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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 6| June 2010| Page o1433
https://doi.org/10.1107/S1600536810018659

2-(2,2-Di­methyl-2,3-di­hydro-1-benzo­furan-7-yl­­oxy)acetic acid monohydrate

Lin-Tao Yang,a Jiao Ye,a Xian-Fu Luoa and Ai-Xi Hua*

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

(Received 21 April 2010; accepted 19 May 2010; online 22 May 2010)

In the title compound, C12H14O4·H2O, the dihydro­benzo­furan ring adopts an envelope conformation with the substituted C atom 0.142 (1) Å out of the least-squares plane. In the crystal, the components are linked via inter­molecular Owater—H⋯O and O—H⋯Owater hydrogen-bonding inter­actions, forming a three-dimensional network.

Related literature

For background to carbamate-based insecticides, 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, o2928.]).

[Scheme 1]

Experimental

Crystal data

  • C12H14O4·H2O

  • Mr = 240.25

  • Monoclinic, P 21 /c

  • a = 10.1692 (7) Å

  • b = 9.2516 (6) Å

  • c = 15.3647 (11) Å

  • β = 121.000 (1)°

  • V = 1239.06 (15) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 173 K

  • 0.46 × 0.42 × 0.30 mm
Data collection

  • Bruker SMART 1000 CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004[Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.]) Tmin = 0.955, Tmax = 0.971

  • 6151 measured reflections

  • 2697 independent reflections

  • 2120 reflections with I > 2σ(I)

  • Rint = 0.019
Refinement

  • R[F2 > 2σ(F2)] = 0.039

  • wR(F2) = 0.111

  • S = 1.04

  • 2697 reflections

  • 163 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.25 e Å−3

  • Δρmin = −0.16 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O5W—H5A⋯O1 0.86 (2) 1.95 (2) 2.8104 (15) 173.0 (19)
O5W—H5B⋯O3 0.85 (2) 1.94 (2) 2.7888 (15) 176.5 (19)
O4—H4A⋯O5Wi 0.84 1.71 2.5416 (15) 171
Symmetry code: (i) [-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}].

Data collection: SMART (Bruker, 2001[Bruker (2001). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2003[Bruker (2003). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810018659/wm2329sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810018659/wm2329Isup2.hkl

checkCIF report


Comment top

2-(2,2-dimethyl-2,3-dihydrobenzofuran-7-yloxy)acetic acid monohydrate (I), C12H14O4.H2O, is a derivative of commercially available Carbofuran which is a carbamate-based insecticide (Xu et al., 2005; Li, et al., 2009), Herein we report the synthesis and structure of the title compound.

The dihedral angle between the plane C7—C3—C2—O1 and the plane C8—O1—C7 is 23.20 (14)°, which indicates that the dihydrobenzofuran ring is in an envelope conformation (Fig. 1). Its substituted C8 atom is 0.142 (1) Å out of the least-squares plane defined by O1, C2, C3, C7 and C8. In the crystal structure, intermolecular Owater—H···O and and O—H···Owater hydrogen bonds link organic molecules and water molecules into a three-dimensional network (Fig. 2).

Related literature top

For background to carbamate-based insecticides, see: Xu et al. (2005); Li et al. (2009).

Experimental top

0.10 mol 2,2-dimethyl-2,3-dihydrobenzofuran-7-ol , 0.12 mol chloroacetic acid, 0.25 mol sodium hydroxide and 70 ml water were stirred and heated under reflux for 3 h. Then the reaction mixture was cooled to 283 K and 15 ml concentrated hydrochloric acid was added to give 2-(2,2-dimethyl-2,3-dihydrobenzofuran-7-yloxy)acetic acid hydrate as amber solid of 21.91 g, yield 98.5%. Single colourless 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.

1H NMR (CDCl3,300 MHz), δ: 1.50(s, 6H, 2CH3), 3.03(s,2H,CH2), 4.71(s,2H,OCH2), 6.74~6.83(m, 2H,ArH), 6.84~6.87(m,1H,ArH).

Refinement top

All H atoms except for the water H atoms were refined in the riding-model approximation, with C—H distances of 0.98 Å (methyl), 0.95Å (aromatic) and 0.99Å (methylene), and with Uiso(H)=1.5 or 1.2Ueq(carrier). The water H atoms were located in Fourier syntheses. Their positions were refined with distance restraints of 0.85 (2) Å, with Uiso(H) values set equal to 1.5Ueq(O). The carboxylate proton was placed in a calculated position.

