4-Nitro­phenyl methacrylate

Xu, Y.-H.; Qu, F.

doi:10.1107/S1600536808025130

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1751

doi:10.1107/S1600536808025130

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4-Nitrophenyl methacrylate

Yun-Hua Xu ^a and Fanqi Qu ^b ^*

^aSchool of Science, Beijing Jiaotong University, Beijing 100044, People's Republic of China, and ^bCollege of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei 430072, People's Republic of China
^*Correspondence e-mail: fanqiqu@whu.edu.cn

(Received 11 July 2008; accepted 5 August 2008; online 13 August 2008)

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 π stacking [3.753 (1) Å] along the b axis.

Related literature

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

Crystal data

C₁₀H₉NO₄
M_r = 207.18
Monoclinic, C 2/c
a = 24.491 (6) Å
b = 3.753 (1) Å
c = 23.428 (6) Å
β = 116.98 (1)°
V = 1919.0 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 90.0 (2) K
0.30 × 0.10 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.967, T_max = 0.996
3936 measured reflections
2193 independent reflections
1380 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.145
S = 1.04
2193 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O1ⁱ	0.95	2.41	3.130 (2)	133
C1—H1B⋯O4ⁱⁱ	0.95	2.64	3.546 (3)	159
C2—H2A⋯O3ⁱⁱ	0.98	2.68	3.611 (2)	159
C9—H9⋯O4ⁱⁱⁱ	0.95	2.46	3.282 (2)	145
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) -x, -y+2, -z.

Data collection: COLLECT (Nonius, 2002 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; 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 and local procedures.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808025130/fl2212sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808025130/fl2212Isup2.hkl

checkCIF report

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.

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

	Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level (arbitrary spheres for the H atoms).
	Fig. 2. A packing diagram of (I) shown looking down the b axis.

4-Nitrophenyl methacrylate top

Crystal data top

C₁₀H₉NO₄	F(000) = 864
M_r = 207.18	D_x = 1.434 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 24.491 (6) Å	Cell parameters from 2523 reflections
b = 3.753 (1) Å	θ = 1.0–27.5°
c = 23.428 (6) Å	µ = 0.11 mm⁻¹
β = 116.98 (1)°	T = 90 K
V = 1919.0 (9) Å³	Thin rod, colorless
Z = 8	0.30 × 0.10 × 0.04 mm

Data collection top

Nonius KappaCCD diffractometer	2193 independent reflections
Radiation source: fine-focus sealed tube	1380 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
Detector resolution: 18 pixels mm^-1	θ_max = 27.5°, θ_min = 1.9°
ω scans at fixed χ = 55°	h = −31→31
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −4→4
T_min = 0.967, T_max = 0.996	l = −30→29
3936 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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0788P)² + 0.0268P] where P = (F_o² + 2F_c²)/3
2193 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₀H₉NO₄	V = 1919.0 (9) Å³
M_r = 207.18	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 24.491 (6) Å	µ = 0.11 mm⁻¹
b = 3.753 (1) Å	T = 90 K
c = 23.428 (6) Å	0.30 × 0.10 × 0.04 mm
β = 116.98 (1)°

