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Acta Crystallogr Sect E Struct Rep Online. 2009 January 1; 65(Pt 1): o47.
Published online 2008 December 10. doi:  10.1107/S1600536808040622
PMCID: PMC2967962

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

Abstract

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.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-65-00o47-scheme1.jpg

Experimental

Crystal data

  • C11H14N2O5
  • M r = 254.24
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-00o47-efi1.jpg
  • a = 5.034 (2) Å
  • b = 10.4221 (16) Å
  • c = 12.6319 (12) Å
  • α = 91.361 (3)°
  • β = 97.492 (2)°
  • γ = 94.6930 (10)°
  • V = 654.5 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 291 (2) K
  • 0.30 × 0.26 × 0.24 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.97, T max = 0.98
  • 7186 measured reflections
  • 3172 independent reflections
  • 2005 reflections with I > 2σ(I)
  • R int = 0.038

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.105
  • S = 1.03
  • 3172 reflections
  • 167 parameters
  • H-atom parameters constrained
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.21 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808040622/fj2175sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808040622/fj2175Isup2.hkl

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

Acknowledgments

This work was supported by the Wu Jieping Medical Foundation (32067500615) and National "863" Project of China (No. 2006AA10Z449)

supplementary crystallographic information

Comment

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).

Experimental

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

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).

Figures

Fig. 1.
The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
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.

Crystal data

C11H14N2O5Z = 2
Mr = 254.24F(000) = 268
Triclinic, P1Dx = 1.290 Mg m3
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 mm1
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

Bruker SMART APEX CCD diffractometer3172 independent reflections
Radiation source: sealed tube2005 reflections with I > 2σ(I)
graphiteRint = 0.038
[var phi] 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

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) = 0.105w = 1/[σ2(Fo2) + (0.04P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
3172 reflectionsΔρmax = 0.25 e Å3
167 parametersΔρmin = −0.21 e Å3
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)

Special details

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)

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)

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, °)

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, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···O5i0.862.052.788 (2)143

Symmetry codes: (i) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FJ2175).

References

  • Allan, J., Oxford, A. E., Robinson, R. & Smith, J. C. (1926). J. Chem. Soc. pp. 401–411.
  • Bruker (2001). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Czugler, M. & Kalman, A. (1975). Cryst. Struct. Commun.4, 531–532.
  • Moreno, M. J., Abad, A. & Montoya, A. (2001). J. Agric. Food Chem.49, 72–78. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, T. C., Chiou, J. M., Chang, Y. L. & Hu, M. C. (1998). Carcinogenesis, 19, 623–629. [PubMed]
  • Xu, L.-Z., Yu, G.-P. & Yang, S.-H. (2005). Acta Cryst. E61, o1924–o1926.

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