Structure description top

2-(2,2-dimethyl-2,3-dihydrobenzofuran-7-yloxy)acetic acid monohydrate (I), C12H14O4.H2O, is a derivative of commercially available Carbofuran which is a carbamate-based insecticide (Xu et al., 2005; Li, et al., 2009), Herein we report the synthesis and structure of the title compound.

The dihedral angle between the plane C7—C3—C2—O1 and the plane C8—O1—C7 is 23.20 (14)°, which indicates that the dihydrobenzofuran ring is in an envelope conformation (Fig. 1). Its substituted C8 atom is 0.142 (1) Å out of the least-squares plane defined by O1, C2, C3, C7 and C8. In the crystal structure, intermolecular Owater—H···O and and O—H···Owater hydrogen bonds link organic molecules and water molecules into a three-dimensional network (Fig. 2).

For background to carbamate-based insecticides, see: Xu et al. (2005); Li et al. (2009).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound showing 30% probability displacement ellipsoids. H atoms are drawn as spheres with arbitrary radius.
[Figure 2] Fig. 2. A packing diagram for the title compound, viewed down [010]. H atoms bonded to C atoms have been omitted for clarity.
2-(2,2-Dimethyl-2,3-dihydro-1-benzofuran-7-yloxy)acetic acid monohydrate top
Crystal data top
C12H14O4·H2OF(000) = 512
Mr = 240.25Dx = 1.288 Mg m−3
Monoclinic, P21/cMelting point: 383.2 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 10.1692 (7) ÅCell parameters from 3163 reflections
b = 9.2516 (6) Åθ = 2.3–27.1°
c = 15.3647 (11) ŵ = 0.10 mm−1
β = 121.000 (1)°T = 173 K
V = 1239.06 (15) Å3Block, colorless
Z = 40.46 × 0.42 × 0.30 mm
Data collection top
Bruker SMART 1000 CCD
diffractometer		2697 independent reflections
Radiation source: fine-focus sealed tube2120 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ω scansθmax = 27.1°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −12→11
Tmin = 0.955, Tmax = 0.971k = −7→11
6151 measured reflectionsl = −19→19
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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0517P)2 + 0.395P]
where P = (Fo2 + 2Fc2)/3
2697 reflections(Δ/σ)max = 0.001
163 parametersΔρmax = 0.25 e Å−3
0 restraintsΔρmin = −0.16 e Å−3
Crystal data top
C12H14O4·H2OV = 1239.06 (15) Å3
Mr = 240.25Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.1692 (7) ŵ = 0.10 mm−1
b = 9.2516 (6) ÅT = 173 K
c = 15.3647 (11) Å0.46 × 0.42 × 0.30 mm
β = 121.000 (1)°
Data collection top
Bruker SMART 1000 CCD
diffractometer		2697 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		2120 reflections with I > 2σ(I)
Tmin = 0.955, Tmax = 0.971Rint = 0.019
6151 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.111H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.25 e Å−3
2697 reflectionsΔρmin = −0.16 e Å−3
163 parameters
Special details top

Experimental. 1H NMR (CDCl3,300 MHz), delta: 1.50(s, 6H, 2CH3), 3.03(s,2H,CH2), 4.71(s,2H,OCH2), 6.74~6.83(m, 2H,ArH), 6.84~6.87(m,1H,ArH).

