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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o846.
Published online 2009 March 25. doi:  10.1107/S1600536809010101
PMCID: PMC2968965

4-[(6-Chloro-2-pyrid­yl)meth­oxy]-3-(2,4-dichloro­phen­yl)-1-oxaspiro­[4.5]dec-3-en-2-one

Abstract

In the title compound, C21H18Cl3NO3, the cyclo­hexane ring is in a chair conformation. The five-membered ring forms a dihedral angle of 69.89 (2)° with the benzene ring. The dihedral angle between the benzene and pyridine rings is 14.03 (7)°.

Related literature

For the biological activity of the title compound and a similar structure, see: Thomas et al. (2003 [triangle]). For its preparation, see: Lu et al. (2008 [triangle]); Sarcevic et al. (1973 [triangle]). For puckering parameters, see: Cremer & Pople (1975 [triangle]).

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Object name is e-65-0o846-scheme1.jpg

Experimental

Crystal data

  • C21H18Cl3NO3
  • M r = 438.71
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o846-efi1.jpg
  • a = 7.2457 (14) Å
  • b = 13.108 (3) Å
  • c = 21.054 (4) Å
  • β = 95.77 (3)°
  • V = 1989.5 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.48 mm−1
  • T = 113 K
  • 0.18 × 0.12 × 0.06 mm

Data collection

  • Rigaku Saturn diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.918, T max = 0.972
  • 14740 measured reflections
  • 3519 independent reflections
  • 3191 reflections with I > 2σ(I)
  • R int = 0.041

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.089
  • S = 1.08
  • 3519 reflections
  • 253 parameters
  • H-atom parameters constrained
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.31 e Å−3

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

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809010101/bx2196sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809010101/bx2196Isup2.hkl

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

supplementary crystallographic information

Comment

The goal of the synthesis of the title compound (I) is to obtain compounds with biological activity (Thomas et al., 2003). We report here the crystal structure of (I), Fig.1.The cyclohexane ring is a chair conformation [Puckering Amplitude (QT) = 0.5531 (18) Å, θ = 4.39 (19) °, [var phi] = 142 (3) °] (Cremer & Pople, 1975).The five membered ring form a dihedral angle of 69.89 (2)° with the benzene ring. In the crystal structure, the molecular packing is stabilized by one intermolecular C—H···O hydrogen bond.

Experimental

3-(2,4-Dichlorophenyl)-2,4-dioxo-1-oxaspiro[4.5]decane (6.26 g ;20.0 mmol), was suspended in a solution of sodium carbonate (1.08 g ;10.2 mmol) in 40 ml of water in a flask equipped with stirrer, water separator and reflux condenser. Toluene (80 ml) was added after 0.5 h, the mixture was heated to dehydration. Then 2-chloro-6-(chloromethyl)pyridine 3.56 g (22.0 mmol) and N,N-dimethylformamide(DMF) (40 ml) were added while maintaining the temperature at 100° C for 4 h. Upon cooling at room temperature. Then water (40 ml) was added. The mixture was extracted with CH2Cl2 (35 ml) and the organic layer was washed with water and dried over sodium sulfate. The excess CH2Cl2 was removed on a water vacuum pump to obtain the oil product which was crystallized from methanol to afford the title compound 7.89 g (90% yield) (Lu et al., 2008; Sarcevic et al., 1973). Single crystals suitable for X-ray measurement 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 or 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

C21H18Cl3NO3F(000) = 904
Mr = 438.71Dx = 1.465 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5265 reflections
a = 7.2457 (14) Åθ = 1.6–28.0°
b = 13.108 (3) ŵ = 0.48 mm1
c = 21.054 (4) ÅT = 113 K
β = 95.77 (3)°Platelet, colourless
V = 1989.5 (7) Å30.18 × 0.12 × 0.06 mm
Z = 4

Data collection

Rigaku Saturn diffractometer3519 independent reflections
Radiation source: rotating anode3191 reflections with I > 2σ(I)
confocalRint = 0.041
ω scansθmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)h = −8→8
Tmin = 0.918, Tmax = 0.972k = −15→15
14740 measured reflectionsl = −25→25

