(E)-2-(2-Formyl­phen­oxy­meth­yl)-3-phenyl­prop-2-ene­nitrile

Swaminathan, K.; Sethusankar, K.; Murugan, G.; Bakthadoss, M.

doi:10.1107/S1600536811025670

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2000

doi:10.1107/S1600536811025670

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(E)-2-(2-Formylphenoxymethyl)-3-phenylprop-2-enenitrile

K. Swaminathan,^a K. Sethusankar,^a ^* G. Murugan ^b and M. Bakthadoss ^b

^aDepartment of Physics, RKM Vivekananda College (Autonomous), Chennai 600 004, India, and ^bDepartment of Organic Chemistry, University of Madras, Maraimalai Campus, Chennai 600 025, India
^*Correspondence e-mail: ksethusankar@yahoo.co.in

(Received 9 May 2011; accepted 29 June 2011; online 9 July 2011)

In the title compound, C₁₇H₁₃NO₂, the dihedral angle between the benzene and the phenyl ring is 65.92 (7)°. The carbonitrile side chain is almost linear, the C—C—N angle being 175.55 (14)°. The crystal structure is stabilized by intermolecular C—H⋯O interactions.

Related literature

For background to the synthesis, see: Bakthadoss & Murugan (2010 ). For a related structure, see: Jasinski et al. (2011 ).

Experimental

Crystal data

C₁₇H₁₃NO₂
M_r = 263.28
Triclinic, $[P \overline 1]$
a = 8.0157 (4) Å
b = 9.2589 (4) Å
c = 10.2348 (5) Å
α = 68.283 (2)°
β = 73.432 (2)°
γ = 79.804 (2)°
V = 674.20 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
12600 measured reflections
2628 independent reflections
2162 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.102
S = 1.03
2628 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O2ⁱ	0.93	2.48	3.2675 (17)	143
Symmetry code: (i) x+1, y, z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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 Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811025670/pv2417sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025670/pv2417Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811025670/pv2417Isup3.cml

checkCIF report

Comment top

The title compound is a stereodefined trisubstituted olefin, synthesized from the corresponding bromoderivative of 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 compund comprises a phenyl ring connected to a benzaldehyde through a chain of acrylonitrile and methoxymethyl groups (Fig. 1). The phenyl rings (C1—C6) and (C11—C16) form dihedral angles of 6.46 (8) and 71.66 (6)°, respectively, with the plane formed by the atoms (N1/C8—C10); the dihedral angle between the two phenyl rings is 65.92 (7)°. The deviation of the atom O2 in the aldehyde group, from the mean plane of the phenyl ring (C11—C16) is 0.0709 (12)Å. The bond angle around C9, in the chain of atoms N1/C9/C8, is 175.55 (14)° and thus the carbonitrile side chain is almost linear. The crystal packing is stabilized by intermolecular C—H···O interactions (Tab. 1 and Fig. 2).

Related literature top

For background to the synthesis, see: Bakthadoss & Murugan (2010). For a related structure, see: Jasinski et al. (2011).

Experimental top

A solution of salicylaldehyde (1.0 mmol, 0.122 g) and potassium carbonate (2.0 mmol, 0.2293 g) in acetonitrile solvent (5 ml) was stirred for 15 minute at room temperature. To this solution, (E)-2-(bromomethyl)-3-phenylacrylonitrile (1.2 mmol, 0.27 g) was added dropwise. 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 the crude product, which was purified through 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 (0.22 g, 84% yield). Recrystallization was carried out using methanol as solvent.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (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) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at 30% probability level.
	Fig. 2. Packing arrangement of the title compound; C—H···O intermolecular interactions are indicated by dashed lines.

