2-[Hy­droxy(2-meth­oxy­phenyl)methyl]acrylonitrile

Bakthadoss, M.; Selvakumar, R.; Madhanraj, R.; Murugavel, S.

doi:10.1107/S1600536812031728

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2467

https://doi.org/10.1107/S1600536812031728

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2-[Hydroxy(2-methoxyphenyl)methyl]acrylonitrile

M. Bakthadoss,^a ‡ R. Selvakumar,^a R. Madhanraj ^b and S. Murugavel ^c ^*

^aDepartment of Organic Chemistry, University of Madras, Maraimalai Campus, Chennai 600 025, India, ^bDepartment of Physics, Ranipettai Engineering College, Thenkadappathangal, Walaja 632 513, India, and ^cDepartment of Physics, Thanthai Periyar Government Institute of Technology, Vellore 632 002, India
^*Correspondence e-mail: smurugavel27@gmail.com

(Received 9 July 2012; accepted 11 July 2012; online 18 July 2012)

In the title compound, C₁₁H₁₁NO₂, the mean planes formed by the benzene ring and the C and N atoms of the acryl group are almost orthogonal to each other, with a dihedral angle of 85.7 (1)°. During the structure analysis, it was observed that the unit cell contains large accessible voids, with a volume of 186.9 Å³, which may host disordered solvent molecules. This affects the diffraction pattern, mostly at low scattering angles. Density identified in these solvent-accessible areas was calculated and corrected for using the SQUEEZE routine in PLATON [Spek (2009 ), Acta Cryst. D65, 148–155]. Despite the presence of the hydroxy group in the molecule, no classical or nonclassical hydrogen bonds are observed in the structure. This may reflect the fact that the O—H group points towards the solvent-accessible void.

Related literature

For the uses of acrylonitrile derivatives, see: Ohsumi et al. (1998 ). For a related structure, see: Cobo et al. (2005 ).

Experimental

Crystal data

C₁₁H₁₁NO₂
M_r = 189.21
Triclinic, $[P \overline 1]$
a = 6.9063 (4) Å
b = 8.7085 (4) Å
c = 11.7294 (6) Å
α = 94.864 (3)°
β = 98.013 (3)°
γ = 106.579 (2)°
V = 663.73 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 293 K
0.25 × 0.23 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.984, T_max = 0.989
14371 measured reflections
3667 independent reflections
2302 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.215
S = 1.08
3667 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.17 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: https://doi.org/10.1107/S1600536812031728/sj5256sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812031728/sj5256Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812031728/sj5256Isup3.cml

checkCIF report

Comment top

Acrylonitrile derivatives have been shown to possess antitubercular and antitumour activities (Ohsumi et al., 1998). In view of this biological importance, the crystal structure of the title compound has been determined and the results are presented here.

In the title compound (Fig. 1), the mean planes formed by the phenyl ring C1–C6 and acryl group (N1/C7–C10) are orthogonal to each other with a dihedral angle 85.7 (1)°. The bond length C8—C9 [1.429 (3) Å] is significantly shorter than the expected value for a C—C single bond because of conjugation effects. The carbonitrile side chain (C8—-C9—-N1) is almost linear, with the angle around central carbon atom being 178.6 (2)°. The title compound exhibits structural similarities with the closely related structure, (E)-3-(4-chlorophenyl)-2-(2-thienyl)acrylonitrile (Cobo et al., 2005).

Related literature top

For the uses of acrylonitrile derivatives, see: Ohsumi et al. (1998). For a related structure, see: Cobo et al. (2005).

Experimental top

A mixture of 2-methoxybenzaldehyde (1 g, 7.3 mmol), acrylonitrile (0.58 g, 11.0 mmol) and 1,4-diazabicyclo[2.2.2]octane (0.20 g, 1.8 mmol) was kept at room temperature for 3 d. Then the reaction mixture was diluted with ethyl acetate and water. The aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over anhydrous sodium sulfate. Solvent was evaporated and the residue subjected to column chromatography. The pure title compound was obtained as a colourless solid (95% yield). Recrystallization was carried out using ethyl acetate as solvent.

Structure description top

For the uses of acrylonitrile derivatives, see: Ohsumi et al. (1998). For a related structure, see: Cobo et al. (2005).

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. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small circles of arbitrary radius.