Data collection top

Nonius KappaCCD diffractometer	2193 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	1380 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.996	R_int = 0.049
3936 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.04	Δρ_max = 0.32 e Å⁻³
2193 reflections	Δρ_min = −0.29 e Å⁻³
137 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
C1	0.34238 (9)	0.3043 (6)	0.08125 (9)	0.0350 (5)
H1A	0.3022	0.2636	0.0481	0.042*
H1B	0.3769	0.2388	0.0753	0.042*
C2	0.41131 (8)	0.5324 (6)	0.19114 (9)	0.0327 (5)
H2A	0.4437	0.4551	0.1803	0.049*
H2B	0.4153	0.4042	0.2293	0.049*
H2C	0.4150	0.7891	0.1998	0.049*
C3	0.35044 (8)	0.4545 (6)	0.13665 (9)	0.0258 (5)
C4	0.29729 (8)	0.5595 (5)	0.14726 (9)	0.0247 (5)
C5	0.18934 (8)	0.4978 (5)	0.10638 (9)	0.0232 (5)
C6	0.18535 (8)	0.3892 (5)	0.16081 (8)	0.0248 (5)
H6	0.2196	0.2858	0.1958	0.030*
C7	0.13046 (8)	0.4341 (5)	0.16321 (9)	0.0249 (5)
H7	0.1262	0.3607	0.1998	0.030*
C8	0.08165 (8)	0.5879 (5)	0.11143 (8)	0.0225 (5)
C9	0.08549 (8)	0.6948 (5)	0.05692 (8)	0.0239 (5)
H9	0.0511	0.7963	0.0218	0.029*
C10	0.14063 (8)	0.6505 (5)	0.05472 (8)	0.0243 (5)
H10	0.1449	0.7242	0.0182	0.029*
N1	0.02377 (7)	0.6382 (5)	0.11468 (7)	0.0273 (4)
O1	0.30028 (5)	0.7338 (4)	0.19146 (6)	0.0309 (4)
O2	0.24257 (5)	0.4394 (4)	0.09952 (6)	0.0265 (4)
O3	0.01867 (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

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0292 (11)	0.0418 (15)	0.0387 (11)	−0.0006 (11)	0.0195 (9)	−0.0047 (11)
C2	0.0274 (11)	0.0333 (14)	0.0390 (12)	0.0015 (10)	0.0165 (10)	−0.0001 (10)
C3	0.0258 (10)	0.0259 (12)	0.0286 (11)	−0.0004 (9)	0.0148 (9)	0.0030 (9)
C4	0.0239 (10)	0.0250 (12)	0.0228 (10)	0.0004 (9)	0.0084 (8)	0.0007 (9)
C5	0.0217 (10)	0.0231 (12)	0.0272 (10)	−0.0010 (9)	0.0133 (8)	−0.0051 (9)
C6	0.0215 (10)	0.0237 (12)	0.0246 (10)	−0.0001 (9)	0.0066 (8)	−0.0014 (9)
C7	0.0258 (10)	0.0254 (12)	0.0238 (10)	−0.0008 (9)	0.0116 (8)	−0.0005 (8)
C8	0.0199 (9)	0.0233 (12)	0.0251 (10)	−0.0017 (9)	0.0107 (8)	−0.0032 (9)
C9	0.0230 (10)	0.0233 (12)	0.0219 (9)	0.0006 (9)	0.0070 (8)	−0.0013 (9)
C10	0.0269 (10)	0.0248 (12)	0.0204 (9)	0.0004 (9)	0.0102 (8)	−0.0007 (9)
N1	0.0238 (9)	0.0312 (11)	0.0268 (9)	0.0008 (8)	0.0113 (7)	−0.0005 (8)
O1	0.0260 (7)	0.0375 (10)	0.0295 (7)	−0.0029 (7)	0.0129 (6)	−0.0088 (7)
O2	0.0201 (7)	0.0343 (8)	0.0258 (7)	−0.0005 (6)	0.0111 (6)	−0.0043 (6)
O3	0.0317 (8)	0.0518 (11)	0.0365 (8)	0.0040 (7)	0.0210 (7)	0.0094 (7)
O4	0.0251 (7)	0.0489 (11)	0.0319 (7)	0.0098 (7)	0.0121 (6)	0.0059 (7)

