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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): o2580.
Published online 2010 September 18. doi:  10.1107/S1600536810036123
PMCID: PMC2983127

2,2-Dimethyl-1,3-benzodioxol-4-yl N-methyl­carbamate

Abstract

In the title compound, C11H13NO4, the two fused rings are almost coplanar, making a dihedral angle of 3.02 (8)°. In the crystal, chains are formed parallel to [010] through N—H(...)O hydrogen bonds between the amine and carbonyl groups.

Related literature

For benzodioxole derivatives, see: Ullrich et al. (2004 [triangle]); Gates & Gillon (1974 [triangle]); Arndt & Franke (1977 [triangle]); Joshi et al. (2005 [triangle]); Jae et al. (2001 [triangle]); Leite et al. (2004 [triangle]).

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Object name is e-66-o2580-scheme1.jpg

Experimental

Crystal data

  • C11H13NO4
  • M r = 223.22
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2580-efi1.jpg
  • a = 9.505 (6) Å
  • b = 9.669 (7) Å
  • c = 12.355 (8) Å
  • β = 94.326 (11)°
  • V = 1132.2 (13) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 298 K
  • 0.24 × 0.18 × 0.16 mm

Data collection

  • Siemens SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Siemens, 1996 [triangle]) T min = 0.976, T max = 0.984
  • 5692 measured reflections
  • 2003 independent reflections
  • 1615 reflections with I > 2σ(I)
  • R int = 0.023

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.098
  • S = 1.03
  • 2003 reflections
  • 146 parameters
  • H-atom parameters constrained
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.13 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); 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/S1600536810036123/bh2301sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036123/bh2301Isup2.hkl

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

supplementary crystallographic information

Comment

Benzodioxoles derivatives can be used as inhibitors of mono-oxygenase enzymes (Ullrich et al., 2004), pesticides or pesticide intermediates (Gates & Gillon, 1974), herbicides (Arndt & Franke, 1977), antioxidants (Joshi et al., 2005), antimicrobials (Jae et al., 2001) and medicines (Leite et al., 2004). As a part of our continuing interest in the synthesis of benzodioxole derivatives, we have isolated the title compound from the reaction of isocyanatomethane, triethylamine and 2,2-dimethylbenzo[d][1,3]dioxol-4-ol, as colorless crystals suitable for X-ray analysis.

As shown in Fig. 1, the molecule is built-up of a five-membered ring and a six-membered ring. Atoms C4, O3, O4, C5, and C6 are coplanar, which is illustrated clearly by the torsion angle O3—C4—C5—C6 [-179.39 (14)°], C3—C4—C5—O4 [177.83 (13)°], C3—C4—C5—C6 [-0.5 (2)°], and O3—C4—C5—O4 [-1.11 (17)°]. In the crystal structure, amino groups and carbonyl groups are involved in the hydrogen-bond network. Carbonyl atom O1 acts as an acceptor, forming the intramolecular hydrogen bonds depicted in Fig. 2.

Experimental

The title compound was synthesized from a mixture of triethylamine (2 mmol, 0.2 g), isocyanatomethane (0.11 mol, 6.3 g) and 2,2-dimethylbenzo[d][1,3]dioxol-4-ol (0.1 mol, 16.6 g). The resulting compound was dissolved in 20 ml of ethanol and 2 ml of water, and refluxed for 10 min. The system was cooled to room temperature and colorless crystals were collected after two weeks.

Refinement

Amine H atom H1 was found in a difference map, and its position fixed. Other H atoms were placed in calculated positions and allowed to ride on their parent atoms at distances of 0.93 (aromatic CH) or 0.96 Å (methyl CH3), with Uiso(H) values fixed to 1.2 or 1.5 times Ueq of the parent atoms.

Figures

Fig. 1.
The asymmetric unit of the title molecule with atom labels, showing 40% probability displacement ellipsoids.
Fig. 2.
Part of the crystal structure, with hydrogen bonds shown as dashed lines.

Crystal data

C11H13NO4F(000) = 472
Mr = 223.22Dx = 1.310 Mg m3
Monoclinic, P21/nMelting point: 408 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 9.505 (6) ÅCell parameters from 2406 reflections
b = 9.669 (7) Åθ = 2.7–26.7°
c = 12.355 (8) ŵ = 0.10 mm1
β = 94.326 (11)°T = 298 K
V = 1132.2 (13) Å3Block, colorless
Z = 40.24 × 0.18 × 0.16 mm

Data collection

Siemens SMART APEX CCD area-detector diffractometer2003 independent reflections
Radiation source: fine-focus sealed tube1615 reflections with I > 2σ(I)
graphiteRint = 0.023
[var phi] and ω scansθmax = 25.1°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Siemens, 1996)h = −11→10
Tmin = 0.976, Tmax = 0.984k = −11→11
5692 measured reflectionsl = −13→14