2-[Hydroxy(2-methoxyphenyl)methyl]acrylonitrile top

Crystal data top

C₁₁H₁₁NO₂	Z = 2
M_r = 189.21	F(000) = 200
Triclinic, P1	D_x = 0.947 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9063 (4) Å	Cell parameters from 3700 reflections
b = 8.7085 (4) Å	θ = 2.5–29.5°
c = 11.7294 (6) Å	µ = 0.07 mm⁻¹
α = 94.864 (3)°	T = 293 K
β = 98.013 (3)°	Block, colourless
γ = 106.579 (2)°	0.25 × 0.23 × 0.17 mm
V = 663.73 (6) Å³

Data collection top

Bruker APEXII CCD diffractometer	3667 independent reflections
Radiation source: fine-focus sealed tube	2302 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
Detector resolution: 10.0 pixels mm^-1	θ_max = 29.5°, θ_min = 2.5°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −11→12
T_min = 0.984, T_max = 0.989	l = −16→14
14371 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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.215	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.1283P)²] where P = (F_o² + 2F_c²)/3
3667 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₁H₁₁NO₂	γ = 106.579 (2)°
M_r = 189.21	V = 663.73 (6) Å³
Triclinic, P1	Z = 2
a = 6.9063 (4) Å	Mo Kα radiation
b = 8.7085 (4) Å	µ = 0.07 mm⁻¹
c = 11.7294 (6) Å	T = 293 K
α = 94.864 (3)°	0.25 × 0.23 × 0.17 mm
β = 98.013 (3)°

Data collection top

Bruker APEXII CCD diffractometer	3667 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2302 reflections with I > 2σ(I)
T_min = 0.984, T_max = 0.989	R_int = 0.024
14371 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.215	H-atom parameters constrained
S = 1.08	Δρ_max = 0.37 e Å⁻³
3667 reflections	Δρ_min = −0.17 e Å⁻³
128 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
C6	0.40136 (19)	0.02493 (15)	0.23097 (11)	0.0512 (3)
O1	0.32726 (19)	0.20317 (15)	0.10146 (8)	0.0785 (4)
H1A	0.2641	0.2678	0.0867	0.118*
C8	0.3411 (2)	0.28106 (17)	0.30328 (11)	0.0594 (4)
C7	0.2833 (2)	0.14393 (17)	0.20547 (11)	0.0553 (3)
H7	0.1361	0.0880	0.1962	0.066*
O2	0.19770 (18)	−0.05952 (14)	0.37012 (10)	0.0761 (4)
C5	0.3559 (2)	−0.07361 (16)	0.31777 (12)	0.0586 (4)
C1	0.5551 (2)	0.01363 (17)	0.17103 (14)	0.0634 (4)
H1	0.5839	0.0773	0.1121	0.076*
C4	0.4708 (3)	−0.17723 (18)	0.34459 (16)	0.0765 (5)
H4	0.4429	−0.2416	0.4032	0.092*
C3	0.6255 (3)	−0.1844 (2)	0.2844 (2)	0.0878 (6)
H3	0.7026	−0.2534	0.3031	0.105*
C9	0.5538 (3)	0.37095 (19)	0.33066 (14)	0.0711 (4)
C2	0.6680 (3)	−0.0914 (2)	0.1970 (2)	0.0828 (5)
H2	0.7714	−0.0986	0.1557	0.099*
C11	0.1371 (3)	−0.1609 (2)	0.45522 (17)	0.0910 (6)
H11A	0.1030	−0.2719	0.4222	0.136*
H11B	0.0195	−0.1415	0.4814	0.136*
H11C	0.2476	−0.1380	0.5197	0.136*
C10	0.2061 (4)	0.3212 (3)	0.36068 (17)	0.0902 (6)
H10A	0.2497	0.4086	0.4193	0.108*
H10B	0.0681	0.2620	0.3422	0.108*
N1	0.7246 (3)	0.4399 (2)	0.35287 (19)	0.1078 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C6	0.0495 (7)	0.0425 (6)	0.0587 (7)	0.0150 (5)	−0.0018 (5)	0.0054 (5)
O1	0.1091 (9)	0.1020 (9)	0.0560 (6)	0.0696 (8)	0.0259 (6)	0.0323 (6)
C8	0.0844 (10)	0.0566 (7)	0.0543 (7)	0.0388 (7)	0.0214 (6)	0.0241 (6)
C7	0.0587 (8)	0.0630 (8)	0.0544 (7)	0.0309 (6)	0.0104 (5)	0.0195 (6)
O2	0.0857 (8)	0.0723 (7)	0.0806 (7)	0.0276 (6)	0.0241 (6)	0.0374 (6)
C5	0.0615 (8)	0.0431 (6)	0.0648 (8)	0.0127 (6)	−0.0055 (6)	0.0096 (5)
C1	0.0574 (8)	0.0508 (7)	0.0811 (9)	0.0177 (6)	0.0089 (7)	0.0037 (6)
C4	0.0866 (11)	0.0470 (7)	0.0893 (11)	0.0224 (7)	−0.0147 (9)	0.0141 (7)
C3	0.0793 (11)	0.0553 (9)	0.1254 (15)	0.0359 (8)	−0.0193 (11)	0.0000 (9)
C9	0.0944 (13)	0.0490 (8)	0.0748 (9)	0.0295 (8)	0.0123 (8)	0.0108 (7)
C2	0.0618 (9)	0.0593 (9)	0.1254 (15)	0.0262 (7)	0.0046 (9)	−0.0082 (9)
C11	0.1114 (15)	0.0760 (11)	0.0767 (11)	0.0088 (10)	0.0148 (10)	0.0323 (9)
C10	0.1299 (17)	0.0953 (13)	0.0781 (10)	0.0637 (12)	0.0510 (11)	0.0319 (9)
N1	0.1053 (14)	0.0681 (10)	0.1354 (17)	0.0171 (10)	0.0003 (12)	−0.0017 (10)