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
C10.31319 (14)−0.08179 (14)0.92110 (10)0.0262 (3)
C20.20485 (15)0.01702 (14)0.85462 (10)0.0267 (3)
C30.12122 (16)0.10425 (15)0.88122 (11)0.0303 (3)
C40.14753 (18)0.09740 (17)0.97925 (12)0.0368 (3)
H40.09040.15590.99890.044*
C50.25901 (18)0.00335 (16)1.04785 (11)0.0360 (3)
H50.2796−0.00051.11550.043*
C60.34170 (16)−0.08577 (15)1.01982 (10)0.0304 (3)
H60.4176−0.14931.06820.036*
C70.01064 (17)0.19009 (17)0.78777 (12)0.0377 (4)
H7A0.01010.29340.80430.045*
H7B−0.09490.15130.75620.045*
C80.07678 (17)0.16885 (15)0.71767 (11)0.0346 (3)
C9−0.0406 (2)0.1410 (2)0.60728 (12)0.0498 (4)
H9A0.01190.11320.57130.075*
H9B−0.10060.22900.57670.075*
H9C−0.10910.06280.60220.075*
C100.1872 (2)0.28869 (18)0.73154 (13)0.0449 (4)
H10A0.26040.30300.80410.067*
H10B0.12990.37830.70210.067*
H10C0.24270.26240.69730.067*
C110.48288 (15)−0.27410 (15)0.94317 (10)0.0288 (3)
H11A0.4348−0.33620.97160.035*
H11B0.5754−0.22871.00020.035*
C120.52628 (16)−0.36346 (15)0.87960 (10)0.0292 (3)
O10.16890 (11)0.03407 (10)0.75592 (7)0.0308 (2)
O20.37837 (11)−0.16642 (10)0.87999 (7)0.0300 (2)
O30.48249 (14)−0.34112 (12)0.79128 (8)0.0443 (3)
O40.61833 (13)−0.46912 (11)0.93349 (8)0.0387 (3)
H4A0.6434−0.51640.89760.058*
O5W0.28781 (13)−0.12943 (12)0.65785 (8)0.0354 (3)
H5A0.259 (2)−0.079 (2)0.6924 (15)0.053*
H5B0.349 (2)−0.191 (2)0.7004 (15)0.053*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0261 (6)0.0248 (6)0.0279 (6)−0.0024 (5)0.0140 (5)−0.0013 (5)
C20.0286 (7)0.0257 (7)0.0248 (6)−0.0032 (5)0.0131 (5)−0.0004 (5)
C30.0302 (7)0.0274 (7)0.0351 (7)0.0001 (5)0.0181 (6)0.0001 (6)
C40.0434 (8)0.0355 (8)0.0406 (8)0.0006 (7)0.0282 (7)−0.0035 (6)
C50.0464 (9)0.0375 (8)0.0300 (7)−0.0025 (6)0.0238 (7)−0.0011 (6)
C60.0336 (7)0.0292 (7)0.0271 (7)−0.0013 (6)0.0148 (6)0.0021 (6)
C70.0374 (8)0.0356 (8)0.0392 (8)0.0077 (6)0.0190 (7)0.0032 (6)
C80.0383 (8)0.0304 (7)0.0315 (7)0.0115 (6)0.0153 (6)0.0067 (6)
C90.0494 (10)0.0519 (10)0.0332 (8)0.0185 (8)0.0106 (7)0.0038 (7)
C100.0559 (10)0.0360 (8)0.0472 (9)0.0062 (7)0.0297 (8)0.0091 (7)
C110.0310 (7)0.0279 (7)0.0256 (6)0.0040 (5)0.0132 (5)0.0053 (5)
C120.0307 (7)0.0263 (7)0.0295 (7)0.0009 (5)0.0147 (6)0.0032 (6)
O10.0356 (5)0.0299 (5)0.0253 (5)0.0089 (4)0.0147 (4)0.0050 (4)
O20.0343 (5)0.0298 (5)0.0247 (5)0.0078 (4)0.0145 (4)0.0043 (4)
O30.0615 (7)0.0419 (6)0.0295 (5)0.0174 (5)0.0234 (5)0.0061 (5)
O40.0495 (6)0.0363 (6)0.0347 (6)0.0162 (5)0.0249 (5)0.0089 (5)
O5W0.0475 (6)0.0314 (6)0.0309 (5)0.0032 (5)0.0227 (5)0.0026 (4)
Geometric parameters (Å, º) top
C1—O21.3720 (16)C8—C101.513 (2)
C1—C61.3903 (19)C9—H9A0.9800
C1—C21.3906 (18)C9—H9B0.9800
C2—O11.3738 (16)C9—H9C0.9800
C2—C31.3781 (19)C10—H10A0.9800
C3—C41.389 (2)C10—H10B0.9800
C3—C71.514 (2)C10—H10C0.9800
C4—C51.386 (2)C11—O21.4147 (16)
C4—H40.9500C11—C121.509 (2)
C5—C61.395 (2)C11—H11A0.9900
C5—H50.9500C11—H11B0.9900
C6—H60.9500C12—O31.2082 (17)
C7—C81.548 (2)C12—O41.3111 (16)
C7—H7A0.9900O4—H4A0.8400
C7—H7B0.9900O5W—H5A0.86 (2)
C8—O11.4868 (16)O5W—H5B0.85 (2)
C8—C91.511 (2)
O2—C1—C6127.47 (12)C9—C8—C7115.32 (13)
O2—C1—C2115.14 (11)C10—C8—C7111.45 (13)
C6—C1—C2117.38 (12)C8—C9—H9A109.5
O1—C2—C3113.96 (12)C8—C9—H9B109.5
O1—C2—C1123.09 (12)H9A—C9—H9B109.5
C3—C2—C1122.93 (13)C8—C9—H9C109.5