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.098w = 1/[σ2(Fo2) + (0.0465P)2 + 0.1766P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2003 reflectionsΔρmax = 0.19 e Å3
146 parametersΔρmin = −0.13 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraintsExtinction coefficient: 0.035 (3)
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.78908 (12)0.22049 (10)0.73401 (10)0.0666 (3)
O20.91170 (11)0.04289 (10)0.81309 (9)0.0614 (3)
O31.07164 (11)0.14292 (11)0.63309 (8)0.0624 (3)
O41.27901 (11)0.26676 (13)0.65853 (9)0.0707 (4)
N10.69122 (14)0.01063 (12)0.74902 (10)0.0589 (4)
H10.7052−0.07230.77260.071*
C10.55627 (18)0.04608 (19)0.69670 (16)0.0748 (5)
H1A0.50960.11030.74120.112*
H1B0.4999−0.03600.68640.112*
H1C0.56890.08760.62750.112*
C20.79399 (16)0.10118 (14)0.76185 (11)0.0491 (4)
C31.03134 (16)0.12582 (15)0.82661 (12)0.0537 (4)
C41.10295 (15)0.16741 (14)0.74063 (11)0.0505 (4)
C51.22535 (16)0.24235 (16)0.75644 (12)0.0554 (4)
C61.28072 (19)0.27957 (18)0.85695 (14)0.0674 (5)
H61.36320.33130.86670.081*
C71.2084 (2)0.23669 (19)0.94372 (14)0.0730 (5)
H71.24350.25971.01370.088*
C81.0863 (2)0.16103 (17)0.92966 (13)0.0670 (5)
H81.04020.13330.98980.080*
C91.17105 (17)0.22577 (17)0.57665 (13)0.0602 (4)
C101.2336 (2)0.1358 (2)0.49544 (16)0.0884 (6)
H10A1.30100.18790.45810.133*
H10B1.16040.10290.44410.133*
H10C1.27980.05860.53160.133*
C111.0989 (2)0.35311 (19)0.53297 (16)0.0795 (5)
H11A1.05800.40140.59080.119*
H11B1.02600.32800.47850.119*
H11C1.16620.41190.50150.119*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0786 (8)0.0347 (6)0.0860 (8)0.0026 (5)0.0022 (6)0.0060 (5)
O20.0715 (7)0.0454 (6)0.0679 (7)0.0011 (5)0.0085 (5)0.0166 (5)
O30.0668 (7)0.0740 (7)0.0466 (6)−0.0115 (5)0.0049 (5)−0.0029 (5)
O40.0564 (6)0.0921 (9)0.0635 (7)−0.0089 (6)0.0032 (5)0.0079 (6)
N10.0698 (8)0.0357 (6)0.0725 (9)−0.0011 (6)0.0139 (7)0.0037 (6)
C10.0679 (11)0.0654 (11)0.0919 (13)−0.0016 (9)0.0109 (10)0.0018 (9)
C20.0669 (9)0.0353 (7)0.0470 (8)0.0064 (7)0.0154 (7)−0.0002 (6)
C30.0642 (9)0.0450 (8)0.0520 (9)0.0082 (7)0.0046 (7)0.0053 (6)
C40.0594 (9)0.0461 (8)0.0454 (8)0.0054 (7)0.0009 (7)−0.0001 (6)
C50.0547 (9)0.0559 (8)0.0547 (9)0.0069 (7)−0.0012 (7)0.0018 (7)
C60.0635 (10)0.0667 (11)0.0695 (11)0.0067 (8)−0.0119 (9)−0.0060 (8)
C70.0874 (13)0.0752 (11)0.0536 (10)0.0159 (10)−0.0133 (9)−0.0085 (8)
C80.0877 (12)0.0655 (10)0.0479 (9)0.0156 (9)0.0055 (8)0.0062 (7)
C90.0618 (9)0.0676 (10)0.0516 (9)−0.0041 (8)0.0069 (7)0.0054 (7)
C100.1012 (15)0.0889 (14)0.0794 (13)−0.0004 (11)0.0356 (11)−0.0040 (10)
C110.0805 (12)0.0732 (12)0.0827 (13)0.0011 (10)−0.0081 (10)0.0106 (9)

Geometric parameters (Å, °)

