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Acta Cryst. (2009). E65, o47    [ doi:10.1107/S1600536808040622 ]

2-(1-Methylethoxy)-5-nitrophenyl N-methylcarbamate

G.-M. Sang, S.-N. Luo, J.-G. Lin, H.-L. Yang and Y.-M. Xia

Abstract top

In the title compound, C11H14N2O5, the nitro group is approximately coplanar with the benzene ring, making a dihedral angle of 4.26 (17)°. The dihedral angle between the methylcarbamate group and the benzene ring is 72.47 (6)°. There is a strong intermolecular N-H...O hydrogen bond between the N and O atoms from adjacent methylcarbamate groups, forming a one-dimensional network along the a axis.

Comment top

2-(1-Methylethoxy)phenyl methylcarbamate (Trade name: Propoxur) is an important economical insecticide. It is widely used to control agricultural and household insect pests due to its low toxicity to mammals and other vertebrates (Wang et al., 1998; Moreno et al., 2001). Immunoassay is one of effective analytical methods of determining the residua of the methylcarbamate pesticide propoxur. Propoxur, like most pesticides, is a small and simple organic molecule, which lacks a functional group (amido or carboxylic acid) for coupling to proteins and is non immunogenic by itself. Therefore, it is necessary to synthesis hapten resembling as much as possible the structural and electronic distribution of propoxur for the production of highaffinity antibodies (Moreno et al., 2001). With this idea in mind, we intend to synthesis 5-amino-2-(1-methylethoxy)phenyl methylcarbamate. As a vital intermediate compound for the stepwise reactions of hapten synthesis, the synthesis and crystal structure of the title compound has been reported herein.

In the title compound (I) (Fig. 1), C11H14N2O5, the nitro group is approximately coplanar with the phenyl ring [dihedral angle = 4.26 (17)°]. All the nonhydrogen atoms in the methylcarbamate group are almost in a plane, and the dihedral angle between methylcarbamate group and phenyl is 72.47 (6)°. There is a strong N—H···O intermolecular hydrogen bond between the N2 atom and O5 atom from adjacent methylcarbamate groups (Table 1). And the crystal structure is stabilized by these strong hydrogen bond interactions to form one-dimensional supramolecular network along a axis (Table 1 and Fig. 2).

Related literature top

For general background, see: Wang et al. (1998); Moreno et al. (2001). For related structures, see: Czugler & Kalman (1975); Xu et al. (2005). For the synthesis, see: Allan et al. (1926).

Experimental top

The title compound (I) was synthesized as follows (Allan et al., 1926): Nitric acid (25 ml, d 1.42, 0.6 mol) was added to a solution of 2-(1-methylethoxy)-phenyl methylcarbamate (20.9 g, 0.1 mol) in acetic acid (30 ml), and the mixture was heated on the oil-bath until the onset of a vigorous reaction was manifested by the copious evolution of red fumes and temperature rising to around 100 °C. Then, the reaction mixture was heated on this condition for 3 h, poured into cool water, and stirred for 30 min. After filtering, washing with water and drying in vacuum, a white powder was then obtained (yield: 75%). mp 120–121 °C. The title compound was recrystallized from ethanol solvent; colourless block-shaped crystals were formed after several days (yield 58%). Analysis calculated for C11H14N2O5: C 51.97, H 5.55, N 11.02%; found: C 51.92, H 5.49, N 11.08%.

