4-[(E)-3-(4-Methyl­phen­yl)-3-oxoprop-1-en-1-yl]benzo­nitrile

Arunkumar, D.; Samshuddin, S.; Ansar, M.; Mague, J.T.; Ramli, Y.

doi:10.1107/S2414314620008007

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 6| June 2020| x200800

https://doi.org/10.1107/S2414314620008007

Open

access

4-[(E)-3-(4-Methylphenyl)-3-oxoprop-1-en-1-yl]benzonitrile

Dandavathi Arunkumar,^a Seranthimata Samshuddin,^a Mhammed Ansar,^b Joel T. Mague ^c and Youssef Ramli ^b ^*

^aDepartment of Chemistry, Sri Dharmasthala Manjunatheshwara Institute of Technology, Ujire -574 240, and affiliated to, Visvesvaraya Technological University, Belagavi, Karnataka, India, ^bLaboratory of Medicinal Chemistry, Drug Sciences Research Center, Faculty of Medicine and Pharmacy, Mohammed V University, Rabat, Morocco, and ^cDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: y.ramli@um5s.net.ma

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 10 June 2020; accepted 15 June 2020; online 26 June 2020)

In the title molecule C₁₇H₁₃NO, the phenyl rings are inclined to one another by 48.04 (9)°. In the crystal, weak C—H⋯π(ring) interactions form a layered structure parallel to the ab plane.

Keywords: crystal structure; olefin; benzonitrile; carbonyl; chalcone.

CCDC reference: 2009913

Structure description

Chalcones are compounds that can be easily synthesized, and their analogs can also be isolated from natural products (Dhar, 1981 ). Apart from their biological applications, some chalcones with appropriate substituents are also reported to be good NLO materials (Shettigar et al., 2006 ). As part of our work in this area, we now describe the synthesis and structure of the title compound (Fig. 1).

Figure 1
The title molecule showing 30% probability ellipsoids.

The 4-cyanophenyl and 4-methylbenzoyl units are disposed in a trans fashion about the C7=C8 double bond. The dihedral angle between the planes of the C1–C6 and C10–C15 benzene rings is 48.04 (9)° and these benzene rings are inclined to the plane defined by the propene atoms C7, C8 and C9 by 16.0 (1) and 32.6 (1)°, respectively, while O1 lies 0.24 (1) Å away from the propene plane.

In the crystal, stacked molecules form layers parallel to the ab plane with the para substituents on the phenyl rings on the outside surfaces of the layers (Figs. 2 and 3). The molecules constituting each layer are associated through very weak C2—H2⋯Cg2, C5—H5⋯Cg2, C12—H12⋯Cg1 and C15—H15⋯Cg1 interactions across centers of symmetry (Table 1; Cg1 and Cg2 are the centroids of rings C1–C6 and C10–C15, respectively).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C1–C6 and C10–C15 benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Cg2ⁱ	0.93	2.98	3.645 (2)	129
C5—H5⋯Cg2ⁱⁱ	0.93	2.91	3.5929 (18)	132
C12—H12⋯Cg1ⁱⁱⁱ	0.93	2.98	3.637 (2)	129
C15—H15⋯Cg1^iv	0.93	2.99	3.604 (2)	125
Symmetry codes: (i) -x, -y+2, -z+1; (ii) -x+1, -y+1, -z+1; (iii) -x+1, -y+2, -z+1; (iv) -x, -y+1, -z+1.

Figure 2
Elevation view of a portion of one layer viewed along the a-axis direction with C—H⋯π(ring) interactions depicted by dashed lines.

Figure 3
View of a portion of one layer viewed along the b-axis direction with C—H⋯π(ring) interactions depicted by dashed lines.

Synthesis and crystallization

An equimolar mixture of 4-methylacetophenone (0.01 mol) and 4-cyanobenzaldehyde (0.01 mol) in ethanol (30 ml) was stirred for 3 h in the presence of NaOH (5 ml, 30%) at 283 K. The crude solid obtained was collected by filtration and dried. It was purified by repeated recrystallization. Thin layer chromatography was used to check the purity of the compound. Single crystals were grown from ethanol solution by slow evaporation, yield 86%, m.p. 415 K.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₃NO
M_r	247.28
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	5.8686 (2), 7.4955 (3), 15.2792 (5)
α, β, γ (°)	102.195 (2), 90.649 (2), 90.454 (2)
V (Å³)	656.86 (4)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	0.61
Crystal size (mm)	0.28 × 0.27 × 0.22

