Methyl (E)-2-[(2-nitro­phen­oxy)meth­yl]-3-phenyl­acrylate

T Anuradha; A Devaraj; P R Seshadri; M Bakthadoss

doi:10.1107/S1600536812021009

. 2012 May 16;68(Pt 6):o1748. doi: 10.1107/S1600536812021009

Methyl (E)-2-[(2-nitrophenoxy)methyl]-3-phenylacrylate

T Anuradha ^a, A Devaraj ^b, P R Seshadri ^a,^*, M Bakthadoss ^b

PMCID: PMC3379335 PMID: 22719533

Abstract

The title compound, C₁₇H₁₅NO₅, adopts an E conformation with respect to the C=C double bond of the phenylacrylate unit. The phenyl ring and methyl acrylate group of the phenylacrylate unit are disordered over two sets of sites with site-occupancy ratios of 0.705 (5):0.295 (5) and 0.683 (3):0.317 (3), respectively. The mean plane through the benzene ring of the phenyl acrylate makes dihedral angles of 88.4 (8) (major component) and 86.7 (8)° (minor component) with the nitrophenoxy ring; the dihedral angle between the two components is 3.64 (6)°. Intramolecular C—H⋯O interactions stabilise the molecular structure. In the crystal, C—H⋯O interactions result in a chain of molecules running along the b axis.

Related literature

For the industrial importance of methyl trans-cinnamates, see: Bhatia et al. (2007 ▶); Huang et al. (2009 ▶); Sharma (2011 ▶). For related structures, see: Anuradha et al. (2011 ▶); Wang et al. (2011 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶). For background to the synthesis, see: Bakthadoss et al. (2009 ▶).

Experimental

Crystal data

C₁₇H₁₅NO₅
M _r = 313.30
Monoclinic,
a = 24.0511 (10) Å
b = 7.8521 (3) Å
c = 19.7403 (9) Å
β = 121.661 (3)°
V = 3173.1 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.971, T _max = 0.981
32853 measured reflections
3695 independent reflections
2356 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.145
S = 1.12
3695 reflections
212 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812021009/pv2539sup1.cif

e-68-o1748-sup1.cif^{(23KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812021009/pv2539Isup2.hkl

e-68-o1748-Isup2.hkl^{(177.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812021009/pv2539Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O3	0.93	2.26	2.683 (5)	107
C11—H11⋯O5	0.93	2.51	3.2734 (17)	140
C2—H2⋯O3ⁱ	0.93	2.56	3.140 (4)	121
C3—H3⋯O3ⁱ	0.93	2.51	3.114 (5)	123
C4—H4⋯O2ⁱⁱ	0.93	2.56	3.255 (2)	132

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors thank Dr Babu Varghese, SAIF, IIT–Madras, India, for the data collection.

supplementary crystallographic information

Comment

Methyl trans-cinnamate can inhibit both monophenolase activity and diphenolase activity of tyrosinase and thus it can be a potential compound used in antibrowning food additive (Huang et al., 2009). It is a fragrance ingredient used in many fragrances and decorative cosmetics (Bhatia et al., 2007; Sharma, 2011). In view of this industrial importance, we have prepared the title compound which is a nitrophenoxymethyl derivative of methyl trans-cinnamate and determined its crystal structure which is presented in this paper.

The title molecule adopts an E configuration with respect to the C8═C9 double bond (Fig. 1). The benzene ring (C10–C15) and methyl acrylate (C16/C17/O3/O4) group of the phenylacrylate unit are disordered over two orientations with site-occupancy ratios of 0.705 (5):0.295 (5) and 0.683 (3):0.317 (3) representing major and minor components, repectively. The mean plane through the benzene ring of the phenyl acrylate makes dihedral angles of 88.4 (8) (major component) and 86.7 (8)° (minor component) with the nitrophenoxy (C1–C6/N1/O1/O2) ring; the dihedral angle between the two components is 3.6 (6)°.

The major and minor components of the methylacrylate (C8/C16/C17/O3/O4) are essentially planar with maximum deviations for atoms O4 and O4', -0.015 (1) and 0.015 (1) Å, respectively. The central unit (C6–C8/O5) is almost equatorial to the major component of methylphenylacrylate group (C8–C17/O1/O2) whereas axial to the nitrobenzene (C1–C6/N1), making dihedral angles of 88.4 (1) and 8.1 (1)°, respectively.

The crystal structure is stabilized by intramolecular bifurcated C—H···O hydrogen bonds involving two hydrogen atoms (H2/H3) of the benzene ring (C1—C6) and O3 of the acrylate resulting in an R²₂(5) ring motif (Bernstein et al., 1995) and C4—H4···O2 interactions resulting in a chain of molecules running along the b-axis (Table 1 and Fig. 2).

The crystal structures of a few related compounds have been reported recently (Anuradha et al., 2011); Wang et al., 2011).

Experimental

To a stirred solution of 2-nitrophenol (0.14 g, 1 mmol) in acetonitrile (7 ml), potassium carbonate (0.35 g, 2.5 mmol) was added and stirred well for five minutes. To this solution, (Z)- methyl 2-(bromomethyl)-3-phenylacrylate (0.26 g, 1 mmol) in acetonitrile (0.5 ml) was added and allowed to stir well for 6 h. After the completion of the reaction, the reaction mixture was poured into water and extracted using ethyl acetate. The organic layer thus obtained was concentrated under reduced pressure and the residual mass thus obtained was purified by column chromatography on silica gel (Acme 100–200) using EtOAc-hexanes (1:9) to afford the title compound in 90% yield. The crystals suitable for X-ray crystallographic analysis were grown from a solution of ethylacetate by slow evaporation at room temperature.