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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o845.
Published online 2009 March 25. doi:  10.1107/S1600536809008356
PMCID: PMC2968969

4-Benz­yloxy-3-(2,4-dichloro­phen­yl)-1-oxaspiro­[4.5]dec-3-en-2-one

Abstract

In the title compound, C22H20Cl2O3, the cyclo­hexyl ring adopts a chair conformation. The furanyl ring plane makes dihedral angles of 70.10 (2) and 86.12 (3)° with the 2,4-dichloro­phenyl ring and aromatic ring of the benzyl group, respectively. The crystal structure features weak inter­molecular C—H(...)O and C—H(...)Cl hydrogen bonds.

Related literature

For similar compounds, see: Bretschneider et al. (2003 [triangle]). For the synthesis, see: Yu et al. (1994 [triangle]); Song et al. (2008 [triangle]).

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Object name is e-65-0o845-scheme1.jpg

Experimental

Crystal data

  • C22H20Cl2O3
  • M r = 403.28
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o845-efi1.jpg
  • a = 7.2624 (15) Å
  • b = 12.117 (2) Å
  • c = 12.679 (3) Å
  • α = 63.30 (2)°
  • β = 87.67 (3)°
  • γ = 73.32 (1)°
  • V = 949.8 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.36 mm−1
  • T = 113 K
  • 0.18 × 0.16 × 0.10 mm

Data collection

  • Rigaku Saturn diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.938, T max = 0.965
  • 7095 measured reflections
  • 3328 independent reflections
  • 2376 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.078
  • S = 1.03
  • 3328 reflections
  • 244 parameters
  • H-atom parameters constrained
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809008356/ng2556sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809008356/ng2556Isup2.hkl

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

supplementary crystallographic information

Comment

The title compound (I) was prepared as part of a project in search for new compounds with biological activity (Bretschneider et al., 2003). We report here the crystal structure of (I).

In (I) (Fig. 1), all bond lengths and angles are normal and in a good agreement with those reported previously (Bretschneider et al., 2003). The cyclohexane ring (C1—C6) adopts a chair conformation. The furan ring (O1/C1/C7/C8/C9) plane forms dihedral angles of 71.10 (2)° and 86.12 (3)° with the benzene ring (C10—C15) and the benzyl plane (C16—C22) respectively. In addition to van der Waals forces, the structure is stabilized by weak C—H···O and C—H···Cl hydrogen bonds.

Experimental

3-(2,4-Dichlorophenyl)-2,4-dioxo-1-oxaspiro[4.5]decane 3.13 g (10.0 mmol), was suspended in a solution of sodium carbonate 0.54 g (5.1 mmol) in 20 ml of water in a flask equipped with stirrer, water separator and reflux condenser. Toluene (40 ml) was added after 0.5 h, the mixture was heated to dehydration to distil the toluene solvent. Then 1-(chloromethyl)benzene 1.39 g (11.0 mmol) and N,N-dimethylformamide(DMF) solvent (20 ml) were added while maintaining the temperature at 373 K for 4 h. Upon cooling at room temperature water (20 ml) was added. The mixture was extracted with CH2Cl2 (15 ml) and the organic layer was washed with water and dried over sodium sulfate. The excess CH2Cl2 was removedon a water vacuum pump to obtain the oily product. Crystallized from methanol to afford the title compound 2.95 g (80% yield) (Yu et al., 1994; Song et al., 2008). Single crystals suitable for X-ray diffraction were obtained by recrystallization from the mixture of acetone and methanol at room temperature.

Refinement

All C-bound H atoms were placed in calculated positions, with C—H = 0.93–0.97 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq(C) for the aryl and methylene H atoms.

Figures

Fig. 1.
View of the title compound (I), with displacement ellipsoids drawn at the 40% probability level.

Crystal data

C22H20Cl2O3Z = 2
Mr = 403.28F(000) = 420
Triclinic, P1Dx = 1.410 Mg m3
Hall symbol: -p 1Mo Kα radiation, λ = 0.71073 Å
a = 7.2624 (15) ÅCell parameters from 2983 reflections
b = 12.117 (2) Åθ = 2.0–27.9°
c = 12.679 (3) ŵ = 0.36 mm1
α = 63.30 (2)°T = 113 K
β = 87.67 (3)°Block, colorless
γ = 73.32 (1)°0.18 × 0.16 × 0.10 mm
V = 949.8 (3) Å3

Data collection

Rigaku Saturn diffractometer3328 independent reflections
Radiation source: rotating anode2376 reflections with I > 2σ(I)
confocalRint = 0.039
ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)h = −8→8
Tmin = 0.938, Tmax = 0.965k = −14→10
7095 measured reflectionsl = −15→14

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.03P)2] where P = (Fo2 + 2Fc2)/3
3328 reflections(Δ/σ)max = 0.001
244 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = −0.22 e Å3

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
Cl10.74501 (6)0.33929 (4)1.10256 (4)0.02229 (14)
Cl21.16128 (7)−0.12117 (5)1.44683 (4)0.02817 (15)
O10.65050 (16)0.34607 (11)0.77085 (11)0.0161 (3)
O20.93505 (17)0.29879 (11)0.86875 (11)0.0195 (3)
O30.37612 (16)0.16179 (11)0.97360 (11)0.0159 (3)
C10.4713 (2)0.31322 (16)0.79970 (16)0.0139 (4)
C20.3139 (3)0.43289 (16)0.79041 (17)0.0181 (4)
H2A0.19820.40930.81940.022*
H2B0.35660.46440.84020.022*
C30.2661 (3)0.54029 (17)0.66320 (18)0.0236 (5)
H3A0.37810.56990.63650.028*
H3B0.16160.61300.66000.028*
C40.2071 (3)0.49221 (18)0.58136 (19)0.0313 (5)
H4A0.08850.46980.60380.038*
H4B0.18270.56080.50030.038*
C50.3647 (3)0.37423 (18)0.58838 (17)0.0295 (5)
H5A0.47810.39950.55680.035*
H5B0.32010.34230.53960.035*
C60.4199 (3)0.26580 (16)0.71537 (16)0.0199 (4)
H6A0.31280.23070.74240.024*
H6B0.52960.19670.71680.024*
C70.5194 (2)0.21147 (15)0.92748 (16)0.0131 (4)
C80.6971 (2)0.19522 (15)0.96996 (16)0.0135 (4)
C90.7788 (3)0.28199 (16)0.87102 (17)0.0156 (4)
C100.8070 (2)0.11567 (16)1.08853 (16)0.0129 (4)
C110.8439 (2)0.17346 (16)1.15576 (16)0.0149 (4)
C120.9524 (2)0.10299 (16)1.26515 (16)0.0172 (4)
H120.97730.14391.30750.021*
C131.0228 (2)−0.02970 (17)1.30966 (16)0.0174 (4)
C140.9885 (2)−0.09177 (16)1.24730 (17)0.0176 (4)
H141.0361−0.18141.27900.021*
C150.8826 (2)−0.01880 (16)1.13717 (16)0.0160 (4)
H150.8612−0.06031.09450.019*
C160.3825 (3)0.08932 (16)1.10127 (16)0.0162 (4)
H16A0.50500.02131.13120.019*
H16B0.28070.04831.11940.019*
C170.3590 (2)0.17132 (17)1.16439 (17)0.0168 (4)
C180.2414 (3)0.29913 (17)1.11236 (18)0.0202 (4)
H180.18030.33611.03610.024*
C190.2147 (3)0.37185 (19)1.17361 (19)0.0278 (5)
H190.13800.45791.13780.033*
C200.3018 (3)0.3168 (2)1.2875 (2)0.0347 (6)
H200.28260.36531.32890.042*
C210.4176 (3)0.1892 (2)1.3404 (2)0.0344 (6)
H210.47590.15201.41750.041*
C220.4468 (3)0.11721 (19)1.27877 (18)0.0248 (5)
H220.52600.03181.31430.030*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0253 (3)0.0150 (2)0.0274 (3)−0.00301 (19)−0.0009 (2)−0.0119 (2)
Cl20.0312 (3)0.0302 (3)0.0146 (3)−0.0031 (2)−0.0051 (2)−0.0062 (2)
O10.0157 (7)0.0161 (6)0.0147 (7)−0.0071 (5)0.0021 (5)−0.0042 (6)
O20.0140 (7)0.0208 (7)0.0240 (8)−0.0086 (6)0.0042 (6)−0.0087 (6)
O30.0160 (7)0.0181 (6)0.0130 (8)−0.0081 (5)0.0023 (6)−0.0049 (6)
C10.0143 (9)0.0136 (9)0.0138 (10)−0.0076 (7)0.0019 (8)−0.0042 (8)
C20.0171 (10)0.0167 (9)0.0189 (11)−0.0040 (8)0.0009 (8)−0.0075 (8)
C30.0210 (11)0.0182 (10)0.0227 (12)−0.0021 (8)−0.0022 (9)−0.0039 (9)
C40.0354 (13)0.0295 (12)0.0186 (12)−0.0115 (10)−0.0100 (10)−0.0001 (10)
C50.0476 (14)0.0311 (11)0.0138 (12)−0.0214 (10)−0.0007 (10)−0.0077 (9)
C60.0280 (11)0.0184 (10)0.0169 (11)−0.0105 (8)0.0028 (9)−0.0090 (9)
C70.0147 (9)0.0117 (9)0.0163 (11)−0.0054 (7)0.0050 (8)−0.0087 (8)
C80.0141 (9)0.0114 (9)0.0160 (11)−0.0030 (7)0.0024 (8)−0.0078 (8)
C90.0159 (10)0.0128 (9)0.0179 (11)−0.0018 (8)0.0011 (8)−0.0082 (8)
C100.0080 (9)0.0159 (9)0.0154 (11)−0.0037 (7)0.0028 (7)−0.0076 (8)
C110.0127 (9)0.0136 (9)0.0177 (11)−0.0039 (7)0.0027 (8)−0.0068 (8)
C120.0178 (10)0.0214 (10)0.0162 (11)−0.0090 (8)0.0040 (8)−0.0102 (9)
C130.0136 (9)0.0225 (10)0.0126 (11)−0.0043 (8)0.0012 (8)−0.0058 (8)
C140.0183 (10)0.0147 (9)0.0168 (11)−0.0041 (8)0.0034 (8)−0.0053 (8)
C150.0144 (10)0.0182 (9)0.0187 (11)−0.0074 (8)0.0047 (8)−0.0101 (8)
C160.0166 (10)0.0157 (9)0.0140 (11)−0.0091 (8)0.0046 (8)−0.0025 (8)
C170.0132 (9)0.0230 (10)0.0162 (11)−0.0114 (8)0.0073 (8)−0.0075 (8)
C180.0197 (10)0.0246 (10)0.0174 (11)−0.0094 (8)0.0071 (8)−0.0093 (9)
C190.0269 (11)0.0285 (11)0.0358 (14)−0.0124 (9)0.0150 (10)−0.0199 (10)
C200.0326 (13)0.0555 (15)0.0384 (15)−0.0225 (11)0.0141 (11)−0.0358 (13)
C210.0277 (12)0.0596 (15)0.0243 (13)−0.0180 (11)0.0051 (10)−0.0236 (12)
C220.0195 (11)0.0326 (11)0.0194 (12)−0.0082 (9)0.0024 (9)−0.0091 (10)

Geometric parameters (Å, °)

Cl1—C111.7325 (18)C8—C91.464 (3)
Cl2—C131.7420 (19)C8—C101.477 (2)
O1—C91.371 (2)C10—C151.396 (2)
O1—C11.454 (2)C10—C111.397 (2)
O2—C91.206 (2)C11—C121.383 (2)
O3—C71.335 (2)C12—C131.379 (2)
O3—C161.449 (2)C12—H120.9300
C1—C71.507 (3)C13—C141.382 (2)
C1—C61.523 (2)C14—C151.382 (2)
C1—C21.526 (2)C14—H140.9300
C2—C31.522 (3)C15—H150.9300
C2—H2A0.9700C16—C171.504 (2)
C2—H2B0.9700C16—H16A0.9700
C3—C41.524 (3)C16—H16B0.9700
C3—H3A0.9700C17—C221.386 (3)
C3—H3B0.9700C17—C181.390 (2)
C4—C51.522 (3)C18—C191.386 (3)
C4—H4A0.9700C18—H180.9300
C4—H4B0.9700C19—C201.377 (3)
C5—C61.526 (3)C19—H190.9300
C5—H5A0.9700C20—C211.384 (3)
C5—H5B0.9700C20—H200.9300
C6—H6A0.9700C21—C221.382 (3)
C6—H6B0.9700C21—H210.9300
C7—C81.345 (2)C22—H220.9300
C9—O1—C1109.44 (14)O2—C9—C8129.10 (17)
C7—O3—C16119.28 (14)O1—C9—C8110.02 (15)
O1—C1—C7102.54 (14)C15—C10—C11117.08 (16)
O1—C1—C6109.19 (15)C15—C10—C8122.16 (15)
C7—C1—C6114.33 (14)C11—C10—C8120.74 (14)
O1—C1—C2108.53 (13)C12—C11—C10122.57 (15)
C7—C1—C2109.95 (15)C12—C11—Cl1118.35 (13)
C6—C1—C2111.78 (14)C10—C11—Cl1119.05 (13)
C3—C2—C1111.71 (16)C13—C12—C11118.09 (16)
C3—C2—H2A109.3C13—C12—H12121.0
C1—C2—H2A109.3C11—C12—H12121.0
C3—C2—H2B109.3C12—C13—C14121.61 (16)
C1—C2—H2B109.3C12—C13—Cl2119.22 (14)
H2A—C2—H2B107.9C14—C13—Cl2119.17 (14)
C2—C3—C4110.71 (16)C13—C14—C15119.12 (16)
C2—C3—H3A109.5C13—C14—H14120.4
C4—C3—H3A109.5C15—C14—H14120.4
C2—C3—H3B109.5C14—C15—C10121.52 (16)
C4—C3—H3B109.5C14—C15—H15119.2
H3A—C3—H3B108.1C10—C15—H15119.2
C5—C4—C3110.90 (16)O3—C16—C17113.48 (14)
C5—C4—H4A109.5O3—C16—H16A108.9
C3—C4—H4A109.5C17—C16—H16A108.9
C5—C4—H4B109.5O3—C16—H16B108.9
C3—C4—H4B109.5C17—C16—H16B108.9
H4A—C4—H4B108.0H16A—C16—H16B107.7
C4—C5—C6112.11 (18)C22—C17—C18119.09 (17)
C4—C5—H5A109.2C22—C17—C16119.83 (16)
C6—C5—H5A109.2C18—C17—C16120.98 (16)
C4—C5—H5B109.2C19—C18—C17120.35 (19)
C6—C5—H5B109.2C19—C18—H18119.8
H5A—C5—H5B107.9C17—C18—H18119.8
C1—C6—C5111.93 (15)C20—C19—C18120.03 (18)
C1—C6—H6A109.2C20—C19—H19120.0
C5—C6—H6A109.2C18—C19—H19120.0
C1—C6—H6B109.2C19—C20—C21120.01 (19)
C5—C6—H6B109.2C19—C20—H20120.0
H6A—C6—H6B107.9C21—C20—H20120.0
O3—C7—C8134.71 (17)C22—C21—C20120.0 (2)
O3—C7—C1113.78 (15)C22—C21—H21120.0
C8—C7—C1111.46 (17)C20—C21—H21120.0
C7—C8—C9106.26 (16)C21—C22—C17120.49 (18)
C7—C8—C10133.14 (17)C21—C22—H22119.8
C9—C8—C10120.56 (15)C17—C22—H22119.8
O2—C9—O1120.86 (17)
C9—O1—C1—C7−5.26 (15)C10—C8—C9—O1−179.53 (13)
C9—O1—C1—C6−126.89 (14)C7—C8—C10—C1571.9 (2)
C9—O1—C1—C2111.04 (15)C9—C8—C10—C15−110.56 (19)
O1—C1—C2—C366.38 (18)C7—C8—C10—C11−109.8 (2)
C7—C1—C2—C3177.80 (15)C9—C8—C10—C1167.8 (2)
C6—C1—C2—C3−54.1 (2)C15—C10—C11—C120.9 (3)
C1—C2—C3—C456.4 (2)C8—C10—C11—C12−177.49 (16)
C2—C3—C4—C5−56.7 (2)C15—C10—C11—Cl1−177.30 (14)
C3—C4—C5—C655.2 (2)C8—C10—C11—Cl14.3 (2)
O1—C1—C6—C5−68.13 (19)C10—C11—C12—C13−1.4 (3)
C7—C1—C6—C5177.68 (15)Cl1—C11—C12—C13176.86 (14)
C2—C1—C6—C552.0 (2)C11—C12—C13—C140.6 (3)
C4—C5—C6—C1−52.9 (2)C11—C12—C13—Cl2179.62 (13)
C16—O3—C7—C813.0 (3)C12—C13—C14—C150.6 (3)
C16—O3—C7—C1−164.16 (13)Cl2—C13—C14—C15−178.43 (14)
O1—C1—C7—O3−177.66 (12)C13—C14—C15—C10−1.0 (3)
C6—C1—C7—O3−59.62 (19)C11—C10—C15—C140.3 (3)
C2—C1—C7—O367.05 (18)C8—C10—C15—C14178.71 (16)
O1—C1—C7—C84.54 (17)C7—O3—C16—C1767.88 (19)
C6—C1—C7—C8122.59 (17)O3—C16—C17—C22−149.82 (16)
C2—C1—C7—C8−110.74 (16)O3—C16—C17—C1833.8 (2)
O3—C7—C8—C9−179.26 (16)C22—C17—C18—C190.9 (3)
C1—C7—C8—C9−2.11 (18)C16—C17—C18—C19177.25 (18)
O3—C7—C8—C10−1.4 (3)C17—C18—C19—C20−1.3 (3)
C1—C7—C8—C10175.71 (16)C18—C19—C20—C210.7 (3)
C1—O1—C9—O2−177.12 (14)C19—C20—C21—C220.3 (3)
C1—O1—C9—C84.38 (16)C20—C21—C22—C17−0.7 (3)
C7—C8—C9—O2−179.72 (16)C18—C17—C22—C210.1 (3)
C10—C8—C9—O22.1 (3)C16—C17—C22—C21−176.28 (18)
C7—C8—C9—O1−1.38 (18)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2A···O2i0.972.543.477 (2)162
C2—H2B···Cl1ii0.972.693.5051 (19)142

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2556).

References

  • Bretschneider, T., Benet-Buchholz, J., Fischer, R. & Nauen, R. (2003). Chimia, 57, 697–701.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Song, R. F. (2008). Fine Chem.25, 708–709.
  • Yu, M. X. (1994). Pestic. Sci.33, 14–15.

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