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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o755.
Published online 2009 March 14. doi:  10.1107/S1600536809008617
PMCID: PMC2968886

4-Hydr­oxy-3-mesityl-1-oxaspiro­[4.4]non-3-en-2-one

Abstract

In the title compound, C17H20O3, the five-membered cyclo­pentyl ring displays an envelope conformation, with the atom at the flap position 0.538 (3) Å out of the mean plane formed by the other four atoms. The dihedral angle between the benzene and furan rings is 63.34 (15)°. In the crystal structure, mol­ecules are linked through inter­molecular O—H(...)O hydrogen bonds, forming a zigzag chain along [101].

Related literature

For related compounds, see: Fischer et al. (1995 [triangle]); Bayer Aktiengesellschaft (1995 [triangle]). For a related structure, see: Yu et al. (2009 [triangle]).

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Object name is e-65-0o755-scheme1.jpg

Experimental

Crystal data

  • C17H20O3
  • M r = 272.33
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o755-efi7.jpg
  • a = 8.8543 (4) Å
  • b = 17.9266 (7) Å
  • c = 9.4883 (4) Å
  • β = 97.809 (2)°
  • V = 1492.09 (11) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 296 K
  • 0.54 × 0.48 × 0.20 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.947, T max = 0.984
  • 14502 measured reflections
  • 3410 independent reflections
  • 2344 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.139
  • S = 1.00
  • 3410 reflections
  • 186 parameters
  • H-atom parameters constrained
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.17 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 [triangle]); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809008617/is2389sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809008617/is2389Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Natural Science Foundation of Zhejiang Province, China, for financial support (2008 C21029) and also thank Professor Jian-Ming Gu for his help with the crystal data analysis.

supplementary crystallographic information

Comment

Substituted 4-hydroxy-1-oxaspiro[4,4]non-3-en-2-one represent an important class of tetronic acids and part of them have high biological activity as herbicides and insecticides (Fischer et al., 1995). Bayer company has developed three tetronic acids pesticides-spirodiclofen, spiromesifen and spirotetramat (Bayer Aktiengesellschaft, 1995). In addition, the title compound 3-mesityl-4-hydroxy-1-oxaspiro[4,4]non-3-en-2-one is the key intermediate in preparing highly efficient acaricide- spiromesifen. As part of our continuing interest in the new acaricide design and synthesis, We have isolated the product, (I), of the cyclized reaction of 1-(2-mesityl-acetoxy)-cyclopentanecarboxylic acid methyl ester as colorless crystals suitable for X-ray analysis.

The molecular structure of (I) is shown in Fig. 1. The molecule contains one benzene ring and two five membered rings. The dihedral angle between benzene and furan rings is 63.28 (15)°, smaller than the angle between benzene and furan rings of the compound 3-Mesityl-2-oxo-1-oxaspiro[4,4]non-3-en-4-yl-2-(4-chlorophenyl) -3-methylbutyrate (Yu et al., 2009). The cyclopentyl ring displays an envelope conformation with C17 atom at the flap position 0.538 (3) Å out of the mean plane formed by the other four atoms. The title molecules are linked through an intermolecular hydrogen bond of O1—H1···O2. As expected, C2—C3 and C4—O2 are typically double bonds with bond distances of 1.344 (2) and 1.220 (2) Å. The bond distance of C3—C4 is 1.457 (2) Å, suggesting that carbonyl group on C4 has formed conjugate system with double bond on C3 and C2.

Experimental

1-(2-Mesityl-acetoxy)-cyclopentanecarboxylic acid methyl ester (10 mmol, 3.04 g) was added to a solution of potassium t-butoxide (12 mmol, 1.34 g) in t-butylalcohol (35 ml) and the mixture was stirred at reflux for 5 h. Then water (70 ml) was added and the solution was acidified with hydrochloric (2M) to give a solid precipitate. The solid was filtrated and recrystallized with 95% ethanol to colourless blocks.

Refinement

H atoms were included in calculated positions (C—H = 0.93–0.97 and O—H = 0.82 Å) and refined using a rinding model, with Uiso(H) = 1.2Ueq(C or O).

Figures

Fig. 1.
The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
Molecular packing arrangement in the unit cell.
Fig. 3.
View showing the O—H···O hydrogen bonding (dashed lines). [Symmetry codes: (i) -1/2 + x, 1/2 - y, -1/2 + z; (ii) 1/2 + x, 1/2 - y, 1/2 + z.]

