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

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K, P = 0.0 kPa
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.056
• wR factor = 0.145
• Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0043 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C16 H12 Cl N O
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......     11.735 Check
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.741 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         11

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT793_ALERT_4_G The Model has Chirality at C7           (Verify)          R
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          4 Why ?

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

Carbon-bound H-atoms were placed in calculated positions (aromatic CH: 0.93 Å; methylene CH₂: 0.97 Å; methine CH: 0.98 Å) and were included in the riding model approximation, with U_iso(H) set to 1.2U_eq(carrier C).

Computing details

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

	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

Crystal data

C16H12ClNO	Dx = 1.332 Mg m^−3
Mr = 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) Å^3	Block, colourless
Z = 8	0.44 × 0.39 × 0.37 mm
F(000) = 1120

Data collection

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

Refinement

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

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

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)