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)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089H-atom parameters constrained
S = 1.08w = 1/[σ2(Fo2) + (0.053P)2] where P = (Fo2 + 2Fc2)/3
3519 reflections(Δ/σ)max = 0.001
253 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = −0.31 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
Cl1−0.28480 (7)−0.08999 (4)0.06950 (2)0.03906 (15)
Cl2−0.06561 (6)0.21586 (3)0.228775 (19)0.02533 (13)
Cl30.36534 (7)0.22352 (4)0.06907 (2)0.03617 (15)
O10.00146 (14)0.14206 (8)0.42592 (5)0.0204 (3)
O2−0.26135 (15)0.13568 (9)0.35960 (5)0.0248 (3)
O30.35068 (14)0.00872 (8)0.35405 (5)0.0226 (3)
N10.4102 (2)0.18419 (11)0.19104 (7)0.0264 (3)
C10.1925 (2)0.10733 (12)0.42562 (7)0.0188 (3)
C20.3193 (2)0.20111 (12)0.42615 (8)0.0239 (4)
H2A0.44360.17950.41900.029*
H2B0.27450.24640.39150.029*
C30.3264 (2)0.25889 (13)0.48925 (8)0.0275 (4)
H3A0.20500.28700.49440.033*
H3B0.41350.31500.48890.033*
C40.3862 (3)0.18769 (13)0.54514 (8)0.0292 (4)
H4A0.51170.16410.54160.035*
H4B0.38620.22510.58490.035*
C50.2574 (2)0.09592 (13)0.54645 (8)0.0259 (4)
H5A0.13510.11880.55510.031*
H5B0.30420.05020.58060.031*
C60.2430 (2)0.03854 (12)0.48280 (7)0.0211 (4)
H6A0.36080.00580.47800.025*
H6B0.1498−0.01450.48350.025*
C70.1869 (2)0.05012 (11)0.36345 (7)0.0182 (3)
C80.3726 (2)−0.04708 (12)0.29626 (8)0.0251 (4)
H8A0.2760−0.09840.29010.030*
H8B0.4911−0.08220.30100.030*
C90.3640 (2)0.01985 (12)0.23785 (8)0.0221 (4)
C100.3138 (2)−0.02018 (13)0.17760 (8)0.0285 (4)
H100.2810−0.08860.17300.034*
C110.3125 (2)0.04149 (14)0.12452 (8)0.0293 (4)
H110.27990.01620.08370.035*
C120.3619 (2)0.14262 (13)0.13470 (8)0.0254 (4)
C130.4111 (2)0.12222 (13)0.24178 (8)0.0247 (4)
H130.44530.14960.28200.030*
C140.0183 (2)0.05485 (11)0.33042 (7)0.0185 (3)
C15−0.0991 (2)0.11385 (12)0.37036 (7)0.0199 (4)
C16−0.0574 (2)0.01791 (12)0.26666 (7)0.0190 (3)
C17−0.0880 (2)−0.08572 (12)0.25352 (8)0.0233 (4)
H17−0.0618−0.13320.28600.028*
C18−0.1565 (2)−0.11919 (13)0.19334 (8)0.0263 (4)
H18−0.1736−0.18850.18530.032*
C19−0.1993 (2)−0.04852 (13)0.14529 (8)0.0253 (4)
C20−0.1746 (2)0.05474 (12)0.15634 (8)0.0229 (4)
H20−0.20480.10200.12400.027*
C21−0.1040 (2)0.08598 (11)0.21652 (8)0.0185 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0450 (3)0.0442 (3)0.0269 (3)−0.0021 (2)−0.0017 (2)−0.0110 (2)
Cl20.0338 (3)0.0155 (2)0.0269 (2)0.00057 (16)0.00361 (19)0.00429 (15)
Cl30.0350 (3)0.0439 (3)0.0300 (3)−0.0021 (2)0.0051 (2)0.00633 (19)
O10.0162 (6)0.0236 (6)0.0215 (6)0.0040 (5)0.0021 (5)0.0022 (5)
O20.0166 (6)0.0297 (6)0.0280 (6)0.0052 (5)0.0021 (5)0.0069 (5)
O30.0187 (6)0.0257 (6)0.0233 (6)0.0067 (5)0.0016 (5)−0.0029 (5)
N10.0241 (8)0.0266 (8)0.0287 (8)−0.0017 (6)0.0034 (6)−0.0031 (6)
C10.0152 (8)0.0185 (8)0.0226 (8)0.0032 (6)0.0020 (7)0.0025 (6)
C20.0237 (9)0.0211 (8)0.0276 (9)−0.0004 (7)0.0062 (7)0.0020 (7)
C30.0257 (10)0.0208 (9)0.0361 (10)−0.0019 (7)0.0043 (8)−0.0039 (7)
C40.0313 (10)0.0279 (9)0.0277 (10)−0.0004 (8)−0.0006 (8)−0.0068 (8)
C50.0262 (9)0.0291 (9)0.0221 (9)0.0026 (7)0.0002 (7)0.0017 (7)
C60.0186 (8)0.0201 (8)0.0242 (9)0.0013 (7)−0.0005 (7)0.0018 (7)
C70.0181 (8)0.0148 (8)0.0220 (8)0.0015 (6)0.0034 (7)0.0037 (6)
C80.0233 (9)0.0229 (9)0.0292 (9)0.0074 (7)0.0027 (7)−0.0058 (7)
C90.0156 (8)0.0231 (9)0.0279 (9)0.0034 (7)0.0038 (7)−0.0053 (7)
C100.0291 (10)0.0248 (9)0.0326 (10)−0.0035 (7)0.0083 (8)−0.0096 (8)
C110.0289 (10)0.0354 (10)0.0240 (9)−0.0051 (8)0.0050 (7)−0.0105 (8)
C120.0168 (9)0.0346 (10)0.0255 (9)−0.0004 (7)0.0051 (7)−0.0024 (7)
C130.0210 (9)0.0291 (9)0.0237 (9)−0.0018 (7)0.0009 (7)−0.0071 (7)
C140.0182 (8)0.0152 (8)0.0221 (8)0.0000 (6)0.0020 (7)0.0047 (6)
C150.0219 (9)0.0170 (8)0.0207 (8)−0.0012 (7)0.0019 (7)0.0071 (6)
C160.0158 (8)0.0186 (8)0.0226 (8)−0.0003 (6)0.0022 (7)0.0024 (6)
C170.0223 (9)0.0184 (8)0.0290 (9)−0.0011 (7)0.0019 (7)0.0048 (7)
C180.0257 (10)0.0199 (9)0.0332 (10)−0.0032 (7)0.0031 (8)−0.0023 (7)
C190.0220 (9)0.0300 (9)0.0237 (9)−0.0023 (7)0.0015 (7)−0.0054 (7)
C200.0202 (9)0.0267 (9)0.0218 (8)0.0022 (7)0.0030 (7)0.0039 (7)
C210.0175 (8)0.0150 (8)0.0234 (9)0.0009 (6)0.0041 (7)−0.0003 (6)

