2-Isopropoxyphenyl N-methyl­carbamate

Wu, J.; Xie, M.-H.; Luo, S.-N.; Zou, P.; He, Y.-J.

doi:10.1107/S1600536809002372

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o381

doi:10.1107/S1600536809002372

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2-Isopropoxyphenyl N-methylcarbamate

Jun Wu,^a Min-Hao Xie,^a ^* Shi-Neng Luo,^a Pei Zou ^a and Yong-Jun He ^a

^aJiangsu Institute of Nuclear Medicine, Wuxi 214063, People's Republic of China
^*Correspondence e-mail: wujunnju@hotmail.com

(Received 25 November 2008; accepted 19 January 2009; online 23 January 2009)

In the title compound, C₁₁H₁₅NO₃, the mean planes of the carboxamide and isopropyl groups are inclined at 109.9 (1) and 128.7 (2)°, respectively, to the mean plane of the phenoxy group. In the crystal structure, molecules are stacked along the b axis, without any π–π interactions. The stacked columns are linked together by intermolecular N—H⋯O hydrogen bonds, with an N⋯O distance of 2.842 (2) Å.

Related literature

For background literature, see: Abburi & Nutalapati (2004 ); Moreno et al. (2001 ); Wang et al. (1998 ). For a report of a similar compound, see: Czugler & Kalman (1975 ).

Experimental

Crystal data

C₁₁H₁₅NO₃
M_r = 209.24
Monoclinic, P 2₁ /c
a = 13.275 (3) Å
b = 8.8890 (18) Å
c = 9.931 (2) Å
β = 90.59 (3)°
V = 1171.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 (2) K
0.30 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (CAD-4 Software; Enraf–Nonius, 1989 ) T_min = 0.975, T_max = 0.991
2257 measured reflections
2121 independent reflections
1255 reflections with I > 2σ(I)
R_int = 0.023
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.152
S = 1.01
2121 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H0A⋯O3ⁱ	0.86	2.02	2.842 (2)	159
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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 I, global. DOI: 10.1107/S1600536809002372/pv2125sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809002372/pv2125Isup2.hkl

checkCIF report

Comment top

The title compound is one of the most important carbamate pesticides. It is widely used to control agricultural and household insect pests due to its low toxicity to mammals and other vertebrates (Abburi & Nutalapati, 2004; Moreno et al., 2001; Wang et al., 1998). We report here the crystal structure of title compound, (I).

The bond lengths and bond angles in title molecule (Fig. 1) are in agreement with those reported for a similar compound incorporating the phenoxycarboxamide group (Czugler & Kalman, 1975). In (I), the O3/C10/N1/C11 plane forms a dihedral angle of 109.9 (1)° with the C4–C9/O2 plane. The C1/C2/C3 plane forms a dihedral angle of 128.7 (2)° with the C4–C9/O1 plane. In the crystal structure, the molecules are stacked along the b axis, without any π–π interaction. The stacked columns are linked together by the intermolecular hydrogen bonds of the type N—- H···O, details have been given in Table 1.

Related literature top

For background literature, see: Abburi & Nutalapati (2004); Moreno et al. (2001); Wang et al. (1998). For a report of a similar compound, see: Czugler & Kalman (1975).

Experimental top

A sample of commercial 2-(1-methylethoxy)phenol methylcarbamate (Aldrich) was crystallized by slow evaporation of a solution in acetone.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

2-Isopropoxyphenyl N-methylcarbamate top

Crystal data top

C₁₁H₁₅NO₃	F(000) = 448
M_r = 209.24	D_x = 1.186 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 13.275 (3) Å	θ = 9–12°
b = 8.8890 (18) Å	µ = 0.09 mm⁻¹
c = 9.931 (2) Å	T = 293 K
β = 90.59 (3)°	Needle, colourless
V = 1171.8 (4) Å³	0.30 × 0.10 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1255 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 25.3°, θ_min = 1.5°
ω/2θ scans	h = −15→15
Absorption correction: ψ scan (CAD-4 Software; Enraf–Nonius, 1989)	k = 0→10
T_min = 0.975, T_max = 0.991	l = 0→11
2257 measured reflections	3 standard reflections every 200 reflections
2121 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.060	H-atom parameters constrained
wR(F²) = 0.152	w = 1/[σ²(F_o²) + (0.06P)² + 0.55P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
2121 reflections	Δρ_max = 0.21 e Å⁻³
136 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: none

Crystal data top

C₁₁H₁₅NO₃	V = 1171.8 (4) Å³
M_r = 209.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.275 (3) Å	µ = 0.09 mm⁻¹
b = 8.8890 (18) Å	T = 293 K
c = 9.931 (2) Å	0.30 × 0.10 × 0.10 mm
β = 90.59 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1255 reflections with I > 2σ(I)
Absorption correction: ψ scan (CAD-4 Software; Enraf–Nonius, 1989)	R_int = 0.023
T_min = 0.975, T_max = 0.991	3 standard reflections every 200 reflections
2257 measured reflections	intensity decay: 1%
2121 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.152	H-atom parameters constrained
S = 1.01	Δρ_max = 0.21 e Å⁻³
2121 reflections	Δρ_min = −0.16 e Å⁻³
136 parameters