Refinement top

H atoms bonded to N atom was located in a difference map and refined with distance restraints of N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(N). Other H atoms were positioned geometrically and refined using a riding model (including free rotation about the ethanol C—C bond), with C—H = 0.93–0.98 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. Perspective view of the supramolecular network along a axis built from strong intermolecular N—H···O hydrogen bonds (dashed lines). H atoms not involved in hydrogen bonds have been omitted.
2-(1-Methylethoxy)-5-nitrophenyl N-methylcarbamate top
Crystal data top
C11H14N2O5Z = 2
Mr = 254.24F(000) = 268
Triclinic, P1Dx = 1.290 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.034 (2) ÅCell parameters from 825 reflections
b = 10.4221 (16) Åθ = 2.1–25.4°
c = 12.6319 (12) ŵ = 0.10 mm−1
α = 91.361 (3)°T = 291 K
β = 97.492 (2)°Block, colourless
γ = 94.693 (1)°0.30 × 0.26 × 0.24 mm
V = 654.5 (3) Å3
Data collection top
Bruker SMART APEX CCD
diffractometer		3172 independent reflections
Radiation source: sealed tube2005 reflections with I > 2σ(I)
graphiteRint = 0.038
φ and ω scansθmax = 28.0°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −6→6
Tmin = 0.97, Tmax = 0.98k = −13→13
7186 measured reflectionsl = −10→16
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)] = 0.049H-atom parameters constrained
wR(F2) = 0.105 w = 1/[σ2(Fo2) + (0.04P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
3172 reflectionsΔρmax = 0.25 e Å−3
167 parametersΔρmin = −0.21 e Å−3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.015 (3)
Crystal data top
C11H14N2O5γ = 94.693 (1)°
Mr = 254.24V = 654.5 (3) Å3
Triclinic, P1Z = 2
a = 5.034 (2) ÅMo Kα radiation
b = 10.4221 (16) ŵ = 0.10 mm−1
c = 12.6319 (12) ÅT = 291 K
α = 91.361 (3)°0.30 × 0.26 × 0.24 mm
β = 97.492 (2)°
Data collection top
Bruker SMART APEX CCD
diffractometer		3172 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2005 reflections with I > 2σ(I)
Tmin = 0.97, Tmax = 0.98Rint = 0.038
7186 measured reflectionsθmax = 28.0°
Refinement top
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.105Δρmax = 0.25 e Å−3
S = 1.03Δρmin = −0.21 e Å−3
3172 reflectionsAbsolute structure: ?
167 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
C10.6429 (3)1.05070 (14)0.65269 (13)0.0418 (3)
C20.4552 (3)1.04573 (14)0.72651 (12)0.0408 (3)
H20.40101.12050.75570.049*
C30.3576 (3)0.92824 (15)0.75300 (12)0.0401 (3)
C40.4281 (3)0.81480 (14)0.70606 (12)0.0404 (3)
C50.6183 (3)0.82349 (14)0.63360 (12)0.0410 (3)
H50.67320.74920.60390.049*
C60.7215 (3)0.94193 (14)0.60731 (12)0.0412 (3)
H60.84500.94870.55860.049*
C70.4126 (3)0.58077 (15)0.71348 (12)0.0419 (3)
H70.60490.59050.70680.050*
C80.3506 (4)0.49615 (16)0.80518 (15)0.0503 (4)
H8A0.41810.54060.87190.075*
H8B0.43510.41730.80040.075*
H8C0.15960.47720.80110.075*
C90.2464 (4)0.52696 (15)0.61402 (13)0.0475 (4)
H9A0.05960.52360.62310.071*
H9B0.29390.44170.59900.071*
H9C0.27830.58090.55560.071*
C100.2341 (3)0.86019 (14)0.91676 (12)0.0379 (3)
C110.0362 (3)0.77353 (16)1.06731 (13)0.0446 (4)
H11A0.13980.70021.06690.067*
H11B−0.14140.74661.08270.067*
H11C0.12170.83561.12110.067*
N10.7563 (3)1.17674 (12)0.62443 (11)0.0435 (3)
N20.0186 (3)0.83114 (12)0.96365 (10)0.0403 (3)
H2A−0.13640.84680.93180.048*
O10.6715 (2)1.27246 (10)0.66209 (9)0.0473 (3)
O20.9315 (2)1.18325 (10)0.56528 (9)0.0446 (3)
O30.3060 (2)0.70444 (10)0.73769 (9)0.0420 (3)
O40.1650 (2)0.91925 (10)0.82168 (9)0.0418 (3)
O50.4638 (2)0.84188 (10)0.95050 (9)0.0421 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0464 (9)0.0377 (7)0.0423 (8)0.0040 (6)0.0085 (7)0.0037 (6)
