organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

aDepartment of Pharmaceutical Sciences, Taishan Medicine College, Taian 271000, People's Republic of China
*Correspondence e-mail: xiachc@163.com

(Received 14 July 2010; accepted 8 September 2010; online 18 September 2010)

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[Ullrich, T., Baumann, K., Welzenbach, K., Schmutz, S., Camenish, G., Meingassner, J. G. & Weitz-Schmidt, G. (2004). Bioorg. Med. Chem. Lett. 14, 2483-2487.]); Gates & Gillon (1974[Gates, P. S. & Gillon, J. (1974). US Patent No. 3 736 338.]); Arndt & Franke (1977[Arndt, F. & Franke, H. (1977). DE Patent No. 2624822.]); Joshi et al. (2005[Joshi, R., Kumar, M. S., Satyamoorthy, K., Unnikrisnan, M. K. & Mukherjee, T. (2005). J. Agric. Food Chem. 53, 2696-2703.]); Jae et al. (2001[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.]); Leite et al. (2004[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.]).

[Scheme 1]

Experimental

Crystal data
  • C11H13NO4

  • Mr = 223.22

  • Monoclinic, P 21 /n

  • 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[Siemens (1996). SMART, SAINT and SADABS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]) Tmin = 0.976, Tmax = 0.984

  • 5692 measured reflections

  • 2003 independent reflections

  • 1615 reflections with I > 2σ(I)

  • Rint = 0.023

Refinement
  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯O1i 0.86 2.01 2.819 (3) 157
Symmetry code: (i) [-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}].

Data collection: SMART (Siemens, 1996[Siemens (1996). SMART, SAINT and SADABS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Siemens, 1996[Siemens (1996). SMART, SAINT and SADABS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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.

Related literature top

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

Experimental top

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 top

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.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title molecule with atom labels, showing 40% probability displacement ellipsoids.
[Figure 2] Fig. 2. Part of the crystal structure, with hydrogen bonds shown as dashed lines.
2,2-Dimethyl-1,3-benzodioxol-4-yl N-methylcarbamate top
Crystal data top
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 top
Siemens SMART APEX CCD area-detector
diffractometer
2003 independent reflections
Radiation source: fine-focus sealed tube1615 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
ϕ and ω scansθmax = 25.1°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Siemens, 1996)
h = 1110
Tmin = 0.976, Tmax = 0.984k = 1111
5692 measured reflectionsl = 1314
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)] = 0.035H-atom parameters constrained
wR(F2) = 0.098 w = 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
Crystal data top
C11H13NO4V = 1132.2 (13) Å3
Mr = 223.22Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.505 (6) ŵ = 0.10 mm1
b = 9.669 (7) ÅT = 298 K
c = 12.355 (8) Å0.24 × 0.18 × 0.16 mm
β = 94.326 (11)°
Data collection top
Siemens SMART APEX CCD area-detector
diffractometer
2003 independent reflections
Absorption correction: multi-scan
(SADABS; Siemens, 1996)
1615 reflections with I > 2σ(I)
Tmin = 0.976, Tmax = 0.984Rint = 0.023
5692 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.098H-atom parameters constrained
S = 1.03Δρmax = 0.19 e Å3
2003 reflectionsΔρmin = 0.13 e Å3
146 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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)
H10.70520.07230.77260.071*
C10.55627 (18)0.04608 (19)0.69670 (16)0.0748 (5)
H1A0.50960.11030.74120.112*
H1B0.49990.03600.68640.112*
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) top
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, º) top
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—C60.5 (2)
C1—N1—C2—O2179.66 (13)O3—C4—C5—O41.11 (17)
C3—O2—C2—O13.81 (19)C3—C4—C5—O4177.83 (13)
C3—O2—C2—N1176.62 (12)O4—C5—C6—C7177.16 (15)
C2—O2—C3—C468.19 (17)C4—C5—C6—C70.8 (2)
C2—O2—C3—C8116.03 (15)C5—C6—C7—C80.4 (3)
C9—O3—C4—C3172.56 (15)C6—C7—C8—C30.3 (3)
C9—O3—C4—C58.60 (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—O315.26 (16)
C8—C3—C4—C50.3 (2)C5—O4—C9—C10131.32 (15)
O2—C3—C4—C5176.13 (13)C5—O4—C9—C11101.61 (15)
C9—O4—C5—C6171.39 (16)C4—O3—C9—O414.55 (15)
C9—O4—C5—C410.45 (17)C4—O3—C9—C10131.69 (14)
O3—C4—C5—C6179.39 (14)C4—O3—C9—C11101.52 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.012.819 (3)157
Symmetry code: (i) x+3/2, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC11H13NO4
Mr223.22
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)9.505 (6), 9.669 (7), 12.355 (8)
β (°) 94.326 (11)
V3)1132.2 (13)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.24 × 0.18 × 0.16
Data collection
DiffractometerSiemens SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Siemens, 1996)
Tmin, Tmax0.976, 0.984
No. of measured, independent and
observed [I > 2σ(I)] reflections
5692, 2003, 1615
Rint0.023
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.098, 1.03
No. of reflections2003
No. of parameters146
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.13

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.012.819 (3)157.1
Symmetry code: (i) x+3/2, y1/2, z+3/2.
 

References

First citationArndt, F. & Franke, H. (1977). DE Patent No. 2624822.  Google Scholar
First citationGates, P. S. & Gillon, J. (1974). US Patent No. 3 736 338.  Google Scholar
First citationJae, 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.  Web of Science CrossRef PubMed CAS Google Scholar
First citationJoshi, R., Kumar, M. S., Satyamoorthy, K., Unnikrisnan, M. K. & Mukherjee, T. (2005). J. Agric. Food Chem. 53, 2696–2703.  Web of Science CrossRef PubMed CAS Google Scholar
First citationLeite, 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.  Web of Science CrossRef PubMed CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSiemens (1996). SMART, SAINT and SADABS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.  Google Scholar
First citationUllrich, T., Baumann, K., Welzenbach, K., Schmutz, S., Camenish, G., Meingassner, J. G. & Weitz-Schmidt, G. (2004). Bioorg. Med. Chem. Lett. 14, 2483–2487.  CrossRef PubMed CAS Google Scholar

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