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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1694.
Published online 2009 June 27. doi:  10.1107/S1600536809023666
PMCID: PMC2969376

5-(4-Fluoro­phen­yl)-2,2,6-trimethyl-4H-1,3-dioxin-4-one

Abstract

The 1,3-dioxine ring in the title compound, C13H13FO3, is in a half-boat conformation with the methyl-bonded C atom 0.612 (2) Å out of the plane defined by the remaining five atoms.

Related literature

For synthetic and structural background, see: Caracelli et al. (2007 [triangle]); Stefani et al. (2007 [triangle]); Vieira et al. (2008 [triangle]). For conformational analysis, see: Cremer & Pople (1975 [triangle]); Iulek & Zukerman-Schpector (1997 [triangle]).

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Object name is e-65-o1694-scheme1.jpg

Experimental

Crystal data

  • C13H13FO3
  • M r = 236.23
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1694-efi1.jpg
  • a = 11.865 (3) Å
  • b = 7.781 (2) Å
  • c = 12.780 (4) Å
  • β = 107.369 (5)°
  • V = 1126.1 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 98 K
  • 0.20 × 0.15 × 0.08 mm

Data collection

  • Rigaku AFC12/SATURN724 diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.977, T max = 1 (expected range = 0.969–0.991)
  • 4071 measured reflections
  • 2058 independent reflections
  • 1895 reflections with I > 2σ(I)
  • R int = 0.058

Refinement

  • R[F 2 > 2σ(F 2)] = 0.052
  • wR(F 2) = 0.150
  • S = 1.15
  • 2058 reflections
  • 157 parameters
  • H-atom parameters constrained
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: CrystalClear (Rigaku/MSC 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 2006 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809023666/ng2601sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023666/ng2601Isup2.hkl

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

Acknowledgments

We thank FAPESP (07/59404–2 to HAS, 08/02531–5 to JZ-S and 06/50190-7 to ASV), CNPq (300613/2007 to HAS and 307121/2006–0 to JZ-S) and CAPES for financial support.

supplementary crystallographic information

Comment

As part of our on-going research interest efforts exploring the chemistry of potassium organotrifluoroborate salts including their potential use as intermediates in organic synthesis (Caracelli et al., 2007; Stefani et al., 2007; Vieira et al. 2008), herein the crystal structure of (I) is described. The molecular structure, Fig. 1, shows the six-membered ring to adopt a half-boat conformation with the C2 atom being 0.612 (2) Å out of the plane defined by the remaining five atoms. The ring-puckering parameters being q2 = 0.415 (2) Å, q3 = 0.189 (1) Å, Q = 0.456 (1) Å, and [var phi]2 = 53.3 (2)°. The aryl ring is twisted with respect to the planar portion of the dioxin-4-one ring, as seen in the C4—C5—C7—C8 tosion angle of 55.8 (2)°.

Experimental

Single crystals of (I) were obtained by slow evaporation from methanol.

Refinement

The H atoms were positioned with idealized geometry using a riding model with C—H = 0.93–0.96 Å, and with Uiso set to 1.2 times (1.5 for methyl) Ueq(parent atom).

Figures

Fig. 1.
The molecular structure of (I) showing atom labelling scheme and displacement ellipsoids at the 50% probability level (arbitrary spheres for the H atoms).

Crystal data

C13H13FO3F(000) = 496
Mr = 236.23Dx = 1.393 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2836 reflections
a = 11.865 (3) Åθ = 2.8–40.2°
b = 7.781 (2) ŵ = 0.11 mm1
c = 12.780 (4) ÅT = 98 K
β = 107.369 (5)°Prism, colourless
V = 1126.1 (5) Å30.20 × 0.15 × 0.08 mm
Z = 4

Data collection

Rigaku AFC12/SATURN724 diffractometer2058 independent reflections
Radiation source: fine-focus sealed tube1895 reflections with I > 2σ(I)
graphiteRint = 0.058
ω scansθmax = 25.5°, θmin = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −14→11
Tmin = 0.977, Tmax = 1k = −6→9
4071 measured reflectionsl = −10→15