C20.0388 (8)0.0429 (8)0.0423 (8)0.0116 (6)0.0067 (6)0.0029 (6)
C30.0387 (8)0.0459 (8)0.0372 (8)0.0083 (6)0.0084 (6)−0.0029 (6)
C40.0410 (8)0.0418 (8)0.0404 (8)0.0090 (6)0.0110 (6)−0.0028 (6)
C50.0468 (9)0.0389 (7)0.0389 (8)0.0066 (6)0.0111 (6)−0.0056 (6)
C60.0428 (8)0.0432 (8)0.0396 (8)0.0111 (6)0.0081 (6)0.0020 (6)
C70.0422 (8)0.0495 (8)0.0368 (8)0.0112 (7)0.0107 (6)0.0048 (6)
C80.0526 (10)0.0487 (9)0.0528 (10)0.0121 (7)0.0124 (8)0.0120 (7)
C90.0516 (10)0.0448 (9)0.0474 (9)0.0104 (7)0.0098 (7)−0.0148 (7)
C100.0319 (7)0.0431 (8)0.0404 (8)0.0099 (6)0.0081 (6)−0.0047 (6)
C110.0439 (9)0.0507 (9)0.0422 (9)0.0122 (7)0.0101 (7)0.0093 (7)
N10.0403 (7)0.0433 (7)0.0477 (8)0.0027 (5)0.0091 (6)0.0016 (5)
N20.0333 (6)0.0458 (7)0.0453 (8)0.0124 (5)0.0118 (5)0.0096 (5)
O10.0508 (7)0.0413 (6)0.0529 (7)0.0042 (5)0.0191 (5)0.0017 (5)
O20.0530 (7)0.0433 (6)0.0387 (6)−0.0037 (5)0.0141 (5)0.0074 (4)
O30.0415 (6)0.0427 (6)0.0437 (6)0.0036 (4)0.0136 (5)−0.0016 (4)
O40.0447 (6)0.0411 (5)0.0450 (6)0.0169 (5)0.0170 (5)0.0039 (4)
O50.0360 (6)0.0487 (6)0.0449 (6)0.0140 (5)0.0097 (5)0.0127 (5)
Geometric parameters (Å, °) top
C1—C61.368 (2)C8—H8A0.9600
C1—C21.410 (2)C8—H8B0.9600
C1—N11.4600 (19)C8—H8C0.9600
C2—C31.348 (2)C9—H9A0.9600
C2—H20.9300C9—H9B0.9600
C3—O41.3818 (18)C9—H9C0.9600
C3—C41.402 (2)C10—O51.2107 (18)
C4—O31.3530 (19)C10—N21.3195 (18)
C4—C51.408 (2)C10—O41.3797 (19)
C5—C61.365 (2)C11—N21.4487 (19)
C5—H50.9300C11—H11A0.9600
C6—H60.9300C11—H11B0.9600
C7—O31.4766 (18)C11—H11C0.9600
C7—C91.486 (2)N1—O11.2263 (17)
C7—C81.521 (2)N1—O21.2270 (17)
C7—H70.9800N2—H2A0.8600
C6—C1—C2122.26 (14)C7—C8—H8C109.5
C6—C1—N1119.34 (15)H8A—C8—H8C109.5
C2—C1—N1118.40 (14)H8B—C8—H8C109.5
C3—C2—C1117.29 (14)C7—C9—H9A109.5
C3—C2—H2121.4C7—C9—H9B109.5
C1—C2—H2121.4H9A—C9—H9B109.5
C2—C3—O4119.06 (13)C7—C9—H9C109.5
C2—C3—C4122.00 (15)H9A—C9—H9C109.5
O4—C3—C4118.72 (13)H9B—C9—H9C109.5
O3—C4—C3115.20 (14)O5—C10—N2126.72 (15)
O3—C4—C5125.76 (13)O5—C10—O4122.87 (14)
C3—C4—C5119.03 (14)N2—C10—O4110.40 (13)
C6—C5—C4119.41 (14)N2—C11—H11A109.5
C6—C5—H5120.3N2—C11—H11B109.5
C4—C5—H5120.3H11A—C11—H11B109.5
C5—C6—C1119.92 (15)N2—C11—H11C109.5
C5—C6—H6120.0H11A—C11—H11C109.5
C1—C6—H6120.0H11B—C11—H11C109.5
O3—C7—C9106.04 (13)O1—N1—O2122.72 (13)
O3—C7—C8104.34 (12)O1—N1—C1117.78 (13)
C9—C7—C8108.30 (15)O2—N1—C1119.50 (13)
O3—C7—H7112.5C10—N2—C11121.78 (13)
C9—C7—H7112.5C10—N2—H2A119.1
C8—C7—H7112.5C11—N2—H2A119.1
C7—C8—H8A109.5C4—O3—C7118.97 (12)
C7—C8—H8B109.5C10—O4—C3116.28 (12)
H8A—C8—H8B109.5
C6—C1—C2—C31.2 (2)C2—C1—N1—O1−3.8 (2)
N1—C1—C2—C3−178.66 (15)C6—C1—N1—O2−4.2 (2)
C1—C2—C3—O4−177.36 (14)C2—C1—N1—O2175.73 (15)
C1—C2—C3—C4−2.9 (2)O5—C10—N2—C111.4 (2)
C2—C3—C4—O3−177.54 (14)O4—C10—N2—C11−177.13 (13)
O4—C3—C4—O3−3.1 (2)C3—C4—O3—C7−165.57 (13)
C2—C3—C4—C53.7 (3)C5—C4—O3—C713.1 (2)
O4—C3—C4—C5178.15 (14)C9—C7—O3—C4−96.64 (16)
O3—C4—C5—C6178.71 (15)C8—C7—O3—C4149.11 (14)
C3—C4—C5—C6−2.7 (2)O5—C10—O4—C315.7 (2)
C4—C5—C6—C11.1 (3)N2—C10—O4—C3−165.71 (12)
C2—C1—C6—C5−0.3 (3)C2—C3—O4—C10−118.54 (16)
N1—C1—C6—C5179.56 (14)C4—C3—O4—C1066.83 (18)
C6—C1—N1—O1176.26 (14)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O5i0.862.052.788 (2)143
Symmetry codes: (i) x−1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O5i0.862.052.788 (2)143
Symmetry codes: (i) x−1, y, z.
Acknowledgements top

This work was supported by the Wu Jieping Medical Found (32067500615) and National "863" Project of China (No. 2006 A A10Z449)

references
References top

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