(E)-2-(2-Formylphenoxymethyl)-3-phenylprop-2-enenitrile top

Crystal data top

C₁₇H₁₃NO₂	Z = 2
M_r = 263.28	F(000) = 276
Triclinic, P1	D_x = 1.297 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0157 (4) Å	Cell parameters from 2628 reflections
b = 9.2589 (4) Å	θ = 1.0–26.0°
c = 10.2348 (5) Å	µ = 0.09 mm⁻¹
α = 68.283 (2)°	T = 293 K
β = 73.432 (2)°	Block, colourless
γ = 79.804 (2)°	0.30 × 0.25 × 0.25 mm
V = 674.20 (6) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	2162 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 26.0°, θ_min = 2.6°
ω scans	h = −9→9
12600 measured reflections	k = −11→11
2628 independent reflections	l = −12→12

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0528P)² + 0.0828P] where P = (F_o² + 2F_c²)/3
2628 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₇H₁₃NO₂	γ = 79.804 (2)°
M_r = 263.28	V = 674.20 (6) Å³
Triclinic, P1	Z = 2
a = 8.0157 (4) Å	Mo Kα radiation
b = 9.2589 (4) Å	µ = 0.09 mm⁻¹
c = 10.2348 (5) Å	T = 293 K
α = 68.283 (2)°	0.30 × 0.25 × 0.25 mm
β = 73.432 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2162 reflections with I > 2σ(I)
12600 measured reflections	R_int = 0.023
2628 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.03	Δρ_max = 0.12 e Å⁻³
2628 reflections	Δρ_min = −0.17 e Å⁻³
181 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
C1	0.26890 (18)	0.64113 (15)	0.64335 (14)	0.0532 (3)
H1	0.3008	0.6132	0.7305	0.064*
C2	0.2241 (2)	0.79493 (15)	0.57315 (15)	0.0595 (4)
H2	0.2270	0.8700	0.6125	0.071*
C3	0.17519 (19)	0.83824 (15)	0.44570 (16)	0.0602 (4)
H3	0.1450	0.9425	0.3981	0.072*
C4	0.1710 (2)	0.72668 (16)	0.38826 (16)	0.0648 (4)
H4	0.1372	0.7556	0.3017	0.078*
C5	0.21649 (18)	0.57237 (15)	0.45793 (15)	0.0570 (3)
H5	0.2129	0.4980	0.4180	0.068*
C6	0.26761 (15)	0.52628 (13)	0.58692 (13)	0.0449 (3)
C7	0.31669 (16)	0.36612 (13)	0.66887 (13)	0.0468 (3)
H7	0.3373	0.3542	0.7574	0.056*
C8	0.33774 (15)	0.23310 (13)	0.64123 (13)	0.0462 (3)
C9	0.31738 (18)	0.22202 (14)	0.51102 (15)	0.0543 (3)
C10	0.38224 (15)	0.08068 (13)	0.74939 (14)	0.0486 (3)
H10A	0.4728	0.0193	0.7021	0.058*
H10B	0.4233	0.0975	0.8227	0.058*
C11	0.23087 (14)	−0.14432 (12)	0.91208 (12)	0.0385 (3)