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)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.150H-atom parameters constrained
S = 1.15w = 1/[σ2(Fo2) + (0.0872P)2 + 0.1727P] where P = (Fo2 + 2Fc2)/3
2058 reflections(Δ/σ)max < 0.001
157 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = −0.25 e Å3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
C20.63242 (13)−0.0457 (2)0.70282 (12)0.0194 (4)
C40.70622 (13)−0.1569 (2)0.56052 (13)0.0193 (4)
C50.71736 (13)0.0244 (2)0.53203 (12)0.0186 (4)
C60.65075 (13)0.1421 (2)0.56386 (12)0.0184 (4)
C70.79551 (13)0.0670 (2)0.46347 (12)0.0192 (4)
C80.77995 (14)−0.0091 (2)0.36116 (13)0.0208 (4)
H80.7177−0.08540.33390.025*
C90.85535 (14)0.0266 (2)0.29960 (13)0.0237 (4)
H90.8447−0.02470.23160.028*
C100.94636 (15)0.1401 (2)0.34182 (14)0.0244 (4)
C110.96583 (14)0.2194 (2)0.44186 (14)0.0240 (4)
H111.02810.29600.46790.029*
C120.88968 (14)0.1817 (2)0.50293 (13)0.0216 (4)
H120.90140.23330.57100.026*
C130.53730 (14)−0.0969 (2)0.75301 (13)0.0229 (4)
H13A0.5194−0.00140.79290.034*
H13B0.5644−0.19180.80210.034*
H13C0.4676−0.13010.69600.034*
C140.74870 (14)−0.0007 (2)0.78687 (13)0.0224 (4)
H14A0.80810.01570.75070.034*
H14B0.7720−0.09240.83910.034*
H14C0.73970.10330.82410.034*
C150.63020 (15)0.3252 (2)0.52936 (13)0.0220 (4)
H15A0.66990.35020.47580.033*
H15B0.66050.39840.59200.033*
H15C0.54700.34500.49820.033*
O10.58727 (9)0.09857 (15)0.63304 (9)0.0209 (3)
O30.64762 (9)−0.18821 (14)0.63603 (9)0.0198 (3)
O40.73951 (10)−0.27917 (15)0.51946 (9)0.0251 (3)
F1.02109 (9)0.17542 (15)0.28148 (9)0.0337 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C20.0239 (8)0.0180 (8)0.0181 (8)0.0005 (6)0.0090 (6)0.0009 (6)
C40.0173 (8)0.0235 (8)0.0169 (7)−0.0010 (6)0.0046 (6)−0.0016 (6)
C50.0192 (7)0.0209 (8)0.0152 (8)−0.0004 (6)0.0042 (6)0.0001 (6)
C60.0175 (8)0.0226 (8)0.0153 (8)−0.0019 (6)0.0049 (6)−0.0002 (6)
C70.0194 (8)0.0195 (8)0.0182 (8)0.0042 (6)0.0048 (6)0.0034 (6)
C80.0215 (8)0.0197 (8)0.0208 (8)0.0021 (6)0.0056 (6)0.0005 (6)
C90.0266 (8)0.0280 (9)0.0175 (8)0.0073 (7)0.0083 (6)0.0031 (7)
C100.0211 (8)0.0305 (9)0.0246 (9)0.0076 (6)0.0115 (7)0.0092 (7)
C110.0190 (8)0.0264 (8)0.0257 (9)−0.0003 (6)0.0051 (6)0.0043 (7)
C120.0211 (8)0.0242 (8)0.0188 (8)0.0021 (6)0.0050 (6)0.0019 (6)
C130.0231 (8)0.0257 (9)0.0222 (8)−0.0009 (6)0.0104 (7)0.0022 (7)
C140.0253 (8)0.0252 (9)0.0181 (8)−0.0027 (6)0.0085 (6)−0.0005 (6)
C150.0257 (8)0.0210 (8)0.0212 (8)0.0017 (6)0.0098 (6)0.0010 (6)
O10.0231 (6)0.0218 (6)0.0205 (6)0.0022 (5)0.0106 (5)0.0030 (5)
O30.0237 (6)0.0181 (6)0.0192 (6)−0.0014 (4)0.0090 (5)−0.0014 (5)
O40.0313 (7)0.0208 (6)0.0265 (7)0.0005 (5)0.0140 (5)−0.0027 (5)
F0.0276 (6)0.0474 (7)0.0327 (6)0.0013 (5)0.0191 (5)0.0079 (5)

Geometric parameters (Å, °)

