Methyl 3-[4-(4-nitro­benz­yloxy)phen­yl]propano­ate

Linden Servinis; Bronwyn L Fox; Peter C Healy; Luke C Henderson

doi:10.1107/S1600536812024701

. 2012 Jun 2;68(Pt 7):o1997–o1998. doi: 10.1107/S1600536812024701

Methyl 3-[4-(4-nitrobenzyloxy)phenyl]propanoate

Linden Servinis ^a, Bronwyn L Fox ^a, Peter C Healy ^b,^*, Luke C Henderson ^a

PMCID: PMC3393271 PMID: 22807828

Abstract

The title compound, C₁₇H₁₇NO₅, crystallizes with two molecules (A and B) in the asymmetric unit. The conformational structures of the two molecules show small but significant differences in the dihedral angles between the two aryl rings with values of 18.8 (1)° for molecule A and 7.5 (1)° for molecule B. In molecule A, the propanoate group is twisted out of the plane of the benzene group [C_ar—C_ar—C—C torsion angle = −44.9 (2)°], while for molecule B, this group lies closer to the plane [C_ar—C_ar—C—C torsion angle = 8.6 (3)°]. C—H⋯O interactions characterize the crystal-packing interactions in this compound.

Related literature

For background to the functionalization of carbon nanostructures and fibres, see: Forohar et al. (2011 ▶); Moradi et al. (2012 ▶); Nierengarten et al. (2004 ▶). For the synthesis, see: Greene et al. (1999 ▶). For related structures, see: Li & Chen (2008 ▶); Wang et al. (2007 ▶).

Experimental

Crystal data

C₁₇H₁₇NO₅
M _r = 315.32
Triclinic,
a = 10.7434 (5) Å
b = 10.9408 (5) Å
c = 14.7225 (6) Å
α = 100.085 (4)°
β = 102.451 (4)°
γ = 110.329 (4)°
V = 1524.34 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 223 K
0.48 × 0.30 × 0.27 mm

Data collection

Oxford Diffraction Gemini S Ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.953, T _max = 0.973
10836 measured reflections
5352 independent reflections
4439 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.113
S = 1.02
5352 reflections
415 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: TEXSAN (Molecular Structure Corporation, 2001 ▶) and SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: TEXSAN and SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812024701/tk5106sup1.cif

e-68-o1997-sup1.cif^{(33.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024701/tk5106Isup2.hkl

e-68-o1997-Isup2.hkl^{(262KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812024701/tk5106Isup3.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
C3—H3⋯O3	0.95	2.43	2.757 (2)	100
C6—H6⋯O6ⁱ	0.95	2.53	3.362 (2)	146
C19—H19⋯O2ⁱⁱ	0.95	2.55	3.430 (2)	153
C20—H20⋯O8	0.95	2.40	2.736 (2)	101
C7—H72⋯O9	0.95	2.49	3.336 (3)	149

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

Acknowledgments

We acknowledge support of this work by Griffith University, the Queensland University of Technology, the Strategic Research Center for Biotechnology, Chemistry and Systems Biology and the Institute for Frontier Materials Deakin University.

supplementary crystallographic information

Comment

The structure of the title compound 1 was determined as part of an ongoing project investigating the surface functionalization of carbon nanostructures and carbon fibers, which have massive application in chemistry and materials science, respectively (Forohar et al., 2011; Moradi et al., 2012; Nierengarten et al., 2004). The oxidized nitro group present on the aryl ring serves as an excellent diagnostic handle for surface characterization using X-Ray Photoelectron Spectroscopy (XPS). This compound provides a synthetically versatile scaffold with an alkyl carboxyl group which can be used for compound derivatization and surface attachment strategies. Additionally the 4-nitrophenyl group serves as an excellent protecting group for alcohols, including phenols, which can readily be removed by hydrogenolysis or electrolytically (Greene et al., 1999).

The compound crystallizes with two independent molecules in the asymmetric unit (Fig. 1). The bond lengths and angles for each molecule are in accord with related structures (e.g. Li & Chen, 2008; Wang et al., 2007). The conformational structure of the two molecules show small but significant differences in the dihedral angles between the two aryl rings with values of 18.8 (1)° for molecule A and 7.5 (1)° for molecule B. In molecule A, the propanoate group is twisted out of the plane of the phenyl group with the C12—C11—C14—C15 torsion angle = -44.9 (2)°, while for molecule B, this group lies closer to the plane with the torsion angle C29—C30—C31—C32 = 8.6 (3)°. C—H···O interactions characterize the crystal packing interactions in this compound (Table 1).

Experimental

To a solution of (CH₃)₂CO (10 ml) and methyl 4-hydroxyphenylpropanoate (0.194 g, 1.28 mmol), was added K₂CO₃ (0.195 g, 1.41 mmol) followed by reflux at 55 °C for 1 h. Nitrobenzyl bromide (0.305 g, 1.41 mmol) and NaI (0.192 g, 1.28 mmol) were added to the solution and the reaction stirred a further 15 h at 55 °C (Fig. 2). The resulting crude mixture was filtered, and the residual precipitate washed with acetone and diethyl ether. The organic phases were combined, dried over MgSO₄, and solvent removed in vacuo. Purification by column chromatography (9:1, PET ether:ethyl acetate) gave a colourless crystalline solid was confirmed to be the desired propanoate 1 (51%, 0.206 g). The purified solid was dissolved in toluene and slowly evaporated over 3 days to give well formed single crystals suitable for X-ray diffraction studies. ν_(max) cm ^-1: 2922 (aromatic C—H), 2830 (methyl C—H, aliphatic –CH₂–), 1728 (ester C=O), 1511 (aromatic C—C=C), 1160 (ether C—O—C). ¹H NMR (270 MHz, CDCl₃): δ= 8.23 (d, 2H, ³J_HH= 8.64 Hz, ArH), 7.59 (d, 2H, ³J_HH = 8.37 Hz, ArH), 7.12 (d, 2H, ³J_HH = 8.64 Hz, ArH), 6.87 (d, 2H, ³J_HH = 8.91 Hz, ArH), 5.14 (s, 2H, CH₂Bn), 3.65 (s, 3H, CH₃), 2.89 (t, 2H, ³J_HH = 7.29, 8.10 Hz, CH₂), 2.59 (t, 2H, ³J_HH = 7.83 Hz, CH₂). ¹³C NMR (400 MHz, CDCl₃): δ = 173.41, 156.74, 147.65, 144.75, 133.69, 129.51, 127.66, 123.91, 114.95, 68.81, 51.69, 35.95, 30.15. M.P. 110.5–116.8 °C. MS, m/z found: MNa⁺ 338.09985, (C₁₇H₁₇NO₅), MNa⁺ requires 338.09989.