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.85, 0.88
No. of measured, independent and observed [I > 2σ(I)] reflections	4923, 2432, 2010
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.188, 1.09
No. of reflections	2432
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.20
Computer programs: APEX3 and SAINT (Bruker, 2016 ), SAINT (Bruker, 2016), SHELXT/5 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 2009913

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314620008007/vm4044sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620008007/vm4044Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314620008007/vm4044Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

4-[(E)-3-(4-Methylphenyl)-3-oxoprop-1-en-1-yl]benzonitrile top

Crystal data top

C₁₇H₁₃NO	Z = 2
M_r = 247.28	F(000) = 260
Triclinic, P1	D_x = 1.250 Mg m⁻³
a = 5.8686 (2) Å	Cu Kα radiation, λ = 1.54178 Å
b = 7.4955 (3) Å	Cell parameters from 3797 reflections
c = 15.2792 (5) Å	θ = 3.0–72.3°
α = 102.195 (2)°	µ = 0.61 mm⁻¹
β = 90.649 (2)°	T = 296 K
γ = 90.454 (2)°	Block, colourless
V = 656.86 (4) Å³	0.28 × 0.27 × 0.22 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2432 independent reflections
Radiation source: INCOATEC IµS micro–focus source	2010 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.029
ω scans	θ_max = 72.4°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −6→7
T_min = 0.85, T_max = 0.88	k = −8→9
4923 measured reflections	l = −17→18

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)] = 0.059	H-atom parameters constrained
wR(F²) = 0.188	w = 1/[σ²(F_o²) + (0.1069P)² + 0.0967P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
2432 reflections	Δρ_max = 0.21 e Å⁻³
174 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL 2018/3 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: dual	Extinction coefficient: 0.045 (6)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.98 Å) and included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms.

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

	x	y	z	U_iso*/U_eq
O1	−0.2283 (2)	0.7780 (2)	0.53901 (10)	0.0780 (5)
N1	0.7607 (4)	0.3451 (3)	0.04455 (13)	0.0857 (6)
C1	0.2420 (3)	0.6151 (2)	0.32693 (12)	0.0518 (4)
C2	0.1652 (3)	0.6113 (3)	0.23990 (13)	0.0580 (5)
H2	0.022952	0.658976	0.231111	0.070*
C3	0.2945 (3)	0.5390 (3)	0.16681 (12)	0.0613 (5)
H3	0.240243	0.537500	0.109219	0.074*
C4	0.5071 (3)	0.4682 (2)	0.17993 (12)	0.0551 (5)
C5	0.5873 (3)	0.4695 (2)	0.26642 (12)	0.0556 (5)
H5	0.729197	0.421032	0.274983	0.067*
C6	0.4562 (3)	0.5427 (3)	0.33882 (12)	0.0558 (5)
H6	0.510499	0.544070	0.396389	0.067*
C7	0.0932 (3)	0.6890 (2)	0.40188 (13)	0.0565 (5)
H7	−0.057548	0.708491	0.387342	0.068*
C8	0.1490 (3)	0.7312 (3)	0.48794 (13)	0.0606 (5)
H8	0.299879	0.721005	0.505402	0.073*
C9	−0.0252 (3)	0.7946 (3)	0.55739 (13)	0.0580 (5)
C10	0.0541 (3)	0.8750 (2)	0.64974 (12)	0.0519 (4)
C11	0.2692 (3)	0.9570 (3)	0.66834 (13)	0.0576 (5)
H11	0.369553	0.959948	0.621986	0.069*
C12	0.3322 (3)	1.0337 (3)	0.75564 (14)	0.0611 (5)
H12	0.474772	1.089423	0.766886	0.073*
C13	0.1902 (3)	1.0302 (2)	0.82681 (13)	0.0587 (5)
C14	−0.0233 (3)	0.9458 (3)	0.80743 (13)	0.0613 (5)
H14	−0.121386	0.939348	0.854076	0.074*
C15	−0.0909 (3)	0.8723 (3)	0.72091 (13)	0.0574 (5)
H15	−0.235381	0.819966	0.709725	0.069*
C16	0.2597 (4)	1.1135 (3)	0.92168 (15)	0.0803 (7)
H16A	0.405925	1.172112	0.922209	0.120*
H16B	0.268634	1.019697	0.955689	0.120*
H16C	0.149003	1.201979	0.947754	0.120*
C17	0.6484 (4)	0.3977 (3)	0.10434 (13)	0.0648 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0489 (7)	0.1059 (12)	0.0725 (9)	−0.0032 (7)	−0.0061 (6)	0.0041 (8)
N1	0.0888 (14)	0.1008 (15)	0.0662 (12)	0.0074 (11)	0.0107 (10)	0.0141 (10)
C1	0.0492 (9)	0.0493 (9)	0.0571 (9)	−0.0090 (7)	−0.0044 (7)	0.0121 (7)
C2	0.0506 (9)	0.0646 (11)	0.0614 (10)	−0.0032 (8)	−0.0078 (8)	0.0195 (8)
C3	0.0596 (10)	0.0720 (12)	0.0545 (10)	−0.0105 (9)	−0.0090 (8)	0.0190 (8)
C4	0.0560 (10)	0.0534 (9)	0.0558 (10)	−0.0086 (7)	−0.0011 (7)	0.0115 (7)
C5	0.0489 (9)	0.0591 (10)	0.0593 (10)	−0.0033 (7)	−0.0044 (7)	0.0139 (8)
C6	0.0543 (9)	0.0619 (10)	0.0515 (9)	−0.0046 (8)	−0.0084 (7)	0.0132 (7)
C7	0.0499 (9)	0.0556 (10)	0.0637 (11)	−0.0027 (7)	−0.0052 (8)	0.0120 (8)
C8	0.0503 (9)	0.0696 (12)	0.0606 (10)	0.0019 (8)	−0.0028 (8)	0.0109 (9)
C9	0.0476 (9)	0.0609 (10)	0.0642 (11)	0.0008 (7)	−0.0032 (8)	0.0105 (8)
C10	0.0443 (8)	0.0508 (9)	0.0604 (10)	0.0019 (7)	0.0004 (7)	0.0109 (7)
C11	0.0450 (9)	0.0593 (10)	0.0672 (11)	−0.0029 (7)	0.0050 (7)	0.0105 (8)
C12	0.0457 (8)	0.0578 (10)	0.0758 (12)	−0.0042 (7)	−0.0042 (8)	0.0055 (9)
C13	0.0576 (10)	0.0524 (10)	0.0643 (11)	0.0019 (8)	−0.0046 (8)	0.0082 (8)
C14	0.0568 (10)	0.0627 (11)	0.0633 (11)	−0.0039 (8)	0.0073 (8)	0.0106 (8)
C15	0.0437 (8)	0.0583 (10)	0.0685 (11)	−0.0044 (7)	0.0026 (7)	0.0099 (8)
C16	0.0880 (15)	0.0769 (14)	0.0691 (13)	−0.0031 (12)	−0.0106 (11)	0.0008 (11)
C17	0.0694 (12)	0.0678 (12)	0.0572 (11)	−0.0050 (9)	−0.0026 (9)	0.0135 (9)

Geometric parameters (Å, º) top

O1—C9	1.220 (2)	C8—H8	0.9300
N1—C17	1.136 (3)	C9—C10	1.481 (3)
C1—C2	1.394 (3)	C10—C15	1.392 (3)
C1—C6	1.398 (3)	C10—C11	1.399 (2)
C1—C7	1.464 (3)	C11—C12	1.381 (3)
C2—C3	1.373 (3)	C11—H11	0.9300
C2—H2	0.9300	C12—C13	1.382 (3)
C3—C4	1.389 (3)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.399 (3)
C4—C5	1.396 (3)	C13—C16	1.503 (3)
C4—C17	1.439 (3)	C14—C15	1.373 (3)
C5—C6	1.373 (3)	C14—H14	0.9300
C5—H5	0.9300	C15—H15	0.9300
C6—H6	0.9300	C16—H16A	0.9600
C7—C8	1.323 (3)	C16—H16B	0.9600
C7—H7	0.9300	C16—H16C	0.9600
C8—C9	1.489 (3)

C2—C1—C6	118.38 (16)	C10—C9—C8	118.29 (15)
C2—C1—C7	118.95 (16)	C15—C10—C11	118.40 (17)
C6—C1—C7	122.64 (16)	C15—C10—C9	119.20 (16)
C3—C2—C1	121.61 (17)	C11—C10—C9	122.39 (16)
C3—C2—H2	119.2	C12—C11—C10	119.91 (17)
C1—C2—H2	119.2	C12—C11—H11	120.0
C2—C3—C4	119.20 (17)	C10—C11—H11	120.0
C2—C3—H3	120.4	C11—C12—C13	122.10 (17)
C4—C3—H3	120.4	C11—C12—H12	119.0
C3—C4—C5	120.28 (17)	C13—C12—H12	119.0
C3—C4—C17	120.01 (17)	C12—C13—C14	117.43 (17)
C5—C4—C17	119.69 (17)	C12—C13—C16	121.89 (18)
C6—C5—C4	119.81 (16)	C14—C13—C16	120.68 (18)
C6—C5—H5	120.1	C15—C14—C13	121.31 (17)
C4—C5—H5	120.1	C15—C14—H14	119.3
C5—C6—C1	120.71 (16)	C13—C14—H14	119.3
C5—C6—H6	119.6	C14—C15—C10	120.83 (16)
C1—C6—H6	119.6	C14—C15—H15	119.6
C8—C7—C1	127.33 (17)	C10—C15—H15	119.6
C8—C7—H7	116.3	C13—C16—H16A	109.5
C1—C7—H7	116.3	C13—C16—H16B	109.5
C7—C8—C9	121.20 (17)	H16A—C16—H16B	109.5
C7—C8—H8	119.4	C13—C16—H16C	109.5
C9—C8—H8	119.4	H16A—C16—H16C	109.5
O1—C9—C10	120.84 (17)	H16B—C16—H16C	109.5
O1—C9—C8	120.86 (17)	N1—C17—C4	178.8 (2)

C6—C1—C2—C3	0.0 (3)	O1—C9—C10—C15	22.7 (3)
C7—C1—C2—C3	−178.17 (16)	C8—C9—C10—C15	−156.09 (18)
C1—C2—C3—C4	−0.1 (3)	O1—C9—C10—C11	−156.2 (2)
C2—C3—C4—C5	0.4 (3)	C8—C9—C10—C11	25.0 (3)
C2—C3—C4—C17	−177.81 (17)	C15—C10—C11—C12	−0.4 (3)
C3—C4—C5—C6	−0.6 (3)	C9—C10—C11—C12	178.50 (16)
C17—C4—C5—C6	177.68 (16)	C10—C11—C12—C13	1.0 (3)
C4—C5—C6—C1	0.4 (3)	C11—C12—C13—C14	−0.2 (3)
C2—C1—C6—C5	−0.1 (3)	C11—C12—C13—C16	179.91 (18)
C7—C1—C6—C5	177.96 (16)	C12—C13—C14—C15	−1.2 (3)
C2—C1—C7—C8	−167.96 (18)	C16—C13—C14—C15	178.69 (19)
C6—C1—C7—C8	14.0 (3)	C13—C14—C15—C10	1.8 (3)
C1—C7—C8—C9	−176.11 (17)	C11—C10—C15—C14	−1.0 (3)
C7—C8—C9—O1	13.5 (3)	C9—C10—C15—C14	−179.91 (16)
C7—C8—C9—C10	−167.68 (18)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C1–C6 and C10–C15 benzene rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cg2ⁱ	0.93	2.98	3.645 (2)	129
C5—H5···Cg2ⁱⁱ	0.93	2.91	3.5929 (18)	132
C12—H12···Cg1ⁱⁱⁱ	0.93	2.98	3.637 (2)	129
C15—H15···Cg1^iv	0.93	2.99	3.604 (2)	125

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

Acknowledgements

DA is grateful to the Directorate of Minorities, Government of Karnataka, for providing a research fellowship and Visvesvaraya Technological University, Belagavi, for access to research facilities.

Funding information

The support of NSF–MRI grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

References

Brandenburg, K. & Putz, H. (2012). DIAMOND, Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2016). APEX3 and SAINT. Bruker AXS, Inc., Madison, Wisconsin, USA. Google Scholar
Dhar, D. N. (1981). The Chemistry of Chalcones and Related Compounds. New York: John Wiley and Sons. Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shettigar, V., Patil, P. S., Naveen, S., Dharmaprakash, S. M., Sridhar, M. A. & Shashidhara Prasad, J. (2006). J. Cryst. Growth, 295, 44–49. Web of Science CSD CrossRef CAS Google Scholar