(Z)-3-o-Tolyl-3-(p-tol­yloxy)acrylonitrile

Zhou, L.; Wang, C.-H.; Zhou, M.

doi:10.1107/S1600536812025858

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2085

https://doi.org/10.1107/S1600536812025858

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(Z)-3-o-Tolyl-3-(p-tolyloxy)acrylonitrile

Li Zhou,^a ^* Chuan-Hu Wang ^a and Mi Zhou ^a

^aDepartment of Applied Chemistry and Environmental Engineering, Bengbu College, Bengbu 233030, Anhui, People's Republic of China
^*Correspondence e-mail: queenzl@163.com

(Received 14 May 2012; accepted 7 June 2012; online 13 June 2012)

The title compound, C₁₇H₁₅NO, exists in a Z conformation. The dihedral angle between the O-bonded benzene ring and the vinyl plane is 80.97 (18)° while the dihedral angle between the rings is 80.06 (10)°. In the crystal structure, no classical hydrogen bonds occur.

Related literature

For general background to acrylonitrile compounds and their biological, medical and pharmacological properties, see: Boedec et al. (2008 ); Napolitano et al. (2001 ); Reggio et al. (1998 ).

Experimental

Crystal data

C₁₇H₁₅NO
M_r = 249.30
Tetragonal, P 4₁
a = 9.8731 (6) Å
c = 14.2455 (17) Å
V = 1388.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 296 K
0.40 × 0.37 × 0.35 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.971, T_max = 0.975
2539 measured reflections
1277 independent reflections
1028 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.111
S = 1.03
1277 reflections
172 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.16 e Å⁻³

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812025858/rk2361sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812025858/rk2361Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812025858/rk2361Isup3.cml

checkCIF report

Comment top

Acrylonitrile compounds have been widely found in dyes, agrochemicals, pharmaceutically active compounds, materials and natural products. Recent studies indicate that acrylonitrile compounds have broad range of biological, medical and pharmacological properties (Boedec et al., 2008; Napolitano et al., 2001; Reggio et al., 1998).

As part of our interest in these materials, we report here the crystal structure of the title compound C₁₇H₁₅NO. The molecular structure of the title compound is shown in Fig. 1. The dihedral angle between phenol ring and vinyl plane is 80.97 (18)°. The any hydrogen bonds in crystal structure are not found.

Related literature top

For general background to acrylonitrile compounds and their biological, medical and pharmacological properties, see: Boedec et al. (2008); Napolitano et al. (2001); Reggio et al. (1998).

Experimental top

For the preparation of the title compound, under nitrogen atmosphere, a sealable reaction tube equipped with a magnetic stirrer bar was charged with (Z)-1-(2-bromo-1-(p-tolyloxy)vinyl)-2-methylbenzene (1.0 mmol), K₄Fe(CN)₆ (0.20 mmol), Pd(OAc)2 (0.01 mmol), PPh₃ (0.02 mmol) and DMF (2.0 ml). Then the reaction vessel placed in an oil bath at 393 K for 12 h and it was cooled to room temperature and diluted with ethyl acetate, washed with brine, dried with MgSO₄. After the solvent was removed under reduced pressure, the residue was purified by column chromatography on silica gel to afford the product. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in dichloromethane at room temperature for three days.

Structure description top

For general background to acrylonitrile compounds and their biological, medical and pharmacological properties, see: Boedec et al. (2008); Napolitano et al. (2001); Reggio et al. (1998).

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.