Geometric parameters (Å, °)

Cl1—C191.7398 (17)C6—H6A0.9700
Cl2—C211.7400 (16)C6—H6B0.9700
Cl3—C121.7440 (17)C7—C141.345 (2)
O1—C151.366 (2)C8—C91.507 (2)
O1—C11.4577 (18)C8—H8A0.9700
O2—C151.2090 (19)C8—H8B0.9700
O3—C71.3375 (18)C9—C131.385 (2)
O3—C81.4421 (18)C9—C101.387 (2)
N1—C121.320 (2)C10—C111.378 (2)
N1—C131.342 (2)C10—H100.9300
C1—C71.505 (2)C11—C121.384 (2)
C1—C61.519 (2)C11—H110.9300
C1—C21.534 (2)C13—H130.9300
C2—C31.526 (2)C14—C151.474 (2)
C2—H2A0.9700C14—C161.480 (2)
C2—H2B0.9700C16—C211.398 (2)
C3—C41.530 (2)C16—C171.400 (2)
C3—H3A0.9700C17—C181.385 (2)
C3—H3B0.9700C17—H170.9300
C4—C51.524 (2)C18—C191.384 (2)
C4—H4A0.9700C18—H180.9300
C4—H4B0.9700C19—C201.382 (2)
C5—C61.531 (2)C20—C211.380 (2)
C5—H5A0.9700C20—H200.9300
C5—H5B0.9700
C15—O1—C1109.69 (12)C9—C8—H8A108.9
C7—O3—C8120.36 (13)O3—C8—H8B108.9
C12—N1—C13116.43 (15)C9—C8—H8B108.9
O1—C1—C7102.52 (12)H8A—C8—H8B107.7
O1—C1—C6109.58 (12)C13—C9—C10117.49 (15)
C7—C1—C6112.12 (13)C13—C9—C8121.71 (15)
O1—C1—C2108.54 (12)C10—C9—C8120.77 (15)
C7—C1—C2111.66 (12)C11—C10—C9119.95 (16)
C6—C1—C2111.93 (14)C11—C10—H10120.0
C3—C2—C1111.83 (13)C9—C10—H10120.0
C3—C2—H2A109.2C10—C11—C12117.11 (16)
C1—C2—H2A109.2C10—C11—H11121.4
C3—C2—H2B109.2C12—C11—H11121.4
C1—C2—H2B109.2N1—C12—C11125.13 (16)
H2A—C2—H2B107.9N1—C12—Cl3115.93 (13)
C2—C3—C4110.44 (14)C11—C12—Cl3118.94 (13)
C2—C3—H3A109.6N1—C13—C9123.89 (15)
C4—C3—H3A109.6N1—C13—H13118.1
C2—C3—H3B109.6C9—C13—H13118.1
C4—C3—H3B109.6C7—C14—C15105.99 (14)
H3A—C3—H3B108.1C7—C14—C16133.52 (14)
C5—C4—C3111.65 (14)C15—C14—C16120.44 (14)
C5—C4—H4A109.3O2—C15—O1121.42 (14)
C3—C4—H4A109.3O2—C15—C14128.58 (15)
C5—C4—H4B109.3O1—C15—C14109.99 (13)
C3—C4—H4B109.3C21—C16—C17116.66 (15)
H4A—C4—H4B108.0C21—C16—C14121.05 (14)
C4—C5—C6111.10 (14)C17—C16—C14122.28 (14)
C4—C5—H5A109.4C18—C17—C16121.58 (15)
C6—C5—H5A109.4C18—C17—H17119.2
C4—C5—H5B109.4C16—C17—H17119.2
C6—C5—H5B109.4C19—C18—C17119.35 (15)
H5A—C5—H5B108.0C19—C18—H18120.3
C1—C6—C5113.06 (13)C17—C18—H18120.3
C1—C6—H6A109.0C20—C19—C18121.13 (16)
C5—C6—H6A109.0C20—C19—Cl1119.24 (13)
C1—C6—H6B109.0C18—C19—Cl1119.63 (13)
C5—C6—H6B109.0C21—C20—C19118.36 (15)
H6A—C6—H6B107.8C21—C20—H20120.8
O3—C7—C14135.67 (15)C19—C20—H20120.8
