(E)-3-(2-Chloro­phen­yl)-2-[(2-formylphen­oxy)meth­yl]prop-2-ene­nitrile

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

doi:10.1107/S1600536812008410

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o934

doi:10.1107/S1600536812008410

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(E)-3-(2-Chlorophenyl)-2-[(2-formylphenoxy)methyl]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, Maraimalai Campus, Chennai 600 025, India
^*Correspondence e-mail: smurugavel27@gmail.com

(Received 22 February 2012; accepted 24 February 2012; online 3 March 2012)

In the title compound, C₁₇H₁₂ClNO₂, the dihedral angle between the two benzene rings is 42.9 (1)°. There are no sgnificant intermolecular interactions.

Related literature

For background to the synthetic procedure, see: Bakthadoss & Murugan (2010 ). For related structures, see: Manikandan et al. (2012 ); Prasanna et al. (2011 ).

Experimental

Crystal data

C₁₇H₁₂ClNO₂
M_r = 297.73
Triclinic, $[P \overline 1]$
a = 7.5022 (4) Å
b = 7.8301 (4) Å
c = 13.2379 (8) Å
α = 75.470 (3)°
β = 84.696 (2)°
γ = 70.935 (2)°
V = 711.43 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 293 K
0.24 × 0.21 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.937, T_max = 0.960
14438 measured reflections
3433 independent reflections
2685 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.114
S = 1.04
3433 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.19 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/S1600536812008410/bt5830sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812008410/bt5830Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812008410/bt5830Isup3.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 & Murugan, 2010).

The title compound comprises a benzaldehyde moiety connected to a chlorophenyl 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 42.9 (1)°. The propenenitrile (N1/C17/C8–C11) plane forms dihedral angles of 12.4 (1)° and 36.0 (1)°, respectively, with the formyl phenyl and chloro phenyl rings. The Cl1 atom deviates from the plane of attached ring by 0.019 (1) Å. The bond length C9—C17 [1.443 (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 C atom being 178.1 (2)°. The geometric parameters of the title molecule agree well with those reported for similar structures (Manikandan et al., 2012; Prasanna et al., 2011).

Related literature top

For background to the synthetic procedure, see: Bakthadoss & Murugan (2010). For related structures, see: Manikandan et al. (2012); Prasanna et al. 2011).

Experimental top

A solution of salicylaldehyde (1.0 mmol, 0.122 g) and potassium carbonate (1.5 mmol, 0.207 g) in acetonitrile solvent was stirred for 15 min at room temperature. To this solution, (E)-2-(bromomethyl)-3-(2-chlorophenyl)prop-2-enenitrile (1.2 mmol, 0.308 g) was added drop wise 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 ethyl acetate and hexanes (1:9) as solvents. The pure title compound was obtained as a colorless solid (0.270 g, 90% yield). Recrystallization was carried out using ethyl acetate as solvent.

Structure description top

For background to the synthetic procedure, see: Bakthadoss & Murugan (2010). For related structures, see: Manikandan et al. (2012); Prasanna et al. 2011).

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.

(E)-3-(2-Chlorophenyl)-2-[(2-formylphenoxy)methyl]prop-2-enenitrile top

Crystal data top

C₁₇H₁₂ClNO₂	Z = 2
M_r = 297.73	F(000) = 308
Triclinic, P1	D_x = 1.390 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5022 (4) Å	Cell parameters from 3463 reflections
b = 7.8301 (4) Å	θ = 2.8–28.1°
c = 13.2379 (8) Å	µ = 0.27 mm⁻¹
α = 75.470 (3)°	T = 293 K
β = 84.696 (2)°	Block, colourless
γ = 70.935 (2)°	0.24 × 0.21 × 0.15 mm
V = 711.43 (7) Å³

