4-Oxo-2,4-diphenyl­butane­nitrile

Abdel-Aziz, A.A.-M.; El-Azab, A.S.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536812006137

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o736

doi:10.1107/S1600536812006137

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4-Oxo-2,4-diphenylbutanenitrile

Alaa A.-M. Abdel-Aziz,^a,^b ‡ Adel S. El-Azab,^a,^c Seik Weng Ng ^d,^e and Edward R. T. Tiekink ^d ^*

^aDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia, ^bDepartment of Medicinal Chemistry, Faculty of Pharmacy, University of Mansoura, Mansoura 35516, Egypt, ^cDepartment of Organic Chemistry, Faculty of Pharmacy, Al-Azhar University, Cairo 11884, Egypt, ^dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^e Chemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 12 February 2012; accepted 12 February 2012; online 17 February 2012)

The title molecule, C₁₆H₁₃NO, is twisted, the dihedral angle between the terminal phenyl rings being 68.40 (6)°. In the crystal, C—H⋯O and C—H⋯N interactions lead to supramolecular layers in the bc plane.

Related literature

For background to the synthetic applications of 2,4-diaryl-4-oxo-butanenitriles, see: Coudert et al. (1990 , 1988 ); Iida et al. (2007 ). For the preparation of the title compound, see Coudert et al. (1990). For the structure of the methoxy derivative, see: Abdel-Aziz et al. (2012 ).

Experimental

Crystal data

C₁₆H₁₃NO
M_r = 235.27
Monoclinic, P 2₁ /c
a = 14.2158 (3) Å
b = 8.9244 (2) Å
c = 9.7553 (2) Å
β = 99.217 (2)°
V = 1221.65 (5) Å³
Z = 4
Cu Kα radiation
μ = 0.63 mm⁻¹
T = 100 K
0.30 × 0.30 × 0.15 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.752, T_max = 1.000
4625 measured reflections
2496 independent reflections
2187 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.097
S = 1.02
2496 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N1ⁱ	0.95	2.62	3.3669 (17)	136
C8—H8b⋯O1ⁱⁱ	0.99	2.56	3.5246 (14)	163
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812006137/xu5469sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812006137/xu5469Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812006137/xu5469Isup3.cml

checkCIF report

Comment top

2,4-Diaryl-4-oxo-butanenitriles constitute an important class of difunctional intermediates for both the synthesis of biologically active heterocycles, such as pyridazine derivatives, and as a source ketone (Coudert et al., 1990; Coudert et al., 1988; Iida et al., 2007). Herein, the crystal structure of a 2,4-diaryl-4-oxo-butanenitrile derivative, 2,4-diphenyl-4-oxo-butanenitrile (I), is described. This compound has been prepared previously (Coudert et al., 1990) and the structure of the methoxy derivative is known (Abdel-Aziz et al., 2012).

The molecule of (I), Fig. 1, is twisted as seen in the value of the dihedral angle between the terminal benzene rings of 68.40 (6)°. The twist occurs between the C9—C11 bond [the C8—C9—C11—C12 torsion angle is 107.79 (12)°] with the other part of the molecule being relatively planar [the C7—C8—C9—C11 torsion angle is -179.69 (9)°].

Supramolecular layers in the bc plane are formed in the crystal packing via C—H···O and C—H···N interactions, Fig. 2 and Table 1. These stack along the a axis with no specific intermolecular interactions between the layers, Fig. 3.

Related literature top

For background to the synthetic applications of 2,4-diaryl-4-oxo-butanenitriles, see: Coudert et al. (1990, 1988); Iida et al. (2007). For the preparation of the title compound, see Coudert et al. (1990). For the structure of the methoxy derivative, see: Abdel-Aziz et al. (2012).

Experimental top

Acetone cyanohydrin (0.045 mol) and 10% aqueous sodium carbonate (0.0015 mol and 1.5 ml water) were added to solution of benzalacetophenone (0.015 mol) in ethanol (50 ml). The mixture was heated at reflux temperature for 4 h. After cooling, the product which separated out was filtered off and recrystallized from methanol.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. A view of the supramolecular in the bc plane in (I). The C—H···O and C—H···N interactions are shown as orange and blue dashed lines, respectively.
	Fig. 3. A view in projection down the c axis of the unit-cell contents for (I). The C—H···O and C—H···N interactions are shown as orange and blue dashed lines, respectively.

