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

Xia, C.-C.

doi:10.1107/S1600536810036123

organic compounds

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Volume 66| Part 10| October 2010| Page o2580

doi:10.1107/S1600536810036123

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

Cheng-Cai Xia ^a ^*

^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 ); Gates & Gillon (1974 ); Arndt & Franke (1977 ); Joshi et al. (2005 ); Jae et al. (2001 ); Leite et al. (2004 ).

Experimental

Crystal data

C₁₁H₁₃NO₄
M_r = 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 ) 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[F² > 2σ(F²)] = 0.035
wR(F²) = 0.098
S = 1.03
2003 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810036123/bh2301sup1.cif

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

checkCIF report

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.

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

	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.

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

Crystal data top

C₁₁H₁₃NO₄	F(000) = 472
M_r = 223.22	D_x = 1.310 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 408 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.505 (6) Å	Cell parameters from 2406 reflections
b = 9.669 (7) Å	θ = 2.7–26.7°
c = 12.355 (8) Å	µ = 0.10 mm⁻¹
β = 94.326 (11)°	T = 298 K
V = 1132.2 (13) Å³	Block, colorless
Z = 4	0.24 × 0.18 × 0.16 mm

Data collection top

Siemens SMART APEX CCD area-detector diffractometer	2003 independent reflections
Radiation source: fine-focus sealed tube	1615 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 25.1°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Siemens, 1996)	h = −11→10
T_min = 0.976, T_max = 0.984	k = −11→11
5692 measured reflections	l = −13→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0465P)² + 0.1766P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2003 reflections	Δρ_max = 0.19 e Å⁻³
146 parameters	Δρ_min = −0.13 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.035 (3)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₁H₁₃NO₄	V = 1132.2 (13) Å³
M_r = 223.22	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.505 (6) Å	µ = 0.10 mm⁻¹
b = 9.669 (7) Å	T = 298 K
c = 12.355 (8) Å	0.24 × 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)
T_min = 0.976, T_max = 0.984	R_int = 0.023
5692 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.03	Δρ_max = 0.19 e Å⁻³
2003 reflections	Δρ_min = −0.13 e Å⁻³
146 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.78908 (12)	0.22049 (10)	0.73401 (10)	0.0666 (3)
O2	0.91170 (11)	0.04289 (10)	0.81309 (9)	0.0614 (3)
O3	1.07164 (11)	0.14292 (11)	0.63309 (8)	0.0624 (3)
O4	1.27901 (11)	0.26676 (13)	0.65853 (9)	0.0707 (4)
N1	0.69122 (14)	0.01063 (12)	0.74902 (10)	0.0589 (4)
H1	0.7052	−0.0723	0.7726	0.071*
C1	0.55627 (18)	0.04608 (19)	0.69670 (16)	0.0748 (5)
H1A	0.5096	0.1103	0.7412	0.112*
H1B	0.4999	−0.0360	0.6864	0.112*
H1C	0.5689	0.0876	0.6275	0.112*
C2	0.79399 (16)	0.10118 (14)	0.76185 (11)	0.0491 (4)
C3	1.03134 (16)	0.12582 (15)	0.82661 (12)	0.0537 (4)
C4	1.10295 (15)	0.16741 (14)	0.74063 (11)	0.0505 (4)
C5	1.22535 (16)	0.24235 (16)	0.75644 (12)	0.0554 (4)
C6	1.28072 (19)	0.27957 (18)	0.85695 (14)	0.0674 (5)
H6	1.3632	0.3313	0.8667	0.081*
C7	1.2084 (2)	0.23669 (19)	0.94372 (14)	0.0730 (5)
H7	1.2435	0.2597	1.0137	0.088*
C8	1.0863 (2)	0.16103 (17)	0.92966 (13)	0.0670 (5)
H8	1.0402	0.1333	0.9898	0.080*
C9	1.17105 (17)	0.22577 (17)	0.57665 (13)	0.0602 (4)
C10	1.2336 (2)	0.1358 (2)	0.49544 (16)	0.0884 (6)
H10A	1.3010	0.1879	0.4581	0.133*
H10B	1.1604	0.1029	0.4441	0.133*
H10C	1.2798	0.0586	0.5316	0.133*
C11	1.0989 (2)	0.35311 (19)	0.53297 (16)	0.0795 (5)
H11A	1.0580	0.4014	0.5908	0.119*
H11B	1.0260	0.3280	0.4785	0.119*
H11C	1.1662	0.4119	0.5015	0.119*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0786 (8)	0.0347 (6)	0.0860 (8)	0.0026 (5)	0.0022 (6)	0.0060 (5)
O2	0.0715 (7)	0.0454 (6)	0.0679 (7)	0.0011 (5)	0.0085 (5)	0.0166 (5)
O3	0.0668 (7)	0.0740 (7)	0.0466 (6)	−0.0115 (5)	0.0049 (5)	−0.0029 (5)
O4	0.0564 (6)	0.0921 (9)	0.0635 (7)	−0.0089 (6)	0.0032 (5)	0.0079 (6)
N1	0.0698 (8)	0.0357 (6)	0.0725 (9)	−0.0011 (6)	0.0139 (7)	0.0037 (6)
C1	0.0679 (11)	0.0654 (11)	0.0919 (13)	−0.0016 (9)	0.0109 (10)	0.0018 (9)
C2	0.0669 (9)	0.0353 (7)	0.0470 (8)	0.0064 (7)	0.0154 (7)	−0.0002 (6)
C3	0.0642 (9)	0.0450 (8)	0.0520 (9)	0.0082 (7)	0.0046 (7)	0.0053 (6)
C4	0.0594 (9)	0.0461 (8)	0.0454 (8)	0.0054 (7)	0.0009 (7)	−0.0001 (6)
C5	0.0547 (9)	0.0559 (8)	0.0547 (9)	0.0069 (7)	−0.0012 (7)	0.0018 (7)
C6	0.0635 (10)	0.0667 (11)	0.0695 (11)	0.0067 (8)	−0.0119 (9)	−0.0060 (8)
C7	0.0874 (13)	0.0752 (11)	0.0536 (10)	0.0159 (10)	−0.0133 (9)	−0.0085 (8)
C8	0.0877 (12)	0.0655 (10)	0.0479 (9)	0.0156 (9)	0.0055 (8)	0.0062 (7)
C9	0.0618 (9)	0.0676 (10)	0.0516 (9)	−0.0041 (8)	0.0069 (7)	0.0054 (7)
C10	0.1012 (15)	0.0889 (14)	0.0794 (13)	−0.0004 (11)	0.0356 (11)	−0.0040 (10)
C11	0.0805 (12)	0.0732 (12)	0.0827 (13)	0.0011 (10)	−0.0081 (10)	0.0106 (9)