O1—C21.2037 (18)C4—C51.372 (2)
O2—C21.3650 (18)C5—C61.360 (2)
O2—C31.3911 (19)C6—C71.380 (3)
O3—C41.3603 (19)C6—H60.9300
O3—C91.4560 (19)C7—C81.372 (3)
O4—C51.368 (2)C7—H70.9300
O4—C91.441 (2)C8—H80.9300
N1—C21.312 (2)C9—C101.485 (2)
N1—C11.434 (2)C9—C111.490 (2)
N1—H10.8600C10—H10A0.9600
C1—H1A0.9600C10—H10B0.9600
C1—H1B0.9600C10—H10C0.9600
C1—H1C0.9600C11—H11A0.9600
C3—C41.365 (2)C11—H11B0.9600
C3—C81.382 (2)C11—H11C0.9600
C2—O2—C3116.85 (11)C7—C6—H6121.7
C4—O3—C9105.66 (12)C8—C7—C6121.86 (16)
C5—O4—C9106.26 (12)C8—C7—H7119.1
C2—N1—C1121.84 (14)C6—C7—H7119.1
C2—N1—H1119.1C7—C8—C3120.35 (16)
C1—N1—H1119.1C7—C8—H8119.8
N1—C1—H1A109.5C3—C8—H8119.8
N1—C1—H1B109.5O4—C9—O3105.58 (12)
H1A—C1—H1B109.5O4—C9—C10109.58 (15)
N1—C1—H1C109.5O3—C9—C10107.98 (14)
H1A—C1—H1C109.5O4—C9—C11108.10 (14)
H1B—C1—H1C109.5O3—C9—C11109.30 (14)
O1—C2—N1126.32 (15)C10—C9—C11115.83 (16)
O1—C2—O2122.75 (14)C9—C10—H10A109.5
N1—C2—O2110.93 (13)C9—C10—H10B109.5
C4—C3—C8117.95 (16)H10A—C10—H10B109.5
C4—C3—O2121.84 (13)C9—C10—H10C109.5
C8—C3—O2120.08 (14)H10A—C10—H10C109.5
O3—C4—C3128.60 (14)H10B—C10—H10C109.5
O3—C4—C5110.59 (13)C9—C11—H11A109.5
C3—C4—C5120.80 (14)C9—C11—H11B109.5
C6—C5—O4128.11 (16)H11A—C11—H11B109.5
C6—C5—C4122.36 (15)C9—C11—H11C109.5
O4—C5—C4109.50 (13)H11A—C11—H11C109.5
C5—C6—C7116.66 (17)H11B—C11—H11C109.5
C5—C6—H6121.7
C1—N1—C2—O10.8 (2)C3—C4—C5—C6−0.5 (2)
C1—N1—C2—O2−179.66 (13)O3—C4—C5—O4−1.11 (17)
C3—O2—C2—O1−3.81 (19)C3—C4—C5—O4177.83 (13)
C3—O2—C2—N1176.62 (12)O4—C5—C6—C7−177.16 (15)
C2—O2—C3—C4−68.19 (17)C4—C5—C6—C70.8 (2)
C2—O2—C3—C8116.03 (15)C5—C6—C7—C8−0.4 (3)
C9—O3—C4—C3172.56 (15)C6—C7—C8—C3−0.3 (3)
C9—O3—C4—C5−8.60 (16)C4—C3—C8—C70.6 (2)
C8—C3—C4—O3178.46 (14)O2—C3—C8—C7176.56 (14)
O2—C3—C4—O32.6 (2)C5—O4—C9—O3−15.26 (16)
C8—C3—C4—C5−0.3 (2)C5—O4—C9—C10−131.32 (15)
O2—C3—C4—C5−176.13 (13)C5—O4—C9—C11101.61 (15)
C9—O4—C5—C6−171.39 (16)C4—O3—C9—O414.55 (15)
C9—O4—C5—C410.45 (17)C4—O3—C9—C10131.69 (14)
O3—C4—C5—C6−179.39 (14)C4—O3—C9—C11−101.52 (15)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.012.819 (3)157

Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2301).

References

  • Arndt, F. & Franke, H. (1977). DE Patent No. 2624822.
  • Gates, P. S. & Gillon, J. (1974). US Patent No. 3 736 338.
  • Jae, H.-S., Win, M., von Geldern, T. W., Sorensen, B. K., Chiou, W. J., Nguyen, B., Marsh, K. C. & Opgenorth, T. J. (2001). J. Med. Chem.44, 3978–3984. [PubMed]
  • Joshi, R., Kumar, M. S., Satyamoorthy, K., Unnikrisnan, M. K. & Mukherjee, T. (2005). J. Agric. Food Chem.53, 2696–2703. [PubMed]
  • Leite, A. C. L., Peixoto da Silva, K., de Souza, I. A., Magali de Araujo, J. & Brondani, D. J. (2004). Eur. J. Med. Chem.39, 1059–1065. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Siemens (1996). SMART, SAINT and SADABS Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
  • Ullrich, T., Baumann, K., Welzenbach, K., Schmutz, S., Camenish, G., Meingassner, J. G. & Weitz-Schmidt, G. (2004). Bioorg. Med. Chem. Lett.14, 2483–2487. [PubMed]

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