(E)-2-[(2-Formyl­phen­oxy)meth­yl]-3-(4-methyl­phen­yl)prop-2-ene­nitrile

Manikandan, N.; Murugavel, S.; Kannan, D.; Bakthadoss, M.

doi:10.1107/S1600536811051415

organic compounds

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Volume 68| Part 1| January 2012| Page o28

doi:10.1107/S1600536811051415

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(E)-2-[(2-Formylphenoxy)methyl]-3-(4-methylphenyl)prop-2-enenitrile

N. Manikandan,^a S. Murugavel,^b ^* D. Kannan ^c and M. Bakthadoss ^c

^aDepartment of Physics, Bharathidasan Engineering College, Nattrampalli, Vellore 635 854, India, ^bDepartment of Physics, Thanthai Periyar Government Institute of Technology, Vellore 632 002, India, and ^cDepartment of Organic Chemistry, University of Madras, Chennai 600 025, India
^*Correspondence e-mail: smurugavel27@gmail.com

(Received 17 November 2011; accepted 29 November 2011; online 7 December 2011)

In the title compound, C₁₈H₁₅NO₂, the dihedral angle between the two benzene rings is 74.8 (1)°. The carbonitrile chain is almost linear, the C—C—N angle being 176.2 (2)°. In the crystal, π–π interactions [centroid–centroid distance = 3.842 (1) Å] are observed.

Related literature

For background to the synthetic procedure, see: Bakthadoss & Murugan (2010 ). For related structures, see: Swaminathan et al. (2011 ); Prasanna et al. (2011 ).

Experimental

Crystal data

C₁₈H₁₅NO₂
M_r = 277.31
Monoclinic, P 2₁ /c
a = 7.0792 (4) Å
b = 13.7006 (7) Å
c = 15.3587 (9) Å
β = 96.782 (2)°
V = 1479.21 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.23 × 0.21 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.982, T_max = 0.988
15027 measured reflections
3321 independent reflections
1950 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.133
S = 1.01
3321 reflections
191 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia (1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811051415/im2342sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811051415/im2342Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811051415/im2342Isup3.cml

checkCIF report

Comment top

The title compound is a stereodefined trisubstituted olefin, synthesized from the corresponding bromoderivative of a Baylis- Hillman adduct with salicylaldehyde via simple SN₂ reaction in good yields. This o-salicyladehyde derivative is an important precursor for many heterocyclic frameworks (Bakthadoss et al., 2010).

The title compound comprises a benzaldehyde moiety connected to a tolyl ring through a chain formed by a methoxy methyl and a propenenitrile group. The X-ray analysis confirms the molecular structure and atom connectivity as illustrated in Fig.1.

The dihedral angle between the two aromatic rings is 74.8 (1)°. The propenenitrile (N1/C17/C8–C11) plane forms dihedral angles of 53.6 (1)° and 22.7 (1)°, respectively, with the formyl phenyl and tolyl rings. The bond length C9—C17 [1.431 (2) Å] is significantly shorter than the expected value for a C—C single bond because of conjugation effects (Prasanna et al., 2011). The carbonitrile side chain (C9–C17–N1) is almost linear, with the angle around the central carbon atom being 176.2 (2)°. The geometric parameters of the title molecule agree well with those reported for similar structures (Swaminathan et al., 2011, Prasanna et al., 2011).

The crystal packing (Fig. 2) is stabilized by intermolecular π—π interactions with a Cg—Cgⁱ seperation of 3.842 (1) Å [Fig. 2; Cg is the centroid of the C1–C6 benzene ring, symmetry code as in Fig. 2].

Related literature top

For background to the synthetic procedure, see: Bakthadoss & Murugan (2010). For related structures, see: Swaminathan et al. (2011); Prasanna et al. (2011).

Experimental top

A solution of salicylaldehyde (1.0 mmol, 0.12 g) and potassium carbonate (1.5 mmol, 0.207 g) in acetonitrile was stirred for 15 minutes at room temperature. To this solution, (E)-2-(bromomethyl)-3-(4-methylphenyl)prop-2-enenitrile (1.2 mmol, 0.28 g) was added dropwise till the addition is complete. After the completion of the reaction, as indicated by TLC, acetonitrile was evaporated. EtOAc (15 ml) and water (15 ml) were added to the crude mass. The organic layer was dried over anhydrous sodium sulfate. Removal of solvent led to a crude product, which was purified through a pad of silica gel (100–200 mesh) using ethylacetate and hexanes (1:9) as solvents. The pure title compound was obtained as a colourless solid (0.24 g, 86 % yield). Recrystallization was carried out using ethylacetate as the solvent.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia (1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of the title compound showing displacement ellipsoids at the 30% probability level. H atoms are presented as a small spheres of arbitrary radii.
	Fig. 2. View of the π—π interactions (dotted lines) in the crystal structure of the title compound. Cg denotes the centroid of the C1–C6 benzene ring. [Symmetry code: (i) -x, 1-y, -z].