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

	x	y	z	U_iso*/U_eq
N1	0.60393 (17)	0.3161 (3)	−0.19856 (18)	0.0506 (6)
H0A	0.6177	0.2831	−0.2777	0.061*
O1	0.82141 (16)	0.1745 (2)	0.0186 (2)	0.0748 (7)
O2	0.66395 (14)	0.0939 (2)	−0.13306 (16)	0.0526 (5)
O3	0.60236 (15)	0.2566 (2)	0.02273 (15)	0.0566 (6)
C1	0.8569 (3)	0.4130 (4)	0.1055 (4)	0.0941 (12)
H1A	0.7868	0.4283	0.1236	0.141*
H1B	0.8712	0.4451	0.0154	0.141*
H1C	0.8968	0.4705	0.1682	0.141*
C2	0.9872 (3)	0.2104 (4)	0.1067 (4)	0.0874 (11)
H2A	0.9973	0.1079	0.1341	0.131*
H2B	1.0274	0.2756	0.1625	0.131*
H2C	1.0067	0.2218	0.0144	0.131*
C3	0.8819 (3)	0.2495 (4)	0.1202 (4)	0.0884 (12)
H3A	0.8594	0.2159	0.2089	0.106*
C4	0.7804 (2)	0.0381 (3)	0.0493 (3)	0.0497 (7)
C5	0.6971 (2)	−0.0015 (3)	−0.0310 (2)	0.0448 (7)
C6	0.6512 (2)	−0.1395 (4)	−0.0155 (3)	0.0587 (8)
H6A	0.5964	−0.1656	−0.0696	0.070*
C7	0.6867 (3)	−0.2379 (4)	0.0800 (3)	0.0692 (9)
H7A	0.6564	−0.3316	0.0899	0.083*
C8	0.7652 (3)	−0.1993 (4)	0.1594 (4)	0.0707 (9)
H8A	0.7882	−0.2667	0.2244	0.085*
C9	0.8130 (2)	−0.0602 (3)	0.1463 (3)	0.0668 (9)
H9A	0.8664	−0.0347	0.2030	0.080*
C10	0.62194 (18)	0.2312 (3)	−0.0929 (2)	0.0386 (6)
C11	0.5614 (2)	0.4638 (3)	−0.1832 (3)	0.0588 (8)
H11A	0.5510	0.5082	−0.2704	0.088*
H11B	0.6067	0.5254	−0.1313	0.088*
H11C	0.4981	0.4564	−0.1378	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0653 (15)	0.0723 (17)	0.0143 (9)	−0.0010 (13)	0.0002 (9)	−0.0007 (9)
O1	0.0689 (15)	0.0644 (14)	0.0905 (15)	−0.0241 (12)	−0.0349 (12)	0.0110 (12)
O2	0.0634 (13)	0.0637 (13)	0.0305 (9)	0.0012 (10)	−0.0072 (8)	−0.0068 (9)
O3	0.0708 (14)	0.0784 (14)	0.0206 (9)	0.0144 (11)	−0.0055 (8)	−0.0029 (9)
C1	0.103 (3)	0.081 (3)	0.097 (3)	−0.006 (2)	0.004 (2)	−0.004 (2)
C2	0.076 (3)	0.095 (3)	0.090 (3)	−0.004 (2)	0.001 (2)	−0.001 (2)
C3	0.080 (3)	0.066 (2)	0.119 (3)	−0.022 (2)	−0.028 (2)	−0.016 (2)
C4	0.0456 (16)	0.0444 (17)	0.0590 (17)	−0.0041 (14)	−0.0059 (13)	0.0040 (13)
C5	0.0429 (15)	0.0550 (18)	0.0365 (13)	−0.0029 (14)	−0.0024 (12)	−0.0027 (12)
C6	0.0532 (19)	0.064 (2)	0.0585 (18)	−0.0117 (16)	−0.0025 (14)	−0.0144 (16)
C7	0.070 (2)	0.0504 (19)	0.087 (2)	−0.0091 (17)	0.0016 (19)	−0.0051 (18)
C8	0.071 (2)	0.057 (2)	0.084 (2)	0.0083 (18)	−0.0022 (18)	0.0126 (17)
C9	0.056 (2)	0.055 (2)	0.088 (2)	0.0049 (16)	−0.0258 (17)	0.0023 (17)
C10	0.0387 (14)	0.0598 (17)	0.0171 (11)	−0.0121 (13)	−0.0076 (9)	0.0017 (11)
C11	0.066 (2)	0.069 (2)	0.0413 (15)	0.0057 (17)	−0.0028 (14)	0.0027 (14)