C12	0.37770 (16)	−0.21887 (14)	0.96098 (14)	0.0496 (3)
H12	0.4804	−0.1690	0.9277	0.059*
C13	0.37016 (19)	−0.36785 (15)	1.05952 (15)	0.0582 (4)
H13	0.4686	−0.4175	1.0935	0.070*
C14	0.2212 (2)	−0.44558 (15)	1.10927 (14)	0.0586 (4)
H14	0.2196	−0.5474	1.1741	0.070*
C15	0.07545 (17)	−0.37049 (14)	1.06170 (13)	0.0497 (3)
H15	−0.0262	−0.4218	1.0954	0.060*
C16	0.07657 (14)	−0.21887 (13)	0.96393 (11)	0.0395 (3)
C17	−0.08123 (16)	−0.14054 (16)	0.91668 (14)	0.0534 (3)
H17	−0.0751	−0.0399	0.8497	0.064*
N1	0.3060 (2)	0.20353 (14)	0.40992 (15)	0.0774 (4)
O1	0.22458 (10)	0.00245 (9)	0.81342 (9)	0.0484 (2)
O2	−0.21885 (12)	−0.19734 (13)	0.95850 (12)	0.0737 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0663 (8)	0.0489 (7)	0.0454 (7)	−0.0121 (6)	−0.0079 (6)	−0.0176 (6)
C2	0.0776 (10)	0.0449 (7)	0.0588 (8)	−0.0084 (6)	−0.0097 (7)	−0.0244 (6)
C3	0.0708 (9)	0.0423 (7)	0.0632 (9)	0.0010 (6)	−0.0138 (7)	−0.0173 (6)
C4	0.0848 (11)	0.0519 (8)	0.0624 (9)	0.0057 (7)	−0.0312 (8)	−0.0195 (7)
C5	0.0736 (9)	0.0456 (7)	0.0589 (8)	−0.0028 (6)	−0.0204 (7)	−0.0230 (6)
C6	0.0463 (7)	0.0423 (6)	0.0428 (6)	−0.0110 (5)	−0.0012 (5)	−0.0145 (5)
C7	0.0499 (7)	0.0448 (6)	0.0421 (6)	−0.0128 (5)	−0.0041 (5)	−0.0117 (5)
C8	0.0454 (7)	0.0422 (6)	0.0461 (7)	−0.0110 (5)	−0.0023 (5)	−0.0124 (5)
C9	0.0643 (8)	0.0384 (6)	0.0577 (8)	−0.0074 (6)	−0.0094 (6)	−0.0158 (6)
C10	0.0411 (7)	0.0437 (6)	0.0548 (7)	−0.0100 (5)	−0.0047 (5)	−0.0119 (5)
C11	0.0407 (6)	0.0357 (5)	0.0382 (6)	−0.0023 (4)	−0.0092 (5)	−0.0121 (5)
C12	0.0421 (7)	0.0504 (7)	0.0583 (8)	0.0000 (5)	−0.0167 (6)	−0.0189 (6)
C13	0.0644 (9)	0.0514 (7)	0.0619 (8)	0.0136 (6)	−0.0308 (7)	−0.0193 (6)
C14	0.0839 (10)	0.0380 (6)	0.0495 (7)	0.0008 (6)	−0.0211 (7)	−0.0087 (5)
C15	0.0609 (8)	0.0451 (6)	0.0419 (6)	−0.0154 (6)	−0.0047 (6)	−0.0139 (5)
C16	0.0416 (6)	0.0421 (6)	0.0358 (6)	−0.0063 (5)	−0.0073 (5)	−0.0145 (5)
C17	0.0436 (7)	0.0618 (8)	0.0535 (7)	−0.0085 (6)	−0.0120 (6)	−0.0159 (6)
N1	0.1142 (12)	0.0570 (7)	0.0704 (9)	−0.0038 (7)	−0.0291 (8)	−0.0284 (7)
O1	0.0401 (5)	0.0395 (4)	0.0557 (5)	−0.0078 (3)	−0.0119 (4)	−0.0026 (4)
O2	0.0447 (6)	0.1005 (8)	0.0789 (7)	−0.0212 (5)	−0.0146 (5)	−0.0272 (6)

