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

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ISSN: 2056-9890

2-(2,2-Di­methyl-2,3-di­hydro-1-benzo­furan-7-yl­­oxy)-N-(o-tol­yl)acetamide

aCollege of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China, and bHunan Research Institute of Chemical Industry, Changsha 410007, People's Republic of China
*Correspondence e-mail: axhu0731@yahoo.com.cn

(Received 1 April 2010; accepted 19 May 2010; online 26 May 2010)

In the title compound, C19H21NO3, the dihedral angle between the mean planes of the two benzene rings is 38.13 (12)°. The furan ring adopts an envelope-like conformation with the C atom bonded to the dimethyl groups displaced by 0.356 (2) Å from the plane through the other four atoms. In the crystal, mol­ecules are linked into inversion dimers by weak C—H⋯O inter­molecular inter­actions.

Related literature

The title compound is a derivative of Carbofuran, a popular carbamate insecticide, see: Tomlin (1994[Tomlin, C. (1994). The Pesticide Manual. A World Compendium, 10th ed., pp 152-153. Bath: The British Crop Protection Council, The Bath Press.]). For related structures, see: Xu et al. (2005[Xu, L.-Z., Yu, G.-P. & Yang, S.-H. (2005). Acta Cryst. E61, o1924-o1926.]); Li et al. (2009[Li, W.-S., Li, L. & Li, J.-S. (2009). Acta Cryst. E65, o2829-o2838.]). For bond-length data, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]).

[Scheme 1]

Experimental

Crystal data
  • C19H21NO3

  • Mr = 311.37

  • Monoclinic, P 21 /n

  • a = 9.0868 (18) Å

  • b = 8.9708 (18) Å

  • c = 20.230 (4) Å

  • β = 92.18 (3)°

  • V = 1647.9 (6) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 293 K

  • 0.32 × 0.28 × 0.21 mm

Data collection
  • Bruker APEXII area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.985, Tmax = 0.991

  • 8246 measured reflections

  • 2961 independent reflections

  • 1649 reflections with I > 2σ(I)

  • Rint = 0.047

Refinement
  • R[F2 > 2σ(F2)] = 0.048

  • wR(F2) = 0.130

  • S = 1.00

  • 2961 reflections

  • 211 parameters

  • H-atom parameters constrained

  • Δρmax = 0.16 e Å−3

  • Δρmin = −0.19 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C12—H12A⋯O3i 0.97 2.60 3.561 (3) 174
Symmetry code: (i) -x+2, -y+1, -z.

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS 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: XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

The title compound, (I), C19H21NO3, is a derivative of the commercial compound Carbofuran (Tomlin, 1994), which is a popular carbamate insecticide. The dihedral angle between the mean planes of the two aromatic rings is 38.13 (12)° (Fig. 1). The five-membered furan ring adopts an envelope-like conformation. All bond lengths (Allen et al. 1987) and angles are within normal ranges. The atom C1 deviates from the C1—C7/O1 plane with a distance of 0.356 (2) Å. Molecules are linked into dimers by weak C—H···O intermolecular interactions which helps stabilize crystal packing(Fig 2).

Related literature top

For background on insecticides, see: Tomlin (1994). For related structures, see: Xu et al. (2005); Li et al. (2009). For bond-length data, see: Allen et al. (1987).

Experimental top

0.10 mol of 2,2-dimethy-2,3-dihydrobenzofuran-7-ol , 0.12 mol chloroacetic acid, 0.25 mol sodium hydrate and 70 ml distilled water were stirred and heated under reflux for 3 h. The reaction mixture was then cooled to 283.15 K and 15 ml concentrated hydrochloric acid was added to give 2-(2,2-dimethyl-2,3-dihydrobenzofuran-7-yloxy)acetic acid as an amber solid of 21.91 g, yield 98.5%. Subsequently, 0.10 mol of dry 2-(2,2-dimethyl-2,3-dihydrobenzofuran-7-yloxy)acetic acid, 0.25 mol thionyl chloride and 80 ml anhydrous was stirred and heated at 353.15 K for 6h. The excess thionyl chloride was then removed under reduced pressure. The residue was cooled to 273.15 K, after which 0.10 mol o-toluidine and 0.20 mol triethylamine was added dropwise. After stirring for an additional 3 h, the reaction mixture was washed with water (3× 40 ml), and the excess toluene removed in vacuo. The residue was purified by recrystallization from a saturated ethanol solution, giving the title compound as a colourless crystalline solid. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of an ethyl acetate solution at room temperature over a period of nine days. The identity of the title compound was confirmed by NMR and LC—MS spectroscopy.