(Z)-3-o-Tolyl-3-(p-tolyloxy)acrylonitrile top

Crystal data top

C₁₇H₁₅NO	D_x = 1.192 Mg m⁻³
M_r = 249.30	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₁	Cell parameters from 2539 reflections
Hall symbol: P 4w	θ = 2.9–25.0°
a = 9.8731 (6) Å	µ = 0.07 mm⁻¹
c = 14.2455 (17) Å	T = 296 K
V = 1388.6 (2) Å³	Block, colourless
Z = 4	0.40 × 0.37 × 0.35 mm
F(000) = 528

Data collection top

Bruker APEXII CCD diffractometer	1277 independent reflections
Radiation source: fine-focus sealed tube	1028 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω–scans	θ_max = 25.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −8→10
T_min = 0.971, T_max = 0.975	k = −1→11
2539 measured reflections	l = −16→9

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) = 0.111	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0658P)² + 0.0136P] where P = (F_o² + 2F_c²)/3
1277 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.11 e Å⁻³
1 restraint	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₇H₁₅NO	Z = 4
M_r = 249.30	Mo Kα radiation
Tetragonal, P4₁	µ = 0.07 mm⁻¹
a = 9.8731 (6) Å	T = 296 K
c = 14.2455 (17) Å	0.40 × 0.37 × 0.35 mm
V = 1388.6 (2) Å³

Data collection top

Bruker APEXII CCD diffractometer	1277 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	1028 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.975	R_int = 0.028
2539 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	1 restraint
wR(F²) = 0.111	H-atom parameters constrained
S = 1.03	Δρ_max = 0.11 e Å⁻³
1277 reflections	Δρ_min = −0.16 e Å⁻³
172 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
N1	0.6863 (4)	0.6337 (4)	−0.0783 (3)	0.1013 (11)
O1	0.8869 (2)	0.4406 (2)	0.07086 (17)	0.0694 (6)
C1	0.6991 (4)	0.6132 (4)	0.0003 (3)	0.0744 (10)
C2	0.7108 (3)	0.5867 (3)	0.0981 (2)	0.0684 (9)
H2	0.6554	0.6339	0.1395	0.082*
C3	0.7979 (3)	0.4971 (3)	0.1321 (2)	0.0566 (8)
C4	0.8057 (3)	0.4605 (3)	0.2332 (2)	0.0548 (7)
C5	0.9274 (3)	0.4663 (3)	0.2842 (2)	0.0631 (9)
C6	0.9215 (4)	0.4387 (4)	0.3795 (3)	0.0772 (10)
H6	1.0008	0.4433	0.4146	0.093*
C7	0.8028 (5)	0.4049 (4)	0.4239 (3)	0.0850 (11)
H7	0.8028	0.3863	0.4879	0.102*
C8	0.6850 (4)	0.3986 (4)	0.3743 (3)	0.0751 (10)
H8	0.6046	0.3749	0.4041	0.090*
