C9—C10—C11	−172.5 (2)
C1—C6—C7—C8	−75.1 (3)	C8—C9—C10—C15	7.6 (4)
C1—C6—C7—C16	49.1 (3)	C9—C10—C11—C12	−179.6 (3)
C2—C1—C6—C5	−1.0 (4)	C9—C10—C15—C14	179.6 (3)
C2—C1—C6—C7	177.1 (3)	C10—C11—C12—C13	−0.1 (5)
C2—C3—C4—C5	−1.8 (4)	C11—C10—C15—C14	−0.3 (4)
C3—C4—C5—C6	0.4 (4)	C11—C12—C13—C14	−0.1 (5)
C4—C5—C6—C1	1.0 (4)	C12—C13—C14—C15	0.1 (5)
C4—C5—C6—C7	−177.2 (2)	C13—C14—C15—C10	0.1 (5)
C5—C6—C7—C8	103.0 (3)	C15—C10—C11—C12	0.3 (4)
C5—C6—C7—C16	−132.8 (3)	C16—C7—C8—C9	68.5 (3)

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂ClNO
M_r	269.72
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	31.247 (13), 9.1889 (10), 9.3719 (12)
V (Å³)	2690.9 (12)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.44 × 0.39 × 0.37

Data collection
Diffractometer	Agilent SuperNova (Dual, Cu at zero, Eos) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013)
T_min, T_max	0.584, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6683, 2642, 1605
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.145, 1.08
No. of reflections	2642
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.23

Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS2013 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Acknowledgements

The authors thank the National Natural Science Foundation of China (grant No. 21362034), Provincial Nature Science Foundation of Gansu (grant No. 1107RJZ189), Northwest Normal University (grant No. NWNU-LKQN-11–15), and Gansu Agricultural University (grant No. GAU-CX1115) for financial support. We also thank Dr Yong-Liang Shao from the Center of Testing and Analysis, Lanzhou University, for the structure determination.

References

Abdel-Aziz, A. A.-M., El-Azab, A. S., Ng, S. W. & Tiekink, E. R. T. (2012a). Acta Cryst. E68, o736. CSD CrossRef IUCr Journals Google Scholar
Abdel-Aziz, A. A.-M., El-Azab, A. S., Ng, S. W. & Tiekink, E. R. T. (2012b). Acta Cryst. E68, o737. CSD CrossRef IUCr Journals Google Scholar
Agilent (2013). CrysAlis PRO. Agilent Technologies Inc., Santa Clara, CA, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals 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
Li, Z., Liu, C., Zhang, Y., Li, R., Ma, B. & Yang, J. (2012). Synlett, 23, 2567–2571. Web of Science CrossRef CAS Google Scholar
Lin, S., Wei, Y. & Liang, F. (2012). Chem. Commun. 64, 9879–9881. Web of Science CSD CrossRef 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., Wu, S. & Chen, F.-X. (2010). Synlett, pp. 2725–2728. Google Scholar
Yang, J., Zhou, H. & Li, Z. (2011). Acta Cryst. E67, o1610. Web of Science CSD CrossRef IUCr Journals Google Scholar