Refinement top

Methyl H atoms were placed in calculated positions, with C–H = 0.96 Å, and torsion angles were refined, with Uiso(H) = 1.5Ueq(C). Other H atoms were placed in geometrically idealized positions and refined as a riding model, with a N–H distance of 0.86 Å, C–H distances of 0.98Å (C3—H3), 0.93Å (aromatic H atoms) and 0.97Å (methylene H atoms). The constraint Uiso(H) = 1.2Ueq(carrier) was applied.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of the title compound showing 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. A packing diagram for the title compound. H atoms bonded to C atoms have been omitted for clarity. Dashed lines indicate weak C—H···O intermolecular interactions forminng dimers.
2-(2,2-Dimethyl-2,3-dihydro-1-benzofuran-7-yloxy)-N- (o-tolyl)acetamide top
Crystal data top
C19H21NO3F(000) = 664
Mr = 311.37Dx = 1.255 Mg m3
Monoclinic, P21/nMelting point: 363.75 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 9.0868 (18) ÅCell parameters from 3600 reflections
b = 8.9708 (18) Åθ = 1.4–28°
c = 20.230 (4) ŵ = 0.09 mm1
β = 92.18 (3)°T = 293 K
V = 1647.9 (6) Å3Block, colourless
Z = 40.32 × 0.28 × 0.21 mm
Data collection top
Bruker APEXII area-detector
diffractometer
2961 independent reflections
Radiation source: fine-focus sealed tube1649 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.047
ϕ and ω scanθmax = 25.2°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 810
Tmin = 0.985, Tmax = 0.991k = 109
8246 measured reflectionsl = 1924
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0561P)2]
where P = (Fo2 + 2Fc2)/3
2961 reflections(Δ/σ)max = 0.001
211 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C19H21NO3V = 1647.9 (6) Å3
Mr = 311.37Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.0868 (18) ŵ = 0.09 mm1
b = 8.9708 (18) ÅT = 293 K
c = 20.230 (4) Å0.32 × 0.28 × 0.21 mm
β = 92.18 (3)°
Data collection top
Bruker APEXII area-detector
diffractometer
2961 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1649 reflections with I > 2σ(I)
Tmin = 0.985, Tmax = 0.991Rint = 0.047
8246 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.130H-atom parameters constrained
S = 1.00Δρmax = 0.16 e Å3
2961 reflectionsΔρmin = 0.19 e Å3
211 parameters
Special details top