C9	0.6856 (3)	0.4278 (3)	0.2792 (2)	0.0624 (8)
H9	0.6048	0.4256	0.2457	0.075*
C10	1.0598 (4)	0.5058 (4)	0.2403 (3)	0.0883 (12)
H10A	1.1021	0.4271	0.2136	0.132*
H10B	1.1180	0.5441	0.2872	0.132*
H10C	1.0439	0.5714	0.1918	0.132*
C11	0.9107 (3)	0.3006 (3)	0.0749 (2)	0.0553 (7)
C12	0.8072 (3)	0.2094 (3)	0.0842 (2)	0.0616 (8)
H12	0.7185	0.2389	0.0922	0.074*
C13	0.8366 (3)	0.0734 (3)	0.0815 (2)	0.0684 (9)
H13	0.7662	0.0115	0.0878	0.082*
C14	0.9668 (3)	0.0254 (3)	0.0699 (2)	0.0619 (8)
C15	1.0682 (3)	0.1212 (4)	0.0605 (2)	0.0664 (9)
H15	1.1571	0.0923	0.0527	0.080*
C16	1.0413 (3)	0.2578 (3)	0.0624 (2)	0.0665 (8)
H16	1.1110	0.3203	0.0554	0.080*
C17	0.9986 (5)	−0.1231 (4)	0.0674 (3)	0.0916 (12)
H17A	0.9627	−0.1619	0.0108	0.137*
H17B	0.9583	−0.1667	0.1207	0.137*
H17C	1.0950	−0.1357	0.0689	0.137*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.103 (3)	0.108 (3)	0.094 (3)	0.0227 (19)	−0.015 (2)	0.010 (2)
O1	0.0669 (13)	0.0668 (13)	0.0746 (14)	0.0157 (10)	0.0185 (11)	0.0127 (12)
C1	0.067 (2)	0.072 (2)	0.084 (3)	0.0144 (17)	−0.008 (2)	0.001 (2)
C2	0.063 (2)	0.064 (2)	0.078 (2)	0.0093 (15)	−0.0049 (17)	−0.0066 (17)
C3	0.0467 (16)	0.0494 (17)	0.074 (2)	−0.0008 (12)	0.0016 (15)	−0.0041 (15)
C4	0.0553 (18)	0.0434 (15)	0.0658 (18)	−0.0004 (12)	−0.0002 (15)	−0.0072 (14)
C5	0.061 (2)	0.0514 (17)	0.077 (2)	0.0031 (13)	−0.0074 (16)	−0.0109 (16)
C6	0.088 (3)	0.067 (2)	0.077 (2)	0.0161 (17)	−0.017 (2)	−0.0199 (19)
C7	0.121 (4)	0.067 (2)	0.068 (2)	0.018 (2)	0.005 (2)	−0.0021 (19)
C8	0.089 (3)	0.059 (2)	0.078 (2)	−0.0003 (17)	0.023 (2)	−0.0041 (18)
C9	0.0614 (19)	0.0491 (17)	0.077 (2)	−0.0019 (13)	0.0068 (17)	−0.0099 (15)
C10	0.057 (2)	0.091 (3)	0.117 (3)	−0.0069 (18)	−0.005 (2)	−0.017 (2)
C11	0.0558 (17)	0.0632 (18)	0.0469 (15)	0.0122 (13)	0.0033 (14)	−0.0001 (15)
C12	0.0468 (17)	0.076 (2)	0.0620 (19)	0.0082 (14)	−0.0024 (15)	−0.0101 (17)
C13	0.065 (2)	0.073 (2)	0.067 (2)	−0.0043 (15)	0.0040 (17)	−0.0162 (17)
C14	0.074 (2)	0.0666 (19)	0.0447 (14)	0.0082 (15)	0.0018 (16)	−0.0084 (15)
C15	0.0545 (18)	0.077 (2)	0.068 (2)	0.0224 (15)	0.0023 (16)	−0.0042 (18)
C16	0.0511 (17)	0.073 (2)	0.076 (2)	0.0045 (15)	0.0126 (16)	0.0005 (18)
C17	0.120 (3)	0.076 (2)	0.078 (2)	0.021 (2)	0.006 (2)	−0.013 (2)