(E)-2-[(2-Formylphenoxy)methyl]-3-(4-methylphenyl)prop-2-enenitrile top

Crystal data top

C₁₈H₁₅NO₂	F(000) = 584
M_r = 277.31	D_x = 1.245 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3403 reflections
a = 7.0792 (4) Å	θ = 2.0–27.5°
b = 13.7006 (7) Å	µ = 0.08 mm⁻¹
c = 15.3587 (9) Å	T = 293 K
β = 96.782 (2)°	Block, yellow
V = 1479.21 (14) Å³	0.23 × 0.21 × 0.15 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	3321 independent reflections
Radiation source: fine-focus sealed tube	1950 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 10.0 pixels mm^-1	θ_max = 27.6°, θ_min = 2.0°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −17→17
T_min = 0.982, T_max = 0.988	l = −19→19
15027 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0553P)² + 0.2089P] where P = (F_o² + 2F_c²)/3
3321 reflections	(Δ/σ)_max < 0.001
191 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₈H₁₅NO₂	V = 1479.21 (14) Å³
M_r = 277.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.0792 (4) Å	µ = 0.08 mm⁻¹
b = 13.7006 (7) Å	T = 293 K
c = 15.3587 (9) Å	0.23 × 0.21 × 0.15 mm
β = 96.782 (2)°

Data collection top

Bruker APEXII CCD diffractometer	3321 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1950 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.988	R_int = 0.022
15027 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.133	H-atom parameters constrained
S = 1.01	Δρ_max = 0.14 e Å⁻³
3321 reflections	Δρ_min = −0.14 e Å⁻³
191 parameters

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.