Data collection top

Bruker APEXII CCD diffractometer	3433 independent reflections
Radiation source: fine-focus sealed tube	2685 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 10.0 pixels mm^-1	θ_max = 28.1°, θ_min = 2.8°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −10→10
T_min = 0.937, T_max = 0.960	l = −17→17
14438 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) = 0.114	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.053P)² + 0.159P] where P = (F_o² + 2F_c²)/3
3433 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₇H₁₂ClNO₂	γ = 70.935 (2)°
M_r = 297.73	V = 711.43 (7) Å³
Triclinic, P1	Z = 2
a = 7.5022 (4) Å	Mo Kα radiation
b = 7.8301 (4) Å	µ = 0.27 mm⁻¹
c = 13.2379 (8) Å	T = 293 K
α = 75.470 (3)°	0.24 × 0.21 × 0.15 mm
β = 84.696 (2)°

Data collection top

Bruker APEXII CCD diffractometer	3433 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2685 reflections with I > 2σ(I)
T_min = 0.937, T_max = 0.960	R_int = 0.029
14438 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.04	Δρ_max = 0.20 e Å⁻³
3433 reflections	Δρ_min = −0.19 e Å⁻³
190 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
Cl1	0.31341 (8)	0.23140 (7)	0.01456 (3)	0.07011 (17)
N1	0.1141 (2)	−0.1357 (2)	0.40658 (12)	0.0660 (4)
O1	0.3876 (2)	−0.21291 (18)	0.75288 (10)	0.0765 (4)
O2	0.28615 (15)	0.15782 (13)	0.48411 (7)	0.0436 (2)
C1	0.32059 (19)	0.22280 (18)	0.56458 (10)	0.0364 (3)
C2	0.3173 (2)	0.4030 (2)	0.55536 (12)	0.0471 (4)
H2	0.2830	0.4913	0.4928	0.057*
C3	0.3655 (3)	0.4509 (2)	0.64002 (14)	0.0562 (4)
H3	0.3639	0.5724	0.6336	0.067*
C4	0.4160 (3)	0.3238 (2)	0.73390 (13)	0.0559 (4)
H4	0.4513	0.3578	0.7896	0.067*
C5	0.4132 (2)	0.1464 (2)	0.74357 (11)	0.0474 (4)
H5	0.4442	0.0603	0.8071	0.057*
C6	0.36463 (19)	0.09286 (18)	0.66019 (10)	0.0377 (3)
C7	0.3555 (2)	−0.0949 (2)	0.67304 (12)	0.0479 (4)
H7	0.3225	−0.1251	0.6153	0.057*
C8	0.1837 (2)	0.2928 (2)	0.39872 (11)	0.0428 (3)
H8A	0.2576	0.3715	0.3627	0.051*
H8B	0.0670	0.3705	0.4233	0.051*
C9	0.1425 (2)	0.1907 (2)	0.32654 (11)	0.0407 (3)
C10	0.1257 (2)	0.2525 (2)	0.22304 (11)	0.0453 (3)