Crystal data

C17H20O3F(000) = 584
Mr = 272.33Dx = 1.212 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ynCell parameters from 9815 reflections
a = 8.8543 (4) Åθ = 3.1–27.5°
b = 17.9266 (7) ŵ = 0.08 mm1
c = 9.4883 (4) ÅT = 296 K
β = 97.809 (2)°Chunk, colorless
V = 1492.09 (11) Å30.54 × 0.48 × 0.20 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer3410 independent reflections
Radiation source: fine-focus sealed tube2344 reflections with I > 2σ(I)
graphiteRint = 0.026
Detector resolution: 10.00 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scansh = −11→11
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)k = −22→23
Tmin = 0.947, Tmax = 0.984l = −12→11
14502 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.139w = 1/[σ2(Fo2) + (0.0705P)2 + 0.2966P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.003
3410 reflectionsΔρmax = 0.21 e Å3
186 parametersΔρmin = −0.17 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.028 (4)

Special details

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)

xyzUiso*/Ueq
O10.58430 (13)0.34534 (6)0.74039 (12)0.0565 (3)
H10.66440.32240.76100.068*
O20.35651 (13)0.19282 (7)0.36494 (12)0.0566 (3)
O30.28216 (11)0.29401 (6)0.47485 (11)0.0509 (3)
C10.34616 (17)0.34474 (8)0.58738 (16)0.0479 (4)
C20.49897 (16)0.31085 (8)0.63500 (15)0.0441 (3)
C30.52342 (15)0.25023 (8)0.55790 (15)0.0423 (3)
C40.38583 (16)0.24044 (8)0.45643 (16)0.0449 (4)
C50.66240 (15)0.20313 (8)0.56780 (14)0.0418 (3)
C60.65908 (17)0.12818 (9)0.60806 (15)0.0466 (4)
C70.7938 (2)0.08727 (10)0.62374 (18)0.0577 (4)
H70.79100.03730.64960.069*
C80.93077 (19)0.11821 (12)0.60223 (19)0.0630 (5)
C90.93142 (18)0.19158 (12)0.55935 (19)0.0632 (5)
H91.02320.21290.54280.076*
C100.79980 (17)0.23510 (10)0.53979 (17)0.0516 (4)
C110.5131 (2)0.09125 (10)0.6355 (2)0.0669 (5)
H11A0.53480.04210.67290.080*
H11B0.44470.08790.54800.080*
H11C0.46650.12020.70290.080*
C121.0770 (2)0.07381 (16)0.6244 (3)0.0992 (9)
H12A1.12970.07950.54300.119*
H12B1.05390.02210.63650.119*
H12C1.14040.09160.70770.119*
C130.8078 (3)0.31327 (12)0.4869 (3)0.0788 (6)
H13A0.72320.32240.41440.095*
H13B0.90140.32020.44810.095*
H13C0.80390.34740.56420.095*
C140.2387 (2)0.35110 (11)0.7003 (2)0.0651 (5)
H14A0.16790.30950.69260.078*
H14B0.29640.35070.79480.078*
C150.1532 (3)0.42400 (14)0.6740 (3)0.0951 (8)
H15A0.04420.41570.66730.114*
H15B0.18360.45880.75090.114*
C160.1930 (3)0.45354 (13)0.5383 (3)0.0983 (9)
H16A0.19410.50760.53930.118*
H16B0.12010.43680.45900.118*
C170.3512 (2)0.42296 (10)0.5263 (2)0.0672 (5)
H17A0.36990.42150.42800.081*
H17B0.42970.45280.58110.081*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O20.0467 (6)0.0659 (7)0.0516 (6)0.0019 (5)−0.0130 (5)−0.0115 (5)
O30.0375 (5)0.0604 (6)0.0503 (6)0.0066 (4)−0.0107 (5)−0.0036 (5)
O10.0467 (6)0.0621 (7)0.0544 (6)0.0071 (5)−0.0158 (5)−0.0121 (5)
C60.0434 (8)0.0533 (8)0.0421 (7)0.0022 (6)0.0023 (6)−0.0025 (6)
C20.0375 (7)0.0511 (8)0.0404 (7)0.0005 (6)−0.0062 (6)0.0018 (6)
C50.0337 (7)0.0544 (8)0.0350 (7)0.0002 (6)−0.0033 (5)−0.0035 (6)
C40.0362 (7)0.0538 (8)0.0420 (7)−0.0003 (6)−0.0040 (6)0.0018 (7)
C70.0587 (10)0.0606 (10)0.0515 (9)0.0148 (8)−0.0014 (8)−0.0052 (8)
C30.0331 (7)0.0508 (8)0.0403 (7)−0.0003 (6)−0.0045 (6)0.0010 (6)
C10.0415 (8)0.0530 (8)0.0450 (8)0.0063 (6)−0.0086 (6)−0.0003 (6)
C100.0393 (8)0.0672 (10)0.0471 (8)−0.0077 (7)0.0016 (6)−0.0061 (7)
C90.0325 (8)0.0966 (14)0.0598 (10)−0.0071 (8)0.0035 (7)−0.0207 (10)
C80.0434 (9)0.0874 (13)0.0544 (9)0.0161 (9)−0.0069 (7)−0.0207 (9)
C110.0600 (11)0.0624 (10)0.0800 (12)−0.0036 (8)0.0157 (9)0.0087 (9)
C140.0505 (10)0.0856 (13)0.0572 (10)0.0117 (9)0.0003 (8)−0.0070 (9)
C170.0730 (12)0.0551 (10)0.0672 (11)0.0017 (8)−0.0126 (9)0.0091 (8)
C130.0677 (13)0.0812 (13)0.0881 (14)−0.0219 (10)0.0133 (11)0.0100 (11)
C160.0885 (17)0.0668 (13)0.127 (2)0.0307 (12)−0.0290 (16)−0.0023 (14)
C120.0569 (12)0.129 (2)0.1046 (17)0.0382 (13)−0.0141 (12)−0.0354 (16)
C150.0583 (12)0.0889 (16)0.135 (2)0.0126 (11)0.0030 (13)−0.0317 (16)