Experimental. 1H NMR in CDCl3 (300 MHz), delta: 1.49(s,6H,2CH3), 2.72(s,3H, ArCH3), 3.06(s,2H,CH2), 4.72 (s,2H, OCH2), 6.76~7.99(m,7H,C6H3,C6H4), 8.53(s,1H, NH). MS: 312.2(M+1)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
xyzUiso*/Ueq
C70.4155 (3)0.3064 (3)0.23529 (11)0.0590 (7)
H7A0.31400.27800.22540.071*
H7B0.42430.34300.28040.071*
C10.6148 (2)0.4224 (2)0.09104 (10)0.0478 (6)
C20.5545 (2)0.3488 (2)0.14345 (10)0.0452 (6)
C30.4665 (2)0.4205 (3)0.18741 (10)0.0508 (6)
C60.5867 (3)0.5737 (3)0.08464 (11)0.0625 (7)
H60.62710.62690.05030.075*
C80.5210 (3)0.1749 (2)0.22464 (10)0.0534 (6)
C50.4988 (3)0.6465 (3)0.12900 (12)0.0697 (7)
H50.48040.74790.12390.084*
C40.4384 (3)0.5705 (3)0.18046 (12)0.0661 (7)
H40.37950.61980.21010.079*
C100.6543 (3)0.1807 (3)0.27130 (12)0.0741 (8)
H10A0.72200.10340.26010.111*
H10B0.62430.16640.31590.111*
H10C0.70140.27590.26770.111*
C90.4475 (3)0.0248 (3)0.22421 (12)0.0761 (8)
H9A0.36730.02430.19190.114*
H9B0.41070.00460.26720.114*
H9C0.51770.05050.21330.114*
O10.57451 (16)0.20069 (15)0.15680 (7)0.0515 (4)
O20.69720 (17)0.34027 (15)0.04836 (7)0.0554 (5)
N10.83327 (19)0.16952 (19)0.03274 (8)0.0500 (5)
H10.77400.14900.00190.060*
C110.8592 (3)0.3146 (3)0.04218 (11)0.0540 (6)
O30.9383 (2)0.36591 (19)0.08343 (9)0.0889 (7)
C120.7796 (3)0.4201 (2)0.00151 (11)0.0569 (6)
H12A0.85030.48440.02460.068*
H12B0.71380.48230.02540.068*
C130.8900 (3)0.0448 (2)0.06653 (10)0.0499 (6)
C140.8094 (3)0.0865 (3)0.06628 (11)0.0611 (7)
C171.0776 (4)0.0718 (4)0.12804 (13)0.0943 (11)
H171.16730.06710.14860.113*
C190.6654 (3)0.0952 (3)0.03299 (13)0.0822 (8)
H19A0.68130.07960.01370.123*
H19B0.62240.19180.04050.123*
H19C0.60010.01990.05080.123*
C150.8674 (4)0.2095 (3)0.09801 (14)0.0891 (10)
H150.81550.29890.09850.107*
C160.9987 (5)0.2025 (4)0.12855 (15)0.1031 (13)
H161.03470.28630.14970.124*
C181.0232 (3)0.0530 (3)0.09684 (10)0.0664 (7)
H181.07610.14170.09630.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C70.0495 (15)0.0799 (17)0.0482 (14)0.0056 (13)0.0113 (11)0.0089 (12)
C10.0495 (14)0.0487 (14)0.0452 (13)0.0017 (11)0.0031 (11)0.0074 (10)
C20.0489 (14)0.0448 (13)0.0419 (13)0.0012 (11)0.0030 (11)0.0075 (10)
C30.0457 (14)0.0594 (15)0.0475 (14)0.0022 (12)0.0034 (11)0.0117 (11)
C60.0803 (19)0.0517 (15)0.0558 (15)0.0002 (13)0.0053 (14)0.0017 (11)
C80.0530 (15)0.0674 (15)0.0406 (13)0.0041 (12)0.0144 (11)0.0004 (11)
C50.089 (2)0.0528 (14)0.0672 (17)0.0128 (14)0.0046 (15)0.0085 (13)
C40.0663 (18)0.0676 (17)0.0647 (17)0.0142 (14)0.0053 (14)0.0208 (13)
C100.0674 (18)0.103 (2)0.0522 (16)0.0144 (15)0.0057 (14)0.0012 (14)
C90.090 (2)0.0737 (18)0.0664 (17)0.0086 (16)0.0263 (15)0.0080 (14)
O10.0605 (10)0.0524 (9)0.0426 (9)0.0055 (8)0.0167 (7)0.0009 (7)
O20.0686 (11)0.0503 (9)0.0489 (9)0.0012 (8)0.0242 (8)0.0000 (7)
N10.0551 (12)0.0523 (12)0.0438 (11)0.0020 (9)0.0175 (9)0.0037 (8)
C110.0602 (16)0.0583 (16)0.0444 (14)0.0096 (12)0.0129 (12)0.0007 (11)
O30.1140 (16)0.0713 (12)0.0856 (13)0.0173 (11)0.0584 (12)0.0004 (9)
C120.0635 (16)0.0550 (14)0.0536 (14)0.0072 (12)0.0190 (12)0.0003 (11)
C130.0599 (16)0.0579 (15)0.0319 (12)0.0128 (12)0.0023 (11)0.0017 (10)
C140.0787 (19)0.0548 (15)0.0485 (14)0.0045 (14)0.0137 (13)0.0024 (12)
C170.106 (3)0.128 (3)0.0505 (17)0.059 (2)0.0147 (17)0.0032 (18)
C190.088 (2)0.0724 (18)0.085 (2)0.0193 (16)0.0079 (17)0.0098 (15)
C150.134 (3)0.0651 (19)0.0653 (19)0.020 (2)0.029 (2)0.0111 (15)
C160.149 (4)0.100 (3)0.058 (2)0.063 (3)0.014 (2)0.0204 (19)
C180.0742 (18)0.0837 (18)0.0421 (14)0.0215 (15)0.0121 (13)0.0088 (13)
Geometric parameters (Å, º) top
C7—C31.495 (3)C9—H9C0.9600
C7—C81.540 (3)O2—C121.423 (2)
C7—H7A0.9700N1—C111.337 (3)