H10	0.0988	0.1754	0.1876	0.054*
C11	0.1448 (2)	0.4273 (2)	0.15926 (11)	0.0450 (3)
C12	0.2291 (2)	0.4332 (2)	0.05996 (12)	0.0505 (4)
C13	0.2510 (3)	0.5949 (3)	−0.00219 (14)	0.0639 (5)
H13	0.3080	0.5953	−0.0676	0.077*
C14	0.1887 (3)	0.7543 (3)	0.03273 (17)	0.0725 (6)
H14	0.2040	0.8635	−0.0090	0.087*
C15	0.1029 (3)	0.7550 (3)	0.12961 (16)	0.0693 (5)
H15	0.0605	0.8643	0.1528	0.083*
C16	0.0804 (3)	0.5936 (2)	0.19183 (13)	0.0562 (4)
H16	0.0212	0.5955	0.2566	0.067*
C17	0.1252 (2)	0.0091 (2)	0.37263 (11)	0.0463 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0911 (4)	0.0811 (3)	0.0395 (2)	−0.0294 (3)	0.0038 (2)	−0.0151 (2)
N1	0.0812 (11)	0.0554 (9)	0.0620 (9)	−0.0321 (8)	0.0090 (8)	−0.0041 (7)
O1	0.1249 (12)	0.0518 (7)	0.0519 (7)	−0.0394 (8)	−0.0187 (7)	0.0113 (6)
O2	0.0599 (6)	0.0349 (5)	0.0322 (5)	−0.0102 (4)	−0.0091 (4)	−0.0044 (4)
C1	0.0398 (7)	0.0358 (7)	0.0329 (6)	−0.0113 (5)	0.0013 (5)	−0.0083 (5)
C2	0.0612 (9)	0.0358 (7)	0.0424 (8)	−0.0170 (7)	0.0022 (7)	−0.0043 (6)
C3	0.0757 (11)	0.0435 (8)	0.0598 (10)	−0.0286 (8)	0.0056 (8)	−0.0197 (7)
C4	0.0689 (11)	0.0625 (10)	0.0472 (9)	−0.0272 (8)	0.0005 (7)	−0.0242 (8)
C5	0.0562 (9)	0.0514 (9)	0.0344 (7)	−0.0170 (7)	−0.0019 (6)	−0.0089 (6)
C6	0.0424 (7)	0.0352 (7)	0.0341 (7)	−0.0121 (6)	0.0002 (5)	−0.0062 (5)
C7	0.0610 (9)	0.0390 (8)	0.0421 (8)	−0.0176 (7)	−0.0056 (7)	−0.0025 (6)
C8	0.0504 (8)	0.0388 (7)	0.0339 (7)	−0.0099 (6)	−0.0036 (6)	−0.0037 (5)
C9	0.0417 (7)	0.0429 (7)	0.0354 (7)	−0.0138 (6)	0.0005 (5)	−0.0050 (6)
C10	0.0520 (8)	0.0507 (8)	0.0358 (7)	−0.0215 (7)	−0.0031 (6)	−0.0069 (6)
C11	0.0469 (8)	0.0512 (9)	0.0339 (7)	−0.0172 (7)	−0.0113 (6)	0.0017 (6)
C12	0.0520 (9)	0.0601 (10)	0.0358 (7)	−0.0200 (7)	−0.0105 (6)	0.0020 (7)
C13	0.0614 (10)	0.0752 (13)	0.0447 (9)	−0.0263 (9)	−0.0070 (8)	0.0132 (8)
C14	0.0733 (13)	0.0589 (12)	0.0736 (13)	−0.0287 (10)	−0.0198 (10)	0.0222 (10)
C15	0.0788 (13)	0.0479 (10)	0.0730 (13)	−0.0153 (9)	−0.0219 (10)	0.0017 (9)
C16	0.0621 (10)	0.0509 (9)	0.0478 (9)	−0.0124 (8)	−0.0107 (7)	−0.0013 (7)
C17	0.0510 (8)	0.0507 (9)	0.0366 (7)	−0.0191 (7)	0.0028 (6)	−0.0062 (6)