C2—C3—C4119.42 (13)H9A—C9—H9C109.5
C2—C3—C7107.23 (12)H9B—C9—H9C109.5
C4—C3—C7133.33 (13)C8—C10—H10A109.5
C5—C4—C3118.58 (13)C8—C10—H10B109.5
C5—C4—H4120.7H10A—C10—H10B109.5
C3—C4—H4120.7C8—C10—H10C109.5
C4—C5—C6121.54 (13)H10A—C10—H10C109.5
C4—C5—H5119.2H10B—C10—H10C109.5
C6—C5—H5119.2O2—C11—C12107.97 (11)
C1—C6—C5120.07 (13)O2—C11—H11A110.1
C1—C6—H6120.0C12—C11—H11A110.1
C5—C6—H6120.0O2—C11—H11B110.1
C3—C7—C8102.50 (11)C12—C11—H11B110.1
C3—C7—H7A111.3H11A—C11—H11B108.4
C8—C7—H7A111.3O3—C12—O4124.54 (13)
C3—C7—H7B111.3O3—C12—C11124.88 (13)
C8—C7—H7B111.3O4—C12—C11110.58 (11)
H7A—C7—H7B109.2C2—O1—C8106.73 (10)
O1—C8—C9105.86 (12)C1—O2—C11117.15 (10)
O1—C8—C10106.75 (12)C12—O4—H4A109.5
C9—C8—C10112.51 (14)H5A—O5W—H5B103.8 (18)
O1—C8—C7104.03 (11)
O2—C1—C2—O1−2.53 (19)C4—C3—C7—C8166.32 (16)
C6—C1—C2—O1178.40 (12)C3—C7—C8—O122.35 (15)
O2—C1—C2—C3175.87 (12)C3—C7—C8—C9137.81 (14)
C6—C1—C2—C3−3.2 (2)C3—C7—C8—C10−92.32 (14)
O1—C2—C3—C4−179.74 (12)O2—C11—C12—O32.6 (2)
C1—C2—C3—C41.7 (2)O2—C11—C12—O4−177.34 (11)
O1—C2—C3—C71.47 (16)C3—C2—O1—C813.73 (15)
C1—C2—C3—C7−177.06 (13)C1—C2—O1—C8−167.74 (12)
C2—C3—C4—C50.7 (2)C9—C8—O1—C2−144.32 (13)
C7—C3—C4—C5179.06 (15)C10—C8—O1—C295.60 (13)
C3—C4—C5—C6−1.5 (2)C7—C8—O1—C2−22.37 (14)
O2—C1—C6—C5−176.62 (13)C6—C1—O2—C112.41 (19)
C2—C1—C6—C52.3 (2)C2—C1—O2—C11−176.54 (11)
C4—C5—C6—C1−0.1 (2)C12—C11—O2—C1173.93 (11)
C2—C3—C7—C8−15.13 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5W—H5A···O10.86 (2)1.95 (2)2.8104 (15)173.0 (19)
O5W—H5B···O30.85 (2)1.94 (2)2.7888 (15)176.5 (19)
O4—H4A···O5Wi0.841.712.5416 (15)171
Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formulaC12H14O4·H2O
Mr240.25
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)10.1692 (7), 9.2516 (6), 15.3647 (11)
β (°) 121.000 (1)
V (Å3)1239.06 (15)
Z4
Radiation typeMo Kα
µ (mm−1)0.10
Crystal size (mm)0.46 × 0.42 × 0.30
Data collection
DiffractometerBruker SMART 1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2004)
Tmin, Tmax0.955, 0.971
No. of measured, independent and
observed [I > 2σ(I)] reflections		6151, 2697, 2120
Rint0.019
(sin θ/λ)max (Å−1)0.641
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.111, 1.04
No. of reflections2697
No. of parameters163
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.25, −0.16

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5W—H5A···O10.86 (2)1.95 (2)2.8104 (15)173.0 (19)
O5W—H5B···O30.85 (2)1.94 (2)2.7888 (15)176.5 (19)
O4—H4A···O5Wi0.841.712.5416 (15)170.5
Symmetry code: (i) −x+1, y−1/2, −z+3/2.
 

Acknowledgements

This work was supported by the Central University Basic Scientific Research Fund of Hunan University.

References

First citationBruker (2001). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationBruker (2003). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationLi, W.-S., Li, L. & Li, J.-S. (2009). Acta Cryst. E65, o2928.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationSheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationXu, L.-Z., Yu, G.-P. & Yang, S.-H. (2005). Acta Cryst. E61, o1924–o1926.  Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 6| June 2010| Page o1433
https://doi.org/10.1107/S1600536810018659
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