Geometric parameters (Å, º) top

C1—C2	1.3719 (18)	C10—O1	1.4324 (13)
C1—C6	1.3879 (17)	C10—H10A	0.9700
C1—H1	0.9300	C10—H10B	0.9700
C2—C3	1.3656 (19)	C11—O1	1.3631 (13)
C2—H2	0.9300	C11—C12	1.3802 (16)
C3—C4	1.3735 (19)	C11—C16	1.3945 (15)
C3—H3	0.9300	C12—C13	1.3743 (18)
C4—C5	1.3758 (18)	C12—H12	0.9300
C4—H4	0.9300	C13—C14	1.374 (2)
C5—C6	1.3865 (17)	C13—H13	0.9300
C5—H5	0.9300	C14—C15	1.3684 (19)
C6—C7	1.4555 (17)	C14—H14	0.9300
C7—C8	1.3351 (16)	C15—C16	1.3900 (16)
C7—H7	0.9300	C15—H15	0.9300
C8—C9	1.4298 (19)	C16—C17	1.4575 (17)
C8—C10	1.4950 (17)	C17—O2	1.2026 (15)
C9—N1	1.1397 (17)	C17—H17	0.9300

C2—C1—C6	121.36 (12)	C8—C10—H10A	110.5
C2—C1—H1	119.3	O1—C10—H10B	110.5
C6—C1—H1	119.3	C8—C10—H10B	110.5
C3—C2—C1	120.28 (12)	H10A—C10—H10B	108.7
C3—C2—H2	119.9	O1—C11—C12	123.92 (10)
C1—C2—H2	119.9	O1—C11—C16	115.88 (9)
C2—C3—C4	119.54 (12)	C12—C11—C16	120.20 (10)
C2—C3—H3	120.2	C13—C12—C11	119.10 (12)
C4—C3—H3	120.2	C13—C12—H12	120.4
C3—C4—C5	120.40 (13)	C11—C12—H12	120.4
C3—C4—H4	119.8	C14—C13—C12	121.87 (12)
C5—C4—H4	119.8	C14—C13—H13	119.1
C4—C5—C6	120.90 (12)	C12—C13—H13	119.1
C4—C5—H5	119.6	C15—C14—C13	118.78 (12)
C6—C5—H5	119.6	C15—C14—H14	120.6
C5—C6—C1	117.51 (11)	C13—C14—H14	120.6
C5—C6—C7	124.85 (11)	C14—C15—C16	121.20 (12)
C1—C6—C7	117.62 (11)	C14—C15—H15	119.4
C8—C7—C6	132.27 (12)	C16—C15—H15	119.4
C8—C7—H7	113.9	C15—C16—C11	118.81 (11)
C6—C7—H7	113.9	C15—C16—C17	120.15 (11)
C7—C8—C9	124.29 (11)	C11—C16—C17	121.04 (10)
C7—C8—C10	121.16 (11)	O2—C17—C16	124.38 (12)
C9—C8—C10	114.54 (10)	O2—C17—H17	117.8
N1—C9—C8	175.55 (14)	C16—C17—H17	117.8
O1—C10—C8	106.15 (9)	C11—O1—C10	118.29 (9)
O1—C10—H10A	110.5

C6—C1—C2—C3	0.6 (2)	C16—C11—C12—C13	0.92 (18)
C1—C2—C3—C4	0.1 (2)	C11—C12—C13—C14	0.9 (2)
C2—C3—C4—C5	−0.3 (2)	C12—C13—C14—C15	−1.7 (2)
C3—C4—C5—C6	−0.1 (2)	C13—C14—C15—C16	0.54 (19)
C4—C5—C6—C1	0.8 (2)	C14—C15—C16—C11	1.25 (17)
C4—C5—C6—C7	179.50 (13)	C14—C15—C16—C17	−179.03 (11)
C2—C1—C6—C5	−1.04 (19)	O1—C11—C16—C15	178.18 (10)
C2—C1—C6—C7	−179.87 (11)	C12—C11—C16—C15	−1.98 (16)
C5—C6—C7—C8	5.5 (2)	O1—C11—C16—C17	−1.54 (16)
C1—C6—C7—C8	−175.73 (13)	C12—C11—C16—C17	178.30 (11)
C6—C7—C8—C9	1.5 (2)	C15—C16—C17—O2	1.27 (19)
C6—C7—C8—C10	−177.29 (12)	C11—C16—C17—O2	−179.01 (12)
C7—C8—C10—O1	104.09 (13)	C12—C11—O1—C10	4.17 (16)
C9—C8—C10—O1	−74.78 (13)	C16—C11—O1—C10	−175.99 (9)
O1—C11—C12—C13	−179.25 (11)	C8—C10—O1—C11	176.89 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O2ⁱ	0.93	2.48	3.2675 (17)	143

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₃NO₂
M_r	263.28
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.0157 (4), 9.2589 (4), 10.2348 (5)
α, β, γ (°)	68.283 (2), 73.432 (2), 79.804 (2)
V (Å³)	674.20 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.25 × 0.25

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	12600, 2628, 2162
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.102, 1.03
No. of reflections	2628
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.17

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O2ⁱ	0.93	2.48	3.2675 (17)	143

Symmetry code: (i) x+1, y, z.

Acknowledgements

K. Swaminathan and K. Sethusankar thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the X-ray intensity data collection and Dr V. Murugan, Head of the Department of Physics, RKM Vivekananda College, Chennai, India, for providing facilities in the department to carry out this work.

References

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