4-Oxo-2,4-diphenylbutanenitrile top

Crystal data top

C₁₆H₁₃NO	F(000) = 496
M_r = 235.27	D_x = 1.279 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2ybc	Cell parameters from 2233 reflections
a = 14.2158 (3) Å	θ = 3.2–76.0°
b = 8.9244 (2) Å	µ = 0.63 mm⁻¹
c = 9.7553 (2) Å	T = 100 K
β = 99.217 (2)°	Prism, colourless
V = 1221.65 (5) Å³	0.30 × 0.30 × 0.15 mm
Z = 4

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2496 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2187 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.016
Detector resolution: 10.4041 pixels mm^-1	θ_max = 76.2°, θ_min = 3.2°
ω scan	h = −17→17
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −11→6
T_min = 0.752, T_max = 1.000	l = −11→12
4625 measured 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.048P)² + 0.3439P] where P = (F_o² + 2F_c²)/3
2496 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₆H₁₃NO	V = 1221.65 (5) Å³
M_r = 235.27	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 14.2158 (3) Å	µ = 0.63 mm⁻¹
b = 8.9244 (2) Å	T = 100 K
c = 9.7553 (2) Å	0.30 × 0.30 × 0.15 mm
β = 99.217 (2)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2496 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	2187 reflections with I > 2σ(I)
T_min = 0.752, T_max = 1.000	R_int = 0.016
4625 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.02	Δρ_max = 0.22 e Å⁻³
2496 reflections	Δρ_min = −0.20 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
O1	0.36576 (6)	0.21438 (10)	0.43914 (9)	0.0285 (2)
N1	0.17432 (7)	0.10500 (12)	0.59790 (12)	0.0279 (2)
C1	0.49902 (8)	0.30995 (13)	0.59134 (12)	0.0208 (2)
C2	0.53560 (8)	0.42071 (14)	0.68608 (12)	0.0247 (3)
H2	0.4947	0.4960	0.7124	0.030*
C3	0.63208 (9)	0.42086 (16)	0.74205 (13)	0.0298 (3)
H3	0.6570	0.4966	0.8062	0.036*
C4	0.69199 (8)	0.31074 (16)	0.70442 (13)	0.0299 (3)
H4	0.7575	0.3102	0.7441	0.036*
C5	0.65640 (9)	0.20143 (15)	0.60905 (14)	0.0297 (3)
H5	0.6976	0.1268	0.5826	0.036*
C6	0.56030 (9)	0.20125 (14)	0.55228 (13)	0.0252 (3)
H6	0.5361	0.1267	0.4865	0.030*
C7	0.39562 (8)	0.30324 (13)	0.53106 (12)	0.0205 (2)