Geometric parameters (Å, °)

O2—C41.2200 (18)C8—C121.510 (2)
O3—C41.3561 (18)C11—H11A0.9600
O3—C11.4574 (18)C11—H11B0.9600
O1—C21.3221 (17)C11—H11C0.9600
O1—H10.8200C14—C151.514 (3)
C6—C71.391 (2)C14—H14A0.9700
C6—C51.398 (2)C14—H14B0.9700
C6—C111.506 (2)C17—C161.523 (3)
C2—C31.344 (2)C17—H17A0.9700
C2—C11.4960 (19)C17—H17B0.9700
C5—C101.402 (2)C13—H13A0.9600
C5—C31.4847 (19)C13—H13B0.9600
C4—C31.4571 (19)C13—H13C0.9600
C7—C81.374 (3)C16—C151.479 (4)
C7—H70.9300C16—H16A0.9700
C1—C171.520 (2)C16—H16B0.9700
C1—C141.531 (3)C12—H12A0.9600
C10—C91.394 (2)C12—H12B0.9600
C10—C131.493 (3)C12—H12C0.9600
C9—C81.377 (3)C15—H15A0.9700
C9—H90.9300C15—H15B0.9700
C4—O3—C1109.49 (10)H11A—C11—H11C109.5
C2—O1—H1109.5H11B—C11—H11C109.5
C7—C6—C5119.10 (15)C15—C14—C1107.09 (18)
C7—C6—C11119.57 (15)C15—C14—H14A110.3
C5—C6—C11121.33 (14)C1—C14—H14A110.3
O1—C2—C3132.24 (13)C15—C14—H14B110.3
O1—C2—C1116.03 (13)C1—C14—H14B110.3
C3—C2—C1111.72 (12)H14A—C14—H14B108.6
C6—C5—C10119.70 (14)C1—C17—C16103.20 (18)
C6—C5—C3121.04 (13)C1—C17—H17A111.1
C10—C5—C3119.24 (14)C16—C17—H17A111.1
O2—C4—O3120.32 (12)C1—C17—H17B111.1
O2—C4—C3129.22 (14)C16—C17—H17B111.1
O3—C4—C3110.45 (13)H17A—C17—H17B109.1
C8—C7—C6122.20 (17)C10—C13—H13A109.5
C8—C7—H7118.9C10—C13—H13B109.5
C6—C7—H7118.9H13A—C13—H13B109.5
C2—C3—C4105.96 (13)C10—C13—H13C109.5
C2—C3—C5128.23 (12)H13A—C13—H13C109.5
C4—C3—C5125.79 (13)H13B—C13—H13C109.5
O3—C1—C2102.33 (11)C15—C16—C17105.47 (17)
O3—C1—C17108.96 (12)C15—C16—H16A110.6
C2—C1—C17114.67 (14)C17—C16—H16A110.6
O3—C1—C14110.02 (13)C15—C16—H16B110.6
C2—C1—C14116.21 (13)C17—C16—H16B110.6
C17—C1—C14104.56 (14)H16A—C16—H16B108.8
C9—C10—C5118.51 (16)C8—C12—H12A109.5
C9—C10—C13119.54 (16)C8—C12—H12B109.5
C5—C10—C13121.93 (16)H12A—C12—H12B109.5
C8—C9—C10122.48 (16)C8—C12—H12C109.5
C8—C9—H9118.8H12A—C12—H12C109.5
C10—C9—H9118.8H12B—C12—H12C109.5
C7—C8—C9117.95 (15)C16—C15—C14106.21 (19)
C7—C8—C12121.6 (2)C16—C15—H15A110.5