Geometric parameters (Å, º) top

C6—C1	1.374 (2)	C1—H1	0.9300
C6—C5	1.3982 (19)	C4—C3	1.373 (3)
C6—C7	1.5149 (16)	C4—H4	0.9300
O1—C7	1.4026 (15)	C3—C2	1.371 (3)
O1—H1A	0.8200	C3—H3	0.9300
C8—C10	1.329 (2)	C9—N1	1.142 (2)
C8—C9	1.429 (3)	C2—H2	0.9300
C8—C7	1.507 (2)	C11—H11A	0.9600
C7—H7	0.9800	C11—H11B	0.9600
O2—C5	1.3549 (19)	C11—H11C	0.9600
O2—C11	1.4165 (18)	C10—H10A	0.9300
C5—C4	1.389 (2)	C10—H10B	0.9300
C1—C2	1.388 (2)

C1—C6—C5	119.23 (12)	C3—C4—C5	119.88 (16)
C1—C6—C7	120.95 (12)	C3—C4—H4	120.1
C5—C6—C7	119.81 (12)	C5—C4—H4	120.1
C7—O1—H1A	109.5	C2—C3—C4	120.98 (14)
C10—C8—C9	120.64 (17)	C2—C3—H3	119.5
C10—C8—C7	123.50 (17)	C4—C3—H3	119.5
C9—C8—C7	115.85 (12)	N1—C9—C8	178.61 (17)
O1—C7—C8	110.27 (11)	C3—C2—C1	119.24 (18)
O1—C7—C6	108.58 (10)	C3—C2—H2	120.4
C8—C7—C6	110.66 (10)	C1—C2—H2	120.4
O1—C7—H7	109.1	O2—C11—H11A	109.5
C8—C7—H7	109.1	O2—C11—H11B	109.5
C6—C7—H7	109.1	H11A—C11—H11B	109.5
C5—O2—C11	118.82 (14)	O2—C11—H11C	109.5
O2—C5—C4	124.63 (14)	H11A—C11—H11C	109.5
O2—C5—C6	115.73 (11)	H11B—C11—H11C	109.5
C4—C5—C6	119.64 (15)	C8—C10—H10A	120.0
C6—C1—C2	121.00 (16)	C8—C10—H10B	120.0
C6—C1—H1	119.5	H10A—C10—H10B	120.0
C2—C1—H1	119.5

C10—C8—C7—O1	116.07 (15)	C1—C6—C5—C4	2.1 (2)
C9—C8—C7—O1	−62.57 (14)	C7—C6—C5—C4	−177.03 (12)
C10—C8—C7—C6	−123.79 (15)	C5—C6—C1—C2	−1.3 (2)
C9—C8—C7—C6	57.57 (15)	C7—C6—C1—C2	177.77 (13)
C1—C6—C7—O1	12.72 (18)	O2—C5—C4—C3	178.66 (14)
C5—C6—C7—O1	−168.18 (12)	C6—C5—C4—C3	−1.2 (2)
C1—C6—C7—C8	−108.43 (14)	C5—C4—C3—C2	−0.5 (3)
C5—C6—C7—C8	70.67 (16)	C10—C8—C9—N1	125 (8)
C11—O2—C5—C4	−2.7 (2)	C7—C8—C9—N1	−56 (8)
C11—O2—C5—C6	177.19 (13)	C4—C3—C2—C1	1.3 (3)
C1—C6—C5—O2	−177.78 (12)	C6—C1—C2—C3	−0.3 (2)
C7—C6—C5—O2	3.11 (19)

Experimental details

Crystal data
Chemical formula	C₁₁H₁₁NO₂
M_r	189.21
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.9063 (4), 8.7085 (4), 11.7294 (6)
α, β, γ (°)	94.864 (3), 98.013 (3), 106.579 (2)
V (Å³)	663.73 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.25 × 0.23 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.984, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	14371, 3667, 2302
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.693

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.215, 1.08
No. of reflections	3667
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.17

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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