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

	x	y	z	U_iso*/U_eq
N1	0.6118 (2)	0.26454 (11)	0.25898 (11)	0.0828 (5)
O1	0.2658 (2)	0.23139 (12)	−0.09622 (11)	0.1133 (5)
O2	0.25632 (15)	0.38860 (8)	0.11791 (7)	0.0726 (3)
C1	0.0835 (2)	0.37959 (11)	0.06904 (11)	0.0621 (4)
C2	−0.0823 (2)	0.42103 (13)	0.09048 (12)	0.0750 (5)
H2	−0.0825	0.4565	0.1421	0.090*
C3	−0.2478 (2)	0.40934 (15)	0.03456 (14)	0.0856 (6)
H3	−0.3599	0.4372	0.0489	0.103*
C4	−0.2505 (3)	0.35721 (16)	−0.04214 (14)	0.0879 (6)
H4	−0.3631	0.3502	−0.0794	0.105*
C5	−0.0866 (3)	0.31602 (14)	−0.06293 (12)	0.0777 (5)
H5	−0.0879	0.2812	−0.1150	0.093*
C6	0.0820 (2)	0.32522 (11)	−0.00780 (11)	0.0648 (4)
C7	0.2538 (3)	0.27629 (15)	−0.02978 (14)	0.0846 (5)
H7	0.3621	0.2802	0.0107	0.101*
C8	0.2646 (2)	0.43560 (13)	0.20139 (11)	0.0716 (5)
H8A	0.1879	0.4003	0.2392	0.086*
H8B	0.2167	0.5018	0.1945	0.086*
C9	0.4680 (2)	0.43625 (11)	0.24015 (10)	0.0627 (4)
C10	0.5640 (2)	0.51893 (12)	0.25968 (10)	0.0691 (5)
H10	0.4965	0.5755	0.2432	0.083*
C11	0.7555 (2)	0.53562 (11)	0.30210 (10)	0.0645 (4)
C12	0.8639 (3)	0.46728 (13)	0.35274 (12)	0.0802 (5)
H12	0.8151	0.4051	0.3595	0.096*
C13	1.0416 (3)	0.49015 (14)	0.39295 (13)	0.0867 (6)
H13	1.1104	0.4430	0.4268	0.104*
C14	1.1218 (3)	0.58109 (14)	0.38479 (12)	0.0775 (5)
C15	1.0151 (3)	0.64806 (14)	0.33374 (14)	0.0858 (6)
H15	1.0656	0.7097	0.3260	0.103*
C16	0.8365 (3)	0.62670 (12)	0.29389 (13)	0.0799 (5)
H16	0.7680	0.6744	0.2606	0.096*
C17	0.5526 (2)	0.34163 (12)	0.25245 (11)	0.0626 (4)
C18	1.3145 (3)	0.60602 (18)	0.43169 (16)	0.1045 (7)
H18A	1.3777	0.6508	0.3967	0.157*
H18B	1.3890	0.5476	0.4411	0.157*
H18C	1.2998	0.6356	0.4872	0.157*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0778 (10)	0.0609 (9)	0.1058 (12)	−0.0005 (7)	−0.0062 (8)	−0.0046 (8)
O1	0.1137 (12)	0.1266 (12)	0.1033 (12)	−0.0130 (9)	0.0288 (9)	−0.0442 (10)
O2	0.0653 (7)	0.0851 (8)	0.0650 (7)	0.0095 (5)	−0.0017 (5)	−0.0154 (6)
C1	0.0592 (9)	0.0628 (9)	0.0630 (10)	−0.0010 (7)	0.0026 (8)	0.0060 (8)
C2	0.0696 (11)	0.0788 (11)	0.0761 (12)	0.0068 (8)	0.0068 (9)	0.0040 (9)
C3	0.0615 (11)	0.0977 (14)	0.0965 (15)	0.0056 (9)	0.0051 (10)	0.0173 (12)
C4	0.0681 (12)	0.1052 (15)	0.0864 (14)	−0.0147 (10)	−0.0076 (10)	0.0145 (12)
C5	0.0758 (12)	0.0859 (12)	0.0700 (12)	−0.0228 (9)	0.0022 (9)	0.0022 (9)
C6	0.0651 (10)	0.0634 (9)	0.0656 (10)	−0.0123 (7)	0.0067 (8)	0.0028 (8)
C7	0.0784 (12)	0.0901 (13)	0.0856 (14)	−0.0107 (10)	0.0112 (10)	−0.0195 (11)
C8	0.0733 (10)	0.0748 (11)	0.0655 (11)	0.0118 (8)	0.0038 (8)	−0.0101 (8)
C9	0.0720 (10)	0.0596 (9)	0.0554 (9)	0.0067 (7)	0.0026 (7)	−0.0061 (7)
C10	0.0839 (11)	0.0567 (9)	0.0656 (10)	0.0108 (8)	0.0037 (9)	−0.0036 (8)
C11	0.0798 (11)	0.0495 (8)	0.0640 (10)	0.0044 (7)	0.0078 (8)	−0.0086 (7)
C12	0.1049 (14)	0.0552 (9)	0.0741 (11)	−0.0040 (9)	−0.0157 (10)	−0.0031 (8)
C13	0.1041 (14)	0.0701 (11)	0.0791 (13)	0.0091 (10)	−0.0170 (11)	−0.0103 (9)
C14	0.0785 (11)	0.0775 (12)	0.0773 (12)	0.0015 (9)	0.0130 (9)	−0.0236 (10)
C15	0.0853 (13)	0.0634 (11)	0.1111 (16)	−0.0060 (9)	0.0212 (12)	−0.0088 (11)
C16	0.0834 (12)	0.0572 (10)	0.0991 (14)	0.0075 (8)	0.0105 (10)	0.0000 (9)
C17	0.0622 (9)	0.0593 (10)	0.0650 (10)	−0.0037 (7)	0.0013 (7)	−0.0061 (8)
C18	0.0862 (14)	0.1194 (17)	0.1068 (17)	−0.0062 (12)	0.0066 (12)	−0.0322 (14)

Geometric parameters (Å, º) top

N1—C17	1.1362 (19)	C9—C10	1.337 (2)
O1—C7	1.203 (2)	C9—C17	1.431 (2)
O2—C1	1.3634 (17)	C10—C11	1.451 (2)
O2—C8	1.4297 (19)	C10—H10	0.9300
C1—C2	1.378 (2)	C11—C16	1.385 (2)
C1—C6	1.395 (2)	C11—C12	1.389 (2)
C2—C3	1.378 (2)	C12—C13	1.371 (2)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.376 (3)	C13—C14	1.381 (3)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.362 (3)	C14—C15	1.374 (3)
C4—H4	0.9300	C14—C18	1.505 (3)
C5—C6	1.385 (2)	C15—C16	1.370 (3)
C5—H5	0.9300	C15—H15	0.9300
C6—C7	1.462 (3)	C16—H16	0.9300
C7—H7	0.9300	C18—H18A	0.9600
C8—C9	1.492 (2)	C18—H18B	0.9600
C8—H8A	0.9700	C18—H18C	0.9600
C8—H8B	0.9700