Geometric parameters (Å, º) top

N1—C10	1.313 (3)	C2—H2C	0.9600
N1—C11	1.438 (4)	C3—H3A	0.9800
N1—H0A	0.8600	C4—C9	1.368 (4)
O1—C4	1.365 (3)	C4—C5	1.402 (4)
O1—C3	1.446 (4)	C5—C6	1.379 (4)
O2—C5	1.390 (3)	C6—C7	1.370 (4)
O2—C10	1.401 (3)	C6—H6A	0.9300
O3—C10	1.201 (3)	C7—C8	1.346 (4)
C1—C3	1.498 (5)	C7—H7A	0.9300
C1—H1A	0.9600	C8—C9	1.395 (4)
C1—H1B	0.9600	C8—H8A	0.9300
C1—H1C	0.9600	C9—H9A	0.9300
C2—C3	1.448 (5)	C11—H11A	0.9600
C2—H2A	0.9600	C11—H11B	0.9600
C2—H2B	0.9600	C11—H11C	0.9600

C10—N1—C11	120.6 (2)	C9—C4—C5	118.8 (3)
C10—N1—H0A	119.7	C6—C5—O2	119.2 (2)
C11—N1—H0A	119.7	C6—C5—C4	120.5 (3)
C4—O1—C3	118.3 (2)	O2—C5—C4	120.2 (2)
C5—O2—C10	116.62 (17)	C7—C6—C5	119.8 (3)
C3—C1—H1A	109.5	C7—C6—H6A	120.1
C3—C1—H1B	109.5	C5—C6—H6A	120.1
H1A—C1—H1B	109.5	C8—C7—C6	120.1 (3)
C3—C1—H1C	109.5	C8—C7—H7A	120.0
H1A—C1—H1C	109.5	C6—C7—H7A	120.0
H1B—C1—H1C	109.5	C7—C8—C9	121.4 (3)
C3—C2—H2A	109.5	C7—C8—H8A	119.3
C3—C2—H2B	109.5	C9—C8—H8A	119.3
H2A—C2—H2B	109.5	C4—C9—C8	119.4 (3)
C3—C2—H2C	109.5	C4—C9—H9A	120.3
H2A—C2—H2C	109.5	C8—C9—H9A	120.3
H2B—C2—H2C	109.5	O3—C10—N1	128.1 (3)
O1—C3—C2	110.8 (3)	O3—C10—O2	121.8 (2)
O1—C3—C1	105.0 (3)	N1—C10—O2	110.05 (19)
C2—C3—C1	115.9 (3)	N1—C11—H11A	109.5
O1—C3—H3A	108.3	N1—C11—H11B	109.5
C2—C3—H3A	108.3	H11A—C11—H11B	109.5
C1—C3—H3A	108.3	N1—C11—H11C	109.5
O1—C4—C9	127.0 (3)	H11A—C11—H11C	109.5
O1—C4—C5	114.2 (2)	H11B—C11—H11C	109.5

C4—O1—C3—C2	91.9 (4)	C4—C5—C6—C7	0.6 (4)
C4—O1—C3—C1	−142.3 (3)	C5—C6—C7—C8	0.9 (5)
C3—O1—C4—C9	−22.3 (5)	C6—C7—C8—C9	−0.6 (5)
C3—O1—C4—C5	158.6 (3)	O1—C4—C9—C8	−176.6 (3)
C10—O2—C5—C6	116.3 (3)	C5—C4—C9—C8	2.5 (5)
C10—O2—C5—C4	−67.7 (3)	C7—C8—C9—C4	−1.1 (5)
O1—C4—C5—C6	176.9 (2)	C11—N1—C10—O3	4.4 (4)
C9—C4—C5—C6	−2.3 (4)	C11—N1—C10—O2	−179.5 (2)
O1—C4—C5—O2	1.0 (4)	C5—O2—C10—O3	−10.2 (3)
C9—C4—C5—O2	−178.1 (3)	C5—O2—C10—N1	173.3 (2)
O2—C5—C6—C7	176.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H0A···O3ⁱ	0.86	2.02	2.842 (2)	159

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₅NO₃
M_r	209.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	13.275 (3), 8.8890 (18), 9.931 (2)
β (°)	90.59 (3)
V (Å³)	1171.8 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (CAD-4 Software; Enraf–Nonius, 1989)
T_min, T_max	0.975, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	2257, 2121, 1255
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.152, 1.01
No. of reflections	2121
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.16

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), 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—H0A···O3ⁱ	0.8600	2.0200	2.842 (2)	159.00

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

The authors acknowledge financial support from the Jiangsu Institute of Nuclear Medicine.

References

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