C2—O11.4345 (19)C9—H90.9300
C2—O31.4429 (19)C10—F1.3655 (19)
C2—C131.509 (2)C10—C111.375 (3)
C2—C141.515 (2)C11—C121.390 (2)
C4—O41.2081 (19)C11—H110.9300
C4—O31.3691 (18)C12—H120.9300
C4—C51.473 (2)C13—H13A0.9600
C5—C61.349 (2)C13—H13B0.9600
C5—C71.491 (2)C13—H13C0.9600
C6—O11.3643 (18)C14—H14A0.9600
C6—C151.490 (2)C14—H14B0.9600
C7—C81.397 (2)C14—H14C0.9600
C7—C121.401 (2)C15—H15A0.9600
C8—C91.385 (2)C15—H15B0.9600
C8—H80.9300C15—H15C0.9600
C9—C101.374 (3)
O1—C2—O3108.85 (12)C10—C11—C12118.05 (16)
O1—C2—C13106.44 (12)C10—C11—H11121.0
O3—C2—C13106.87 (12)C12—C11—H11121.0
O1—C2—C14110.59 (13)C11—C12—C7120.97 (15)
O3—C2—C14110.43 (12)C11—C12—H12119.5
C13—C2—C14113.46 (13)C7—C12—H12119.5
O4—C4—O3117.84 (14)C2—C13—H13A109.5
O4—C4—C5125.57 (15)C2—C13—H13B109.5
O3—C4—C5116.51 (14)H13A—C13—H13B109.5
C6—C5—C4118.14 (14)C2—C13—H13C109.5
C6—C5—C7123.34 (15)H13A—C13—H13C109.5
C4—C5—C7118.39 (14)H13B—C13—H13C109.5
C5—C6—O1120.89 (14)C2—C14—H14A109.5
C5—C6—C15128.21 (15)C2—C14—H14B109.5
O1—C6—C15110.85 (13)H14A—C14—H14B109.5
C8—C7—C12118.39 (14)C2—C14—H14C109.5
C8—C7—C5121.63 (14)H14A—C14—H14C109.5
C12—C7—C5119.94 (14)H14B—C14—H14C109.5
C9—C8—C7121.29 (15)C6—C15—H15A109.5
C9—C8—H8119.4C6—C15—H15B109.5
C7—C8—H8119.4H15A—C15—H15B109.5
C10—C9—C8118.12 (15)C6—C15—H15C109.5
C10—C9—H9120.9H15A—C15—H15C109.5
C8—C9—H9120.9H15B—C15—H15C109.5
F—C10—C9118.29 (16)C6—O1—C2114.91 (12)
F—C10—C11118.53 (15)C4—O3—C2117.38 (12)
C9—C10—C11123.18 (15)
O4—C4—C5—C6163.49 (15)C8—C9—C10—C110.0 (3)
O3—C4—C5—C6−13.0 (2)F—C10—C11—C12−179.58 (14)
O4—C4—C5—C7−12.6 (2)C9—C10—C11—C120.3 (3)
O3—C4—C5—C7170.94 (12)C10—C11—C12—C7−0.3 (2)
C4—C5—C6—O18.8 (2)C8—C7—C12—C110.2 (2)
C7—C5—C6—O1−175.29 (13)C5—C7—C12—C11178.08 (14)
C4—C5—C6—C15−168.39 (15)C5—C6—O1—C225.3 (2)
C7—C5—C6—C157.5 (3)C15—C6—O1—C2−157.02 (13)
C6—C5—C7—C8−120.06 (18)O3—C2—O1—C6−52.77 (16)
C4—C5—C7—C855.8 (2)C13—C2—O1—C6−167.62 (12)
C6—C5—C7—C1262.1 (2)C14—C2—O1—C668.72 (16)
C4—C5—C7—C12−122.05 (16)O4—C4—O3—C2165.97 (14)
C12—C7—C8—C90.1 (2)C5—C4—O3—C2−17.28 (18)
C5—C7—C8—C9−177.78 (14)O1—C2—O3—C448.96 (16)
C7—C8—C9—C10−0.2 (2)C13—C2—O3—C4163.53 (12)
C8—C9—C10—F179.84 (14)C14—C2—O3—C4−72.62 (16)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2601).

References

  • Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst.32, 115–119.
  • Brandenburg, K. (2006). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Caracelli, I., Stefani, H. A., Vieira, A. S., Machado, M. M. P. & Zukerman-Schpector, J. (2007). Z. Kristallogr. New Cryst. Struct.222, 345–346.
  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc.97, 1354–1358.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Iulek, J. & Zukerman-Schpector, J. (1997). Quim. Nova, 20, 433–434.
  • Rigaku/MSC (2005). CrystalClear Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Stefani, H. A., Cella, R. & Vieira, A. S. (2007). Tetrahedron, 63, 3623–3658.
  • Vieira, A. S., Fiorante, P. F., Zukerman-Schpector, J., Alves, D., Botteselle, G. V. & Stefani, H. A. (2008). Tetrahedron, 64, 7234–7241.

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