C7—H7B0.9700N1—C131.418 (3)
C1—O21.378 (2)N1—H10.8600
C1—C21.380 (3)C11—O31.213 (2)
C1—C61.386 (3)C11—C121.500 (3)
C2—O11.367 (2)C12—H12A0.9700
C2—C31.378 (3)C12—H12B0.9700
C3—C41.376 (3)C13—C181.380 (3)
C6—C51.387 (3)C13—C141.387 (3)
C6—H60.9300C14—C151.390 (4)
C8—O11.492 (2)C14—C191.497 (3)
C8—C91.503 (3)C17—C161.374 (4)
C8—C101.508 (3)C17—C181.386 (3)
C5—C41.376 (3)C17—H170.9300
C5—H50.9300C19—H19A0.9600
C4—H40.9300C19—H19B0.9600
C10—H10A0.9600C19—H19C0.9600
C10—H10B0.9600C15—C161.366 (4)
C10—H10C0.9600C15—H150.9300
C9—H9A0.9600C16—H160.9300
C9—H9B0.9600C18—H180.9300
C3—C7—C8102.93 (17)H9A—C9—H9C109.5
C3—C7—H7A111.2H9B—C9—H9C109.5
C8—C7—H7A111.2C2—O1—C8106.68 (14)
C3—C7—H7B111.2C1—O2—C12117.43 (16)
C8—C7—H7B111.2C11—N1—C13129.02 (18)
H7A—C7—H7B109.1C11—N1—H1115.5
O2—C1—C2117.83 (18)C13—N1—H1115.5
O2—C1—C6124.60 (19)O3—C11—N1125.5 (2)
C2—C1—C6117.56 (19)O3—C11—C12118.5 (2)
O1—C2—C3113.71 (19)N1—C11—C12116.00 (18)
O1—C2—C1124.27 (18)O2—C12—C11110.67 (18)
C3—C2—C1122.0 (2)O2—C12—H12A109.5
C4—C3—C2120.0 (2)C11—C12—H12A109.5
C4—C3—C7132.5 (2)O2—C12—H12B109.5
C2—C3—C7107.51 (19)C11—C12—H12B109.5
C1—C6—C5120.6 (2)H12A—C12—H12B108.1
C1—C6—H6119.7C18—C13—C14121.3 (2)
C5—C6—H6119.7C18—C13—N1120.9 (2)
O1—C8—C9107.10 (17)C14—C13—N1117.8 (2)
O1—C8—C10106.75 (18)C13—C14—C15117.6 (3)
C9—C8—C10112.3 (2)C13—C14—C19121.1 (2)
O1—C8—C7103.68 (16)C15—C14—C19121.3 (3)
C9—C8—C7114.1 (2)C16—C17—C18119.9 (3)
C10—C8—C7112.06 (19)C16—C17—H17120.1
C4—C5—C6120.8 (2)C18—C17—H17120.1
C4—C5—H5119.6C14—C19—H19A109.5
C6—C5—H5119.6C14—C19—H19B109.5
C5—C4—C3119.0 (2)H19A—C19—H19B109.5
C5—C4—H4120.5C14—C19—H19C109.5
C3—C4—H4120.5H19A—C19—H19C109.5
C8—C10—H10A109.5H19B—C19—H19C109.5
C8—C10—H10B109.5C16—C15—C14121.7 (3)
H10A—C10—H10B109.5C16—C15—H15119.2
C8—C10—H10C109.5C14—C15—H15119.2
H10A—C10—H10C109.5C15—C16—C17120.0 (3)
H10B—C10—H10C109.5C15—C16—H16120.0
C8—C9—H9A109.5C17—C16—H16120.0
C8—C9—H9B109.5C13—C18—C17119.6 (3)
H9A—C9—H9B109.5C13—C18—H18120.2
C8—C9—H9C109.5C17—C18—H18120.2
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12A···O3i0.972.603.561 (3)174
Symmetry code: (i) x+2, y+1, z.

Experimental details

Crystal data
Chemical formulaC19H21NO3
Mr311.37
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)9.0868 (18), 8.9708 (18), 20.230 (4)
β (°) 92.18 (3)
V3)1647.9 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.32 × 0.28 × 0.21
Data collection
DiffractometerBruker APEXII area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.985, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
8246, 2961, 1649
Rint0.047
(sin θ/λ)max1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.130, 1.00
No. of reflections2961
No. of parameters211
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.16, 0.19

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12A···O3i0.972.603.561 (3)174
Symmetry code: (i) x+2, y+1, z.
 

Acknowledgements

We would like to thank the National High Technology Research and Development Program of China (No. 2006 A A03Z460) for financial suppport.

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Web of Science
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationLi, W.-S., Li, L. & Li, J.-S. (2009). Acta Cryst. E65, o2829–o2838.
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationTomlin, C. (1994). The Pesticide Manual. A World Compendium, 10th ed., pp 152-153. Bath: The British Crop Protection Council, The Bath Press.
First citationXu, L.-Z., Yu, G.-P. & Yang, S.-H. (2005). Acta Cryst. E61, o1924–o1926.  Web of Science CSD CrossRef IUCr Journals

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