O3—C7—C1112.59 (13)C20—C21—C16122.90 (14)
C14—C7—C1111.73 (13)C20—C21—Cl2117.74 (12)
O3—C8—C9113.22 (12)C16—C21—Cl2119.32 (12)
O3—C8—H8A108.9
C15—O1—C1—C7−2.79 (15)C12—N1—C13—C9−0.3 (2)
C15—O1—C1—C6−122.03 (13)C10—C9—C13—N10.2 (2)
C15—O1—C1—C2115.46 (13)C8—C9—C13—N1178.20 (15)
O1—C1—C2—C368.12 (17)O3—C7—C14—C15179.93 (16)
C7—C1—C2—C3−179.60 (13)C1—C7—C14—C15−1.50 (17)
C6—C1—C2—C3−52.96 (18)O3—C7—C14—C16−2.6 (3)
C1—C2—C3—C455.70 (18)C1—C7—C14—C16175.99 (15)
C2—C3—C4—C5−57.18 (19)C1—O1—C15—O2−179.05 (13)
C3—C4—C5—C655.15 (19)C1—O1—C15—C142.09 (16)
O1—C1—C6—C5−69.25 (17)C7—C14—C15—O2−179.10 (15)
C7—C1—C6—C5177.61 (13)C16—C14—C15—O23.0 (2)
C2—C1—C6—C551.22 (18)C7—C14—C15—O1−0.35 (16)
C4—C5—C6—C1−52.32 (18)C16—C14—C15—O1−178.24 (13)
C8—O3—C7—C140.0 (3)C7—C14—C16—C21−109.1 (2)
C8—O3—C7—C1−178.59 (12)C15—C14—C16—C2168.14 (19)
O1—C1—C7—O3−178.43 (12)C7—C14—C16—C1771.7 (2)
C6—C1—C7—O3−60.99 (17)C15—C14—C16—C17−111.08 (17)
C2—C1—C7—O365.55 (16)C21—C16—C17—C181.7 (2)
O1—C1—C7—C142.66 (16)C14—C16—C17—C18−179.07 (15)
C6—C1—C7—C14120.10 (15)C16—C17—C18—C19−1.3 (2)
C2—C1—C7—C14−113.36 (15)C17—C18—C19—C200.1 (3)
C7—O3—C8—C969.36 (18)C17—C18—C19—Cl1179.83 (12)
O3—C8—C9—C1326.2 (2)C18—C19—C20—C210.7 (2)
O3—C8—C9—C10−155.88 (14)Cl1—C19—C20—C21−179.05 (12)
C13—C9—C10—C110.1 (2)C19—C20—C21—C16−0.3 (2)
C8—C9—C10—C11−177.88 (16)C19—C20—C21—Cl2177.62 (12)
C9—C10—C11—C12−0.3 (2)C17—C16—C21—C20−0.9 (2)
C13—N1—C12—C110.2 (2)C14—C16—C21—C20179.87 (14)
C13—N1—C12—Cl3−178.92 (12)C17—C16—C21—Cl2−178.75 (12)
C10—C11—C12—N10.2 (3)C14—C16—C21—Cl22.0 (2)
C10—C11—C12—Cl3179.21 (13)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C13—H13···O30.932.532.864 (2)102

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BX2196).

References

  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc 97, 1354–1358.
  • Lu, Y., Tao, J. Z. & Zhang, Z. R. (2008). Chem. Intermed.10, 25–28.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sarcevic, N., Zsindely, J. & Schmid, H. (1973). Helv. Chim. Acta, 56, 1457–1476.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Thomas, B., Jordi, B. B., Reiner, F. & Ralf, N. (2003). Chimia, 57, 697–701.

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