C1—O2—C8	118.26 (12)	C17—C9—C8	114.60 (13)
O2—C1—C2	124.43 (15)	C9—C10—C11	131.12 (15)
O2—C1—C6	115.50 (14)	C9—C10—H10	114.4
C2—C1—C6	120.06 (15)	C11—C10—H10	114.4
C3—C2—C1	119.25 (18)	C16—C11—C12	116.81 (16)
C3—C2—H2	120.4	C16—C11—C10	118.41 (15)
C1—C2—H2	120.4	C12—C11—C10	124.76 (16)
C4—C3—C2	121.25 (18)	C13—C12—C11	121.01 (17)
C4—C3—H3	119.4	C13—C12—H12	119.5
C2—C3—H3	119.4	C11—C12—H12	119.5
C5—C4—C3	119.34 (17)	C12—C13—C14	122.04 (18)
C5—C4—H4	120.3	C12—C13—H13	119.0
C3—C4—H4	120.3	C14—C13—H13	119.0
C4—C5—C6	121.04 (18)	C15—C14—C13	116.75 (18)
C4—C5—H5	119.5	C15—C14—C18	121.87 (19)
C6—C5—H5	119.5	C13—C14—C18	121.36 (19)
C5—C6—C1	119.04 (16)	C16—C15—C14	121.92 (18)
C5—C6—C7	119.82 (17)	C16—C15—H15	119.0
C1—C6—C7	121.13 (15)	C14—C15—H15	119.0
O1—C7—C6	125.05 (18)	C15—C16—C11	121.46 (17)
O1—C7—H7	117.5	C15—C16—H16	119.3
C6—C7—H7	117.5	C11—C16—H16	119.3
O2—C8—C9	107.21 (13)	N1—C17—C9	176.18 (17)
O2—C8—H8A	110.3	C14—C18—H18A	109.5
C9—C8—H8A	110.3	C14—C18—H18B	109.5
O2—C8—H8B	110.3	H18A—C18—H18B	109.5
C9—C8—H8B	110.3	C14—C18—H18C	109.5
H8A—C8—H8B	108.5	H18A—C18—H18C	109.5
C10—C9—C17	122.98 (14)	H18B—C18—H18C	109.5
C10—C9—C8	122.40 (14)

C8—O2—C1—C2	6.6 (2)	O2—C8—C9—C17	−59.52 (19)
C8—O2—C1—C6	−174.26 (14)	C17—C9—C10—C11	−6.1 (3)
O2—C1—C2—C3	178.05 (15)	C8—C9—C10—C11	175.59 (16)
C6—C1—C2—C3	−1.0 (2)	C9—C10—C11—C16	163.39 (19)
C1—C2—C3—C4	0.0 (3)	C9—C10—C11—C12	−18.2 (3)
C2—C3—C4—C5	0.3 (3)	C16—C11—C12—C13	0.6 (3)
C3—C4—C5—C6	0.5 (3)	C10—C11—C12—C13	−177.83 (17)
C4—C5—C6—C1	−1.5 (3)	C11—C12—C13—C14	−0.5 (3)
C4—C5—C6—C7	177.08 (18)	C12—C13—C14—C15	−0.4 (3)
O2—C1—C6—C5	−177.37 (13)	C12—C13—C14—C18	178.02 (19)
C2—C1—C6—C5	1.8 (2)	C13—C14—C15—C16	1.1 (3)
O2—C1—C6—C7	4.1 (2)	C18—C14—C15—C16	−177.31 (19)
C2—C1—C6—C7	−176.79 (16)	C14—C15—C16—C11	−1.0 (3)
C5—C6—C7—O1	4.5 (3)	C12—C11—C16—C15	0.1 (3)
C1—C6—C7—O1	−176.95 (19)	C10—C11—C16—C15	178.63 (17)
C1—O2—C8—C9	−179.60 (13)	C10—C9—C17—N1	−160 (3)
O2—C8—C9—C10	118.94 (17)	C8—C9—C17—N1	19 (3)

Experimental details

Crystal data
Chemical formula	C₁₈H₁₅NO₂
M_r	277.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.0792 (4), 13.7006 (7), 15.3587 (9)
β (°)	96.782 (2)
V (Å³)	1479.21 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.23 × 0.21 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.982, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	15027, 3321, 1950
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.133, 1.01
No. of reflections	3321
No. of parameters	191
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.14

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia (1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

The authors thank Dr Babu Vargheese, SAIF, IIT, Madras, India, for his help with the data collection.

References

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