C9—C8—C12120.4 (2)C14—C15—H15A110.5
C6—C11—H11A109.5C16—C15—H15B110.5
C6—C11—H11B109.5C14—C15—H15B110.5
H11A—C11—H11B109.5H15A—C15—H15B108.7
C6—C11—H11C109.5
C7—C6—C5—C101.9 (2)C3—C2—C1—O31.92 (17)
C11—C6—C5—C10−178.43 (15)O1—C2—C1—C1763.07 (19)
C7—C6—C5—C3−176.40 (13)C3—C2—C1—C17−115.89 (16)
C11—C6—C5—C33.2 (2)O1—C2—C1—C14−59.24 (19)
C1—O3—C4—O2−178.53 (14)C3—C2—C1—C14121.80 (16)
C1—O3—C4—C31.85 (17)C6—C5—C10—C9−2.9 (2)
C5—C6—C7—C80.6 (2)C3—C5—C10—C9175.51 (14)
C11—C6—C7—C8−179.04 (16)C6—C5—C10—C13175.74 (16)
O1—C2—C3—C4−179.64 (16)C3—C5—C10—C13−5.9 (2)
C1—C2—C3—C4−0.90 (18)C5—C10—C9—C81.3 (3)
O1—C2—C3—C5−1.5 (3)C13—C10—C9—C8−177.29 (17)
C1—C2—C3—C5177.20 (14)C6—C7—C8—C9−2.1 (2)
O2—C4—C3—C2179.84 (16)C6—C7—C8—C12177.94 (17)
O3—C4—C3—C2−0.58 (18)C10—C9—C8—C71.1 (3)
O2—C4—C3—C51.7 (3)C10—C9—C8—C12−178.93 (18)
O3—C4—C3—C5−178.75 (13)O3—C1—C14—C15−101.66 (17)
C6—C5—C3—C2116.31 (18)C2—C1—C14—C15142.70 (16)
C10—C5—C3—C2−62.0 (2)C17—C1—C14—C1515.21 (19)
C6—C5—C3—C4−65.9 (2)O3—C1—C17—C1685.95 (18)
C10—C5—C3—C4115.72 (17)C2—C1—C17—C16−160.07 (16)
C4—O3—C1—C2−2.22 (16)C14—C1—C17—C16−31.65 (18)
C4—O3—C1—C17119.58 (15)C1—C17—C16—C1537.3 (2)
C4—O3—C1—C14−126.33 (14)C17—C16—C15—C14−27.9 (2)
O1—C2—C1—O3−179.12 (13)C1—C14—C15—C167.8 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.821.872.6267 (14)154

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2389).

References

  • Bayer Aktiengesellschaft (1995). WO Patent No. 9 504 719A1.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Fischer, R., Santel, B. W. & Erdelen, C. (1995). German Patent No. 4 337 853.
  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Rigaku (1998). PROCESS-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalStructure Rigaku/MSC, The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Yu, C.-M., Zhou, Y., Cheng, J.-L. & Zhao, J.-H. (2009). Acta Cryst. E65, o183. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography