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Acta Cryst. (2008). E64, o1751    [ doi:10.1107/S1600536808025130 ]

4-Nitrophenyl methacrylate

Y.-H. Xu and F. Qu

Abstract top

The title compound, C10H9NO4, was obtained serendipitously during the preparation of benzyl cyclohexylcarbamate. The molecule consists of two approximately planar parts, the nitrophenyl ring and the rest of the non-H atoms, with a dihedral angle of 55.05 (6)° between the two segments. The crystal structure is stabilized by weak C-H...O interactions and [pi] stacking [3.753 (1) Å] along the b axis.

Comment top

The title compound (I) is an important building block in the preparation of functional block polymers (Tang, et al. 2007; Hwang, et al. 2007; Li, et al. 2007). Although it has been widely used as a monomer in polymerization reactions for a long time (Otsu, et al. 1968), the crystal structure, as far as we know, has never been reported before.

Traditonally, (I) has been synthesized by refluxing methacryloyl chloride and para-nitrophenol (Banks, et al. 1977). Here it was obtained unexpectedly during an attempt to make benzyl cyclohexylcarbamate as described in the experimental section.

The asymmetric unit of (I) (Fig. 1) contains one molecule and bond lengths and angles are within normal ranges. The molecule consists of two approximately planar parts: the nitrophenyl ring and the rest of the non-hydrogen atoms (dihedral angle between the two segments is 55.05 (6)°). The nitro group is nearly coplanar with the phenyl ring as indicated by the torsion angle O3-N1-C8-C7 of -7.48 °. The remaining non-hydrogen atoms are almost coplanar as suggested by the torsion angle C2-C3-C4-O1 at 9.35 °. Since (I) has no classic hydrogen bonding donors, the crystal packng is stabilized by C—H···O interactions (Table 1)in two directions with aromatic C-H atoms as the donors and both oxygen atoms of the nitro group and the carbonyl oxygen as the acceptors. There is also π-stacking along the third direction, the shortest (b), where the aromatic rings are separated by a unit cell translation of 3.753 (1) Å (Fig. 2).

Related literature top

For related literature, see: Banks et al. (1977); Hwang et al. (2007); Li et al. (2007); Otsu et al. (1968); Tang et al. (2007).

Experimental top

4-nitrophenyl cyclohexylcarbamate (0.95 g, 3.5 mmol), phenylmethanol (0.40 g, 3.7 mmol) and triethylamine (0.36 g, 3.6 mmol) were reflxued overnight in 20 ml methylene chloride. The solution was washed with 1 N NaOH, water and brine, and then dried with anhydrous Na2SO4. After removal of the solvent, the product was recovered as a colorless solid (0.5 g). Crystals of (I) were obtained by recrystallization from ethyl acetate as colorless rods.

Refinement top

H atoms were found in difference Fourier maps and subsequently placed in idealized positions with constrained C—H distances of 0.95 Å (CArH) and 0.98 Å (Csp3H). Uiso(H) values were set to 1.2Ueq for all H atoms.

Computing details top

Data collection: COLLECT (Nonius, 2002); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and local procedures.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level (arbitrary spheres for the H atoms).
[Figure 2] Fig. 2. A packing diagram of (I) shown looking down the b axis.
4-Nitrophenyl methacrylate top
Crystal data top
C10H9NO4F000 = 864
Mr = 207.18Dx = 1.434 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
a = 24.491 (6) ÅCell parameters from 2523 reflections
b = 3.753 (1) Åθ = 1.0–27.5º
c = 23.428 (6) ŵ = 0.11 mm−1
β = 116.98 (1)ºT = 90.0 (2) K
V = 1919.0 (9) Å3Thin rod, colorless
Z = 80.30 × 0.10 × 0.04 mm
Data collection top
Nonius KappaCCD
diffractometer		2193 independent reflections
Radiation source: fine-focus sealed tube1380 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.049
Detector resolution: 18 pixels mm-1θmax = 27.5º
T = 90.0(2) Kθmin = 1.9º
ω scans at fixed χ = 55°h = −31→31
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)		k = −4→4
Tmin = 0.967, Tmax = 0.996l = −30→29
3936 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.145  w = 1/[σ2(Fo2) + (0.0788P)2 + 0.0268P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2193 reflectionsΔρmax = 0.32 e Å−3
137 parametersΔρmin = −0.28 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C10H9NO4V = 1919.0 (9) Å3
Mr = 207.18Z = 8
Monoclinic, C2/cMo Kα
a = 24.491 (6) ŵ = 0.11 mm−1
b = 3.753 (1) ÅT = 90.0 (2) K
c = 23.428 (6) Å0.30 × 0.10 × 0.04 mm
β = 116.98 (1)º
Data collection top
Nonius KappaCCD
diffractometer		2193 independent reflections
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)		1380 reflections with I > 2σ(I)
Tmin = 0.967, Tmax = 0.996Rint = 0.049
3936 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.053137 parameters
wR(F2) = 0.145H-atom parameters constrained
S = 1.04Δρmax = 0.32 e Å−3
2193 reflectionsΔρmin = −0.28 e Å−3
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
xyzUiso*/Ueq
C10.34238 (9)0.3043 (6)0.08125 (9)0.0350 (5)
H1A0.30220.26360.04810.042*
H1B0.37690.23880.07530.042*
C20.41131 (8)0.5324 (6)0.19114 (9)0.0327 (5)
H2A0.44370.45510.18030.049*
H2B0.41530.40420.22930.049*
H2C0.41500.78910.19980.049*
C30.35044 (8)0.4545 (6)0.13665 (9)0.0258 (5)
C40.29729 (8)0.5595 (5)0.14726 (9)0.0247 (5)
C50.18934 (8)0.4978 (5)0.10638 (9)0.0232 (5)
C60.18535 (8)0.3892 (5)0.16081 (8)0.0248 (5)
H60.21960.28580.19580.030*
C70.13046 (8)0.4341 (5)0.16321 (9)0.0249 (5)
H70.12620.36070.19980.030*
C80.08165 (8)0.5879 (5)0.11143 (8)0.0225 (5)
C90.08549 (8)0.6948 (5)0.05692 (8)0.0239 (5)
H90.05110.79630.02180.029*
C100.14063 (8)0.6505 (5)0.05472 (8)0.0243 (5)
H100.14490.72420.01820.029*
N10.02377 (7)0.6382 (5)0.11468 (7)0.0273 (4)
O10.30028 (5)0.7338 (4)0.19146 (6)0.0309 (4)
O20.24257 (5)0.4394 (4)0.09952 (6)0.0265 (4)
O30.01867 (6)0.5094 (4)0.16001 (7)0.0379 (4)
O4−0.01732 (6)0.8076 (4)0.07152 (6)0.0356 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0292 (11)0.0418 (15)0.0387 (11)−0.0006 (11)0.0195 (9)−0.0047 (11)
C20.0274 (11)0.0333 (14)0.0390 (12)0.0015 (10)0.0165 (10)−0.0001 (10)
C30.0258 (10)0.0259 (12)0.0286 (11)−0.0004 (9)0.0148 (9)0.0030 (9)
C40.0239 (10)0.0250 (12)0.0228 (10)0.0004 (9)0.0084 (8)0.0007 (9)
C50.0217 (10)0.0231 (12)0.0272 (10)−0.0010 (9)0.0133 (8)−0.0051 (9)
C60.0215 (10)0.0237 (12)0.0246 (10)−0.0001 (9)0.0066 (8)−0.0014 (9)
C70.0258 (10)0.0254 (12)0.0238 (10)−0.0008 (9)0.0116 (8)−0.0005 (8)
C80.0199 (9)0.0233 (12)0.0251 (10)−0.0017 (9)0.0107 (8)−0.0032 (9)
C90.0230 (10)0.0233 (12)0.0219 (9)0.0006 (9)0.0070 (8)−0.0013 (9)
C100.0269 (10)0.0248 (12)0.0204 (9)0.0004 (9)0.0102 (8)−0.0007 (9)
N10.0238 (9)0.0312 (11)0.0268 (9)0.0008 (8)0.0113 (7)−0.0005 (8)
O10.0260 (7)0.0375 (10)0.0295 (7)−0.0029 (7)0.0129 (6)−0.0088 (7)
O20.0201 (7)0.0343 (8)0.0258 (7)−0.0005 (6)0.0111 (6)−0.0043 (6)
O30.0317 (8)0.0518 (11)0.0365 (8)0.0040 (7)0.0210 (7)0.0094 (7)
O40.0251 (7)0.0489 (11)0.0319 (7)0.0098 (7)0.0121 (6)0.0059 (7)
Geometric parameters (Å, °) top
C1—C31.345 (3)C5—O21.402 (2)
C1—H1A0.9500C6—C71.381 (3)
C1—H1B0.9500C6—H60.9500
C2—C31.487 (2)C7—C81.385 (3)
C2—H2A0.9800C7—H70.9500
C2—H2B0.9800C8—C91.382 (2)
C2—H2C0.9800C8—N11.466 (2)
C3—C41.485 (3)C9—C101.385 (3)
C4—O11.199 (2)C9—H90.9500
C4—O21.375 (2)C10—H100.9500
C5—C101.381 (3)N1—O31.224 (2)
C5—C61.384 (3)N1—O41.231 (2)
C3—C1—H1A120.0C7—C6—H6120.7
C3—C1—H1B120.0C5—C6—H6120.7
H1A—C1—H1B120.0C6—C7—C8119.00 (17)
C3—C2—H2A109.5C6—C7—H7120.5
C3—C2—H2B109.5C8—C7—H7120.5
H2A—C2—H2B109.5C9—C8—C7122.47 (17)
C3—C2—H2C109.5C9—C8—N1118.91 (16)
H2A—C2—H2C109.5C7—C8—N1118.62 (16)
H2B—C2—H2C109.5C8—C9—C10118.42 (17)
C1—C3—C4121.11 (17)C8—C9—H9120.8
C1—C3—C2124.19 (18)C10—C9—H9120.8
C4—C3—C2114.70 (17)C5—C10—C9119.11 (17)
O1—C4—O2122.47 (17)C5—C10—H10120.4
O1—C4—C3125.08 (17)C9—C10—H10120.4
O2—C4—C3112.45 (16)O3—N1—O4123.34 (16)
C10—C5—C6122.41 (17)O3—N1—C8118.44 (15)
C10—C5—O2116.30 (16)O4—N1—C8118.22 (15)
C6—C5—O2121.19 (16)C4—O2—C5118.00 (14)
C7—C6—C5118.58 (17)
C1—C3—C4—O1−170.1 (2)C6—C5—C10—C9−0.5 (3)
C2—C3—C4—O19.4 (3)O2—C5—C10—C9176.01 (16)
C1—C3—C4—O28.8 (3)C8—C9—C10—C50.8 (3)
C2—C3—C4—O2−171.74 (17)C9—C8—N1—O3172.43 (18)
C10—C5—C6—C70.3 (3)C7—C8—N1—O3−7.5 (3)
O2—C5—C6—C7−176.06 (18)C9—C8—N1—O4−7.5 (3)
C5—C6—C7—C8−0.4 (3)C7—C8—N1—O4172.65 (18)
C6—C7—C8—C90.8 (3)O1—C4—O2—C5−5.8 (3)
C6—C7—C8—N1−179.34 (17)C3—C4—O2—C5175.30 (15)
C7—C8—C9—C10−1.0 (3)C10—C5—O2—C4129.61 (19)
N1—C8—C9—C10179.14 (16)C6—C5—O2—C4−53.8 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C7—H7···O1i0.952.413.130 (2)133
C1—H1B···O4ii0.952.643.546 (3)159
C2—H2A···O3ii0.982.683.611 (2)159
C9—H9···O4iii0.952.463.282 (2)145
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1/2, y−1/2, z; (iii) −x, −y+2, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C7—H7···O1i0.952.413.130 (2)133
C1—H1B···O4ii0.952.643.546 (3)159
C2—H2A···O3ii0.982.683.611 (2)159
C9—H9···O4iii0.952.463.282 (2)145
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1/2, y−1/2, z; (iii) −x, −y+2, −z.
Acknowledgements top

YX and FQ thank Dr Sihui Long for helpful discussions and invaluable suggestions.

references
References top

Banks, A. R., Fibiger, R. F. & Jones, T. (1977). J. Org. Chem. 42, 3965–3966.

Hwang, J., Li, R. C. & Maynard, H. D. (2007). J. Controlled Release, 122, 279–286.

Li, R. C., Hwang, J. & Maynard, H. D. (2007). Chem. Commun. 35, 3631–3633.

Nonius (2002). COLLECT. Nonius BV, Delft, The Netherlands.

Otsu, T., Ito, T., Fujii, Y. & Imoto, M. (1968). Bull. Chem. Soc. Jpn, 4, 204–207.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Tang, X., Hu, Y. & Pan, C. (2007). Polymer, 48, 6354–6365.