C8	0.32829 (7)	0.40714 (13)	0.59087 (12)	0.0201 (2)
H8	0.3436	0.5120	0.5698	0.024*
H8B	0.3386	0.3957	0.6931	0.024*
C9	0.22257 (7)	0.37701 (13)	0.53382 (12)	0.0198 (2)
H9	0.2119	0.3901	0.4307	0.024*
C10	0.19687 (8)	0.22196 (13)	0.56679 (12)	0.0211 (2)
C11	0.15783 (7)	0.48444 (12)	0.59617 (12)	0.0187 (2)
C12	0.11047 (8)	0.59901 (13)	0.51696 (12)	0.0218 (2)
H12	0.1195	0.6126	0.4233	0.026*
C13	0.04974 (8)	0.69400 (13)	0.57491 (13)	0.0232 (3)
H13	0.0177	0.7726	0.5207	0.028*
C14	0.03583 (8)	0.67459 (13)	0.71113 (13)	0.0224 (2)
H14	−0.0067	0.7384	0.7496	0.027*
C15	0.08427 (8)	0.56136 (13)	0.79140 (12)	0.0234 (2)
H15	0.0755	0.5483	0.8852	0.028*
C16	0.14544 (8)	0.46762 (12)	0.73418 (12)	0.0211 (2)
H16	0.1792	0.3913	0.7895	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0216 (4)	0.0328 (5)	0.0314 (5)	−0.0005 (4)	0.0048 (3)	−0.0109 (4)
N1	0.0227 (5)	0.0233 (5)	0.0370 (6)	0.0003 (4)	0.0031 (4)	−0.0017 (4)
C1	0.0179 (5)	0.0224 (5)	0.0228 (5)	0.0004 (4)	0.0057 (4)	0.0020 (4)
C2	0.0196 (5)	0.0287 (6)	0.0265 (6)	−0.0012 (5)	0.0058 (4)	−0.0036 (5)
C3	0.0223 (6)	0.0390 (7)	0.0281 (6)	−0.0062 (5)	0.0038 (5)	−0.0029 (6)
C4	0.0165 (5)	0.0441 (8)	0.0290 (6)	−0.0001 (5)	0.0032 (5)	0.0087 (6)
C5	0.0217 (6)	0.0319 (7)	0.0365 (7)	0.0067 (5)	0.0081 (5)	0.0053 (5)
C6	0.0233 (6)	0.0239 (6)	0.0294 (6)	0.0020 (5)	0.0071 (5)	0.0007 (5)
C7	0.0187 (5)	0.0212 (5)	0.0223 (5)	−0.0007 (4)	0.0052 (4)	0.0003 (4)
C8	0.0155 (5)	0.0214 (5)	0.0233 (5)	−0.0004 (4)	0.0032 (4)	−0.0014 (4)
C9	0.0163 (5)	0.0210 (5)	0.0222 (5)	0.0011 (4)	0.0030 (4)	−0.0002 (4)
C10	0.0145 (5)	0.0231 (6)	0.0250 (5)	0.0026 (4)	0.0012 (4)	−0.0036 (5)
C11	0.0136 (5)	0.0177 (5)	0.0248 (5)	−0.0015 (4)	0.0029 (4)	−0.0007 (4)
C12	0.0171 (5)	0.0243 (6)	0.0241 (6)	−0.0001 (4)	0.0042 (4)	0.0043 (5)
C13	0.0167 (5)	0.0208 (5)	0.0317 (6)	0.0019 (4)	0.0023 (4)	0.0047 (5)
C14	0.0175 (5)	0.0193 (5)	0.0308 (6)	0.0011 (4)	0.0054 (4)	−0.0021 (5)
C15	0.0239 (6)	0.0220 (5)	0.0250 (6)	0.0006 (5)	0.0060 (4)	−0.0002 (5)
C16	0.0207 (5)	0.0180 (5)	0.0243 (6)	0.0007 (4)	0.0027 (4)	0.0012 (4)