Geometric parameters (Å, º) top

C1—C3	1.345 (3)	C5—O2	1.402 (2)
C1—H1A	0.9500	C6—C7	1.381 (3)
C1—H1B	0.9500	C6—H6	0.9500
C2—C3	1.487 (2)	C7—C8	1.385 (3)
C2—H2A	0.9800	C7—H7	0.9500
C2—H2B	0.9800	C8—C9	1.382 (2)
C2—H2C	0.9800	C8—N1	1.466 (2)
C3—C4	1.485 (3)	C9—C10	1.385 (3)
C4—O1	1.199 (2)	C9—H9	0.9500
C4—O2	1.375 (2)	C10—H10	0.9500
C5—C10	1.381 (3)	N1—O3	1.224 (2)
C5—C6	1.384 (3)	N1—O4	1.231 (2)

C3—C1—H1A	120.0	C7—C6—H6	120.7
C3—C1—H1B	120.0	C5—C6—H6	120.7
H1A—C1—H1B	120.0	C6—C7—C8	119.00 (17)
C3—C2—H2A	109.5	C6—C7—H7	120.5
C3—C2—H2B	109.5	C8—C7—H7	120.5
H2A—C2—H2B	109.5	C9—C8—C7	122.47 (17)
C3—C2—H2C	109.5	C9—C8—N1	118.91 (16)
H2A—C2—H2C	109.5	C7—C8—N1	118.62 (16)
H2B—C2—H2C	109.5	C8—C9—C10	118.42 (17)
C1—C3—C4	121.11 (17)	C8—C9—H9	120.8
C1—C3—C2	124.19 (18)	C10—C9—H9	120.8
C4—C3—C2	114.70 (17)	C5—C10—C9	119.11 (17)
O1—C4—O2	122.47 (17)	C5—C10—H10	120.4
O1—C4—C3	125.08 (17)	C9—C10—H10	120.4
O2—C4—C3	112.45 (16)	O3—N1—O4	123.34 (16)
C10—C5—C6	122.41 (17)	O3—N1—C8	118.44 (15)
C10—C5—O2	116.30 (16)	O4—N1—C8	118.22 (15)
C6—C5—O2	121.19 (16)	C4—O2—C5	118.00 (14)
C7—C6—C5	118.58 (17)

C1—C3—C4—O1	−170.1 (2)	C6—C5—C10—C9	−0.5 (3)
C2—C3—C4—O1	9.4 (3)	O2—C5—C10—C9	176.01 (16)
C1—C3—C4—O2	8.8 (3)	C8—C9—C10—C5	0.8 (3)
C2—C3—C4—O2	−171.74 (17)	C9—C8—N1—O3	172.43 (18)
C10—C5—C6—C7	0.3 (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—O4	172.65 (18)
C6—C7—C8—C9	0.8 (3)	O1—C4—O2—C5	−5.8 (3)
C6—C7—C8—N1	−179.34 (17)	C3—C4—O2—C5	175.30 (15)
C7—C8—C9—C10	−1.0 (3)	C10—C5—O2—C4	129.61 (19)
N1—C8—C9—C10	179.14 (16)	C6—C5—O2—C4	−53.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	0.95	2.41	3.130 (2)	133
C1—H1B···O4ⁱⁱ	0.95	2.64	3.546 (3)	159
C2—H2A···O3ⁱⁱ	0.98	2.68	3.611 (2)	159
C9—H9···O4ⁱⁱⁱ	0.95	2.46	3.282 (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.

Experimental details

Crystal data
Chemical formula	C₁₀H₉NO₄
M_r	207.18
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	90
a, b, c (Å)	24.491 (6), 3.753 (1), 23.428 (6)
β (°)	116.98 (1)
V (Å³)	1919.0 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.10 × 0.04

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.967, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	3936, 2193, 1380
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.145, 1.04
No. of reflections	2193
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.29

Computer programs: COLLECT (Nonius, 2002), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and local procedures.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	0.95	2.41	3.130 (2)	132.7
C1—H1B···O4ⁱⁱ	0.95	2.64	3.546 (3)	158.5
C2—H2A···O3ⁱⁱ	0.98	2.68	3.611 (2)	158.5
C9—H9···O4ⁱⁱⁱ	0.95	2.46	3.282 (2)	145.3

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

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

References

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