Geometric parameters (Å, º) top

Cl1—C12	1.7353 (18)	C8—C9	1.499 (2)
N1—C17	1.137 (2)	C8—H8A	0.9700
O1—C7	1.2004 (18)	C8—H8B	0.9700
O2—C1	1.3672 (16)	C9—C10	1.3367 (19)
O2—C8	1.4199 (16)	C9—C17	1.443 (2)
C1—C2	1.378 (2)	C10—C11	1.460 (2)
C1—C6	1.3992 (18)	C10—H10	0.9300
C2—C3	1.379 (2)	C11—C16	1.395 (2)
C2—H2	0.9300	C11—C12	1.402 (2)
C3—C4	1.378 (2)	C12—C13	1.376 (2)
C3—H3	0.9300	C13—C14	1.364 (3)
C4—C5	1.369 (2)	C13—H13	0.9300
C4—H4	0.9300	C14—C15	1.381 (3)
C5—C6	1.390 (2)	C14—H14	0.9300
C5—H5	0.9300	C15—C16	1.377 (3)
C6—C7	1.460 (2)	C15—H15	0.9300
C7—H7	0.9300	C16—H16	0.9300

C1—O2—C8	116.56 (10)	H8A—C8—H8B	108.5
O2—C1—C2	123.98 (12)	C10—C9—C17	117.74 (14)
O2—C1—C6	115.96 (11)	C10—C9—C8	125.17 (13)
C2—C1—C6	120.05 (13)	C17—C9—C8	117.06 (12)
C1—C2—C3	119.14 (14)	C9—C10—C11	127.43 (14)
C1—C2—H2	120.4	C9—C10—H10	116.3
C3—C2—H2	120.4	C11—C10—H10	116.3
C4—C3—C2	121.89 (14)	C16—C11—C12	117.11 (14)
C4—C3—H3	119.1	C16—C11—C10	122.99 (14)
C2—C3—H3	119.1	C12—C11—C10	119.90 (14)
C5—C4—C3	118.66 (15)	C13—C12—C11	121.65 (17)
C5—C4—H4	120.7	C13—C12—Cl1	118.70 (14)
C3—C4—H4	120.7	C11—C12—Cl1	119.63 (12)
C4—C5—C6	121.20 (14)	C14—C13—C12	119.65 (18)
C4—C5—H5	119.4	C14—C13—H13	120.2
C6—C5—H5	119.4	C12—C13—H13	120.2
C5—C6—C1	118.97 (13)	C13—C14—C15	120.53 (17)
C5—C6—C7	120.44 (13)	C13—C14—H14	119.7
C1—C6—C7	120.58 (12)	C15—C14—H14	119.7
O1—C7—C6	124.58 (15)	C16—C15—C14	120.0 (2)
O1—C7—H7	117.7	C16—C15—H15	120.0
C6—C7—H7	117.7	C14—C15—H15	120.0
O2—C8—C9	107.51 (11)	C15—C16—C11	121.09 (18)
O2—C8—H8A	110.2	C15—C16—H16	119.5
C9—C8—H8A	110.2	C11—C16—H16	119.5
O2—C8—H8B	110.2	N1—C17—C9	178.10 (17)
C9—C8—H8B	110.2

C8—O2—C1—C2	−21.16 (19)	C17—C9—C10—C11	−177.54 (15)
C8—O2—C1—C6	160.05 (12)	C8—C9—C10—C11	0.5 (3)
O2—C1—C2—C3	−176.06 (14)	C9—C10—C11—C16	−37.5 (2)
C6—C1—C2—C3	2.7 (2)	C9—C10—C11—C12	143.27 (17)
C1—C2—C3—C4	−0.3 (3)	C16—C11—C12—C13	1.2 (2)
C2—C3—C4—C5	−1.7 (3)	C10—C11—C12—C13	−179.48 (15)
C3—C4—C5—C6	1.4 (3)	C16—C11—C12—Cl1	179.72 (12)
C4—C5—C6—C1	0.9 (2)	C10—C11—C12—Cl1	−1.0 (2)
C4—C5—C6—C7	−177.70 (15)	C11—C12—C13—C14	−0.4 (3)
O2—C1—C6—C5	175.89 (12)	Cl1—C12—C13—C14	−178.89 (14)
C2—C1—C6—C5	−2.9 (2)	C12—C13—C14—C15	−0.3 (3)
O2—C1—C6—C7	−5.54 (19)	C13—C14—C15—C16	0.2 (3)
C2—C1—C6—C7	175.62 (13)	C14—C15—C16—C11	0.7 (3)
C5—C6—C7—O1	0.0 (3)	C12—C11—C16—C15	−1.4 (2)
C1—C6—C7—O1	−178.53 (16)	C10—C11—C16—C15	179.34 (15)
C1—O2—C8—C9	−173.38 (11)	C10—C9—C17—N1	36 (6)
O2—C8—C9—C10	−149.36 (14)	C8—C9—C17—N1	−142 (6)
O2—C8—C9—C17	28.70 (17)

Experimental details

Crystal data
Chemical formula	C₁₇H₁₂ClNO₂
M_r	297.73
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.5022 (4), 7.8301 (4), 13.2379 (8)
α, β, γ (°)	75.470 (3), 84.696 (2), 70.935 (2)
V (Å³)	711.43 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.24 × 0.21 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.937, 0.960
No. of measured, independent and observed [I > 2σ(I)] reflections	14438, 3433, 2685
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.662

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.114, 1.04
No. of reflections	3433
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.19

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).

Footnotes

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

Acknowledgements

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

References

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