Geometric parameters (Å, º) top

O1—C7	1.2212 (14)	C8—H8	0.9900
N1—C10	1.1470 (16)	C8—H8B	0.9900
C1—C2	1.3956 (17)	C9—C10	1.4796 (16)
C1—C6	1.3970 (16)	C9—C11	1.5217 (14)
C1—C7	1.4944 (15)	C9—H9	1.0000
C2—C3	1.3926 (17)	C11—C12	1.3889 (16)
C2—H2	0.9500	C11—C16	1.3936 (16)
C3—C4	1.3879 (19)	C12—C13	1.3929 (16)
C3—H3	0.9500	C12—H12	0.9500
C4—C5	1.386 (2)	C13—C14	1.3853 (17)
C4—H4	0.9500	C13—H13	0.9500
C5—C6	1.3894 (17)	C14—C15	1.3914 (16)
C5—H5	0.9500	C14—H14	0.9500
C6—H6	0.9500	C15—C16	1.3868 (16)
C7—C8	1.5151 (15)	C15—H15	0.9500
C8—C9	1.5403 (14)	C16—H16	0.9500

C2—C1—C6	119.34 (11)	H8—C8—H8B	107.7
C2—C1—C7	121.85 (10)	C10—C9—C11	108.43 (9)
C6—C1—C7	118.81 (11)	C10—C9—C8	110.20 (9)
C3—C2—C1	119.96 (11)	C11—C9—C8	111.29 (9)
C3—C2—H2	120.0	C10—C9—H9	109.0
C1—C2—H2	120.0	C11—C9—H9	109.0
C4—C3—C2	120.21 (12)	C8—C9—H9	109.0
C4—C3—H3	119.9	N1—C10—C9	176.20 (12)
C2—C3—H3	119.9	C12—C11—C16	119.46 (10)
C3—C4—C5	120.15 (11)	C12—C11—C9	120.78 (10)
C3—C4—H4	119.9	C16—C11—C9	119.76 (10)
C5—C4—H4	119.9	C11—C12—C13	119.93 (11)
C4—C5—C6	119.88 (12)	C11—C12—H12	120.0
C4—C5—H5	120.1	C13—C12—H12	120.0
C6—C5—H5	120.1	C14—C13—C12	120.41 (11)
C5—C6—C1	120.44 (12)	C14—C13—H13	119.8
C5—C6—H6	119.8	C12—C13—H13	119.8
C1—C6—H6	119.8	C13—C14—C15	119.79 (11)
O1—C7—C1	121.29 (10)	C13—C14—H14	120.1
O1—C7—C8	120.89 (10)	C15—C14—H14	120.1
C1—C7—C8	117.79 (10)	C16—C15—C14	119.82 (11)
C7—C8—C9	113.21 (9)	C16—C15—H15	120.1
C7—C8—H8	108.9	C14—C15—H15	120.1
C9—C8—H8	108.9	C15—C16—C11	120.55 (10)
C7—C8—H8B	108.9	C15—C16—H16	119.7
C9—C8—H8B	108.9	C11—C16—H16	119.7

C6—C1—C2—C3	−0.85 (18)	C7—C8—C9—C10	59.99 (12)
C7—C1—C2—C3	178.58 (11)	C7—C8—C9—C11	−179.69 (9)
C1—C2—C3—C4	−0.31 (19)	C10—C9—C11—C12	−130.84 (11)
C2—C3—C4—C5	1.11 (19)	C8—C9—C11—C12	107.79 (12)
C3—C4—C5—C6	−0.74 (19)	C10—C9—C11—C16	48.89 (13)
C4—C5—C6—C1	−0.44 (19)	C8—C9—C11—C16	−72.47 (13)
C2—C1—C6—C5	1.23 (18)	C16—C11—C12—C13	−1.27 (16)
C7—C1—C6—C5	−178.23 (11)	C9—C11—C12—C13	178.47 (10)
C2—C1—C7—O1	173.35 (11)	C11—C12—C13—C14	−0.31 (17)
C6—C1—C7—O1	−7.21 (17)	C12—C13—C14—C15	1.28 (17)
C2—C1—C7—C8	−8.53 (16)	C13—C14—C15—C16	−0.67 (17)
C6—C1—C7—C8	170.91 (10)	C14—C15—C16—C11	−0.91 (17)
O1—C7—C8—C9	5.29 (15)	C12—C11—C16—C15	1.88 (17)
C1—C7—C8—C9	−172.83 (9)	C9—C11—C16—C15	−177.85 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1ⁱ	0.95	2.62	3.3669 (17)	136
C8—H8b···O1ⁱⁱ	0.99	2.56	3.5246 (14)	163

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₃NO
M_r	235.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	14.2158 (3), 8.9244 (2), 9.7553 (2)
β (°)	99.217 (2)
V (Å³)	1221.65 (5)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.63
Crystal size (mm)	0.30 × 0.30 × 0.15

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.752, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4625, 2496, 2187
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.630

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.097, 1.02
No. of reflections	2496
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.20

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1ⁱ	0.95	2.62	3.3669 (17)	136
C8—H8b···O1ⁱⁱ	0.99	2.56	3.5246 (14)	163

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, −y+1/2, z+1/2.

Footnotes

‡Additional correspondence author, e-mail: alaa_moenes@yahoo.com.

Acknowledgements

This work was supported by the Research Center of Pharmacy, King Saud University, Riyadh, Saudi Arabia. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM·C/HIR/MOHE/SC/12).

References

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