Geometric parameters (Å, º) top

O1—C2	1.2037 (18)	C4—C5	1.372 (2)
O2—C2	1.3650 (18)	C5—C6	1.360 (2)
O2—C3	1.3911 (19)	C6—C7	1.380 (3)
O3—C4	1.3603 (19)	C6—H6	0.9300
O3—C9	1.4560 (19)	C7—C8	1.372 (3)
O4—C5	1.368 (2)	C7—H7	0.9300
O4—C9	1.441 (2)	C8—H8	0.9300
N1—C2	1.312 (2)	C9—C10	1.485 (2)
N1—C1	1.434 (2)	C9—C11	1.490 (2)
N1—H1	0.8600	C10—H10A	0.9600
C1—H1A	0.9600	C10—H10B	0.9600
C1—H1B	0.9600	C10—H10C	0.9600
C1—H1C	0.9600	C11—H11A	0.9600
C3—C4	1.365 (2)	C11—H11B	0.9600
C3—C8	1.382 (2)	C11—H11C	0.9600

C2—O2—C3	116.85 (11)	C7—C6—H6	121.7
C4—O3—C9	105.66 (12)	C8—C7—C6	121.86 (16)
C5—O4—C9	106.26 (12)	C8—C7—H7	119.1
C2—N1—C1	121.84 (14)	C6—C7—H7	119.1
C2—N1—H1	119.1	C7—C8—C3	120.35 (16)
C1—N1—H1	119.1	C7—C8—H8	119.8
N1—C1—H1A	109.5	C3—C8—H8	119.8
N1—C1—H1B	109.5	O4—C9—O3	105.58 (12)
H1A—C1—H1B	109.5	O4—C9—C10	109.58 (15)
N1—C1—H1C	109.5	O3—C9—C10	107.98 (14)
H1A—C1—H1C	109.5	O4—C9—C11	108.10 (14)
H1B—C1—H1C	109.5	O3—C9—C11	109.30 (14)
O1—C2—N1	126.32 (15)	C10—C9—C11	115.83 (16)
O1—C2—O2	122.75 (14)	C9—C10—H10A	109.5
N1—C2—O2	110.93 (13)	C9—C10—H10B	109.5
C4—C3—C8	117.95 (16)	H10A—C10—H10B	109.5
C4—C3—O2	121.84 (13)	C9—C10—H10C	109.5
C8—C3—O2	120.08 (14)	H10A—C10—H10C	109.5
O3—C4—C3	128.60 (14)	H10B—C10—H10C	109.5
O3—C4—C5	110.59 (13)	C9—C11—H11A	109.5
C3—C4—C5	120.80 (14)	C9—C11—H11B	109.5
C6—C5—O4	128.11 (16)	H11A—C11—H11B	109.5
C6—C5—C4	122.36 (15)	C9—C11—H11C	109.5
O4—C5—C4	109.50 (13)	H11A—C11—H11C	109.5
C5—C6—C7	116.66 (17)	H11B—C11—H11C	109.5
C5—C6—H6	121.7

C1—N1—C2—O1	0.8 (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—O4	177.83 (13)
C3—O2—C2—N1	176.62 (12)	O4—C5—C6—C7	−177.16 (15)
C2—O2—C3—C4	−68.19 (17)	C4—C5—C6—C7	0.8 (2)
C2—O2—C3—C8	116.03 (15)	C5—C6—C7—C8	−0.4 (3)
C9—O3—C4—C3	172.56 (15)	C6—C7—C8—C3	−0.3 (3)
C9—O3—C4—C5	−8.60 (16)	C4—C3—C8—C7	0.6 (2)
C8—C3—C4—O3	178.46 (14)	O2—C3—C8—C7	176.56 (14)
O2—C3—C4—O3	2.6 (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—C11	101.61 (15)
C9—O4—C5—C6	−171.39 (16)	C4—O3—C9—O4	14.55 (15)
C9—O4—C5—C4	10.45 (17)	C4—O3—C9—C10	131.69 (14)
O3—C4—C5—C6	−179.39 (14)	C4—O3—C9—C11	−101.52 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.01	2.819 (3)	157

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃NO₄
M_r	223.22
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	9.505 (6), 9.669 (7), 12.355 (8)
β (°)	94.326 (11)
V (Å³)	1132.2 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.24 × 0.18 × 0.16

Data collection
Diffractometer	Siemens SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Siemens, 1996)
T_min, T_max	0.976, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	5692, 2003, 1615
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.098, 1.03
No. of reflections	2003
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.01	2.819 (3)	157.1

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

References

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Volume 66| Part 10| October 2010| Page o2580

doi:10.1107/S1600536810036123

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