Geometric parameters (Å, º) top

N1—C1	1.145 (5)	C10—H10A	0.9600
O1—C3	1.358 (4)	C10—H10B	0.9600
O1—C11	1.403 (4)	C10—H10C	0.9600
C1—C2	1.421 (5)	C11—C12	1.369 (5)
C2—C3	1.326 (4)	C11—C16	1.368 (4)
C2—H2	0.9300	C12—C13	1.374 (5)
C3—C4	1.487 (4)	C12—H12	0.9300
C4—C9	1.393 (4)	C13—C14	1.380 (5)
C4—C5	1.406 (4)	C13—H13	0.9300
C5—C6	1.386 (5)	C14—C15	1.383 (5)
C5—C10	1.501 (5)	C14—C17	1.500 (5)
C6—C7	1.373 (6)	C15—C16	1.375 (5)
C6—H6	0.9300	C15—H15	0.9300
C7—C8	1.362 (6)	C16—H16	0.9300
C7—H7	0.9300	C17—H17A	0.9600
C8—C9	1.384 (5)	C17—H17B	0.9600
C8—H8	0.9300	C17—H17C	0.9600
C9—H9	0.9300

C3—O1—C11	119.2 (2)	H10A—C10—H10B	109.5
N1—C1—C2	178.3 (4)	C5—C10—H10C	109.5
C3—C2—C1	122.2 (3)	H10A—C10—H10C	109.5
C3—C2—H2	118.9	H10B—C10—H10C	109.5
C1—C2—H2	118.9	C12—C11—C16	120.8 (3)
C2—C3—O1	117.3 (3)	C12—C11—O1	121.8 (2)
C2—C3—C4	123.4 (3)	C16—C11—O1	117.2 (3)
O1—C3—C4	119.3 (3)	C11—C12—C13	118.9 (3)
C9—C4—C5	119.6 (3)	C11—C12—H12	120.6
C9—C4—C3	117.9 (3)	C13—C12—H12	120.6
C5—C4—C3	122.3 (3)	C12—C13—C14	122.4 (3)
C6—C5—C4	117.5 (3)	C12—C13—H13	118.8
C6—C5—C10	119.8 (3)	C14—C13—H13	118.8
C4—C5—C10	122.6 (3)	C13—C14—C15	116.8 (3)
C7—C6—C5	122.4 (4)	C13—C14—C17	122.2 (3)
C7—C6—H6	118.8	C15—C14—C17	121.0 (3)
C5—C6—H6	118.8	C16—C15—C14	122.0 (3)
C8—C7—C6	120.0 (4)	C16—C15—H15	119.0
C8—C7—H7	120.0	C14—C15—H15	119.0
C6—C7—H7	120.0	C11—C16—C15	119.2 (3)
C7—C8—C9	119.6 (4)	C11—C16—H16	120.4
C7—C8—H8	120.2	C15—C16—H16	120.4
C9—C8—H8	120.2	C14—C17—H17A	109.5
C8—C9—C4	120.8 (3)	C14—C17—H17B	109.5
C8—C9—H9	119.6	H17A—C17—H17B	109.5
C4—C9—H9	119.6	C14—C17—H17C	109.5
C5—C10—H10A	109.5	H17A—C17—H17C	109.5
C5—C10—H10B	109.5	H17B—C17—H17C	109.5

C1—C2—C3—O1	6.7 (5)	C7—C8—C9—C4	1.5 (5)
C1—C2—C3—C4	−175.6 (3)	C5—C4—C9—C8	−1.2 (4)
C11—O1—C3—C2	−135.9 (3)	C3—C4—C9—C8	−177.1 (3)
C11—O1—C3—C4	46.3 (4)	C3—O1—C11—C12	44.3 (4)
C2—C3—C4—C9	49.1 (4)	C3—O1—C11—C16	−140.2 (3)
O1—C3—C4—C9	−133.3 (3)	C16—C11—C12—C13	0.5 (5)
C2—C3—C4—C5	−126.8 (3)	O1—C11—C12—C13	175.8 (3)
O1—C3—C4—C5	50.8 (4)	C11—C12—C13—C14	0.1 (5)
C9—C4—C5—C6	0.0 (4)	C12—C13—C14—C15	−0.2 (5)
C3—C4—C5—C6	175.7 (3)	C12—C13—C14—C17	179.8 (3)
C9—C4—C5—C10	−177.6 (3)	C13—C14—C15—C16	−0.2 (5)
C3—C4—C5—C10	−1.9 (4)	C17—C14—C15—C16	179.9 (3)
C4—C5—C6—C7	0.9 (5)	C12—C11—C16—C15	−0.8 (5)
C10—C5—C6—C7	178.6 (3)	O1—C11—C16—C15	−176.4 (3)
C5—C6—C7—C8	−0.6 (5)	C14—C15—C16—C11	0.7 (5)
C6—C7—C8—C9	−0.7 (5)

Experimental details

Crystal data
Chemical formula	C₁₇H₁₅NO
M_r	249.30
Crystal system, space group	Tetragonal, P4₁
Temperature (K)	296
a, c (Å)	9.8731 (6), 14.2455 (17)
V (Å³)	1388.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.40 × 0.37 × 0.35

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.971, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	2539, 1277, 1028
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.111, 1.03
No. of reflections	1277
No. of parameters	172
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.16

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

This work was supported by the National Natural Science Foundation (No. 21101053).

References

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