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

Zukerman-Schpector, J.; Vieira, A.S.; Stefani, H.A.; Tiekink, E.R.T.

doi:10.1107/S1600536809023666

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1694

doi:10.1107/S1600536809023666

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

Julio Zukerman-Schpector,^a ^* Adriano S. Vieira,^b Hélio A. Stefani ^b and Edward R. T. Tiekink ^a

^aDepartment of Chemistry, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, and ^bDepartamento de Farmácia, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, São Paulo-SP, Brazil
^*Correspondence e-mail: julio@power.ufscar.br

(Received 18 June 2009; accepted 19 June 2009; online 27 June 2009)

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 ); Stefani et al. (2007 ); Vieira et al. (2008 ). For conformational analysis, see: Cremer & Pople (1975 ); Iulek & Zukerman-Schpector (1997 ).

Experimental

Crystal data

C₁₃H₁₃FO₃
M_r = 236.23
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.052
wR(F²) = 0.150
S = 1.15
2058 reflections
157 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.25 e Å⁻³

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

Supporting information

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

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

checkCIF report

Comment top

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 ϕ₂ = 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)°.

Related literature top

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

Experimental top

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

Computing details top

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

Figures top

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).

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

Crystal data top

C₁₃H₁₃FO₃	F(000) = 496
M_r = 236.23	D_x = 1.393 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2836 reflections
a = 11.865 (3) Å	θ = 2.8–40.2°
b = 7.781 (2) Å	µ = 0.11 mm⁻¹
c = 12.780 (4) Å	T = 98 K
β = 107.369 (5)°	Prism, colourless
V = 1126.1 (5) Å³	0.20 × 0.15 × 0.08 mm
Z = 4

Data collection top

Rigaku AFC12/SATURN724 diffractometer	2058 independent reflections
Radiation source: fine-focus sealed tube	1895 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
ω scans	θ_max = 25.5°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −14→11
T_min = 0.977, T_max = 1	k = −6→9
4071 measured reflections	l = −10→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.150	H-atom parameters constrained
S = 1.15	w = 1/[σ²(F_o²) + (0.0872P)² + 0.1727P] where P = (F_o² + 2F_c²)/3
2058 reflections	(Δ/σ)_max < 0.001
157 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₃H₁₃FO₃	V = 1126.1 (5) Å³
M_r = 236.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.865 (3) Å	µ = 0.11 mm⁻¹
b = 7.781 (2) Å	T = 98 K
c = 12.780 (4) Å	0.20 × 0.15 × 0.08 mm
β = 107.369 (5)°

Data collection top

Rigaku AFC12/SATURN724 diffractometer	2058 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1895 reflections with I > 2σ(I)
T_min = 0.977, T_max = 1	R_int = 0.058
4071 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.150	H-atom parameters constrained
S = 1.15	Δρ_max = 0.32 e Å⁻³
2058 reflections	Δρ_min = −0.25 e Å⁻³
157 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
C2	0.63242 (13)	−0.0457 (2)	0.70282 (12)	0.0194 (4)
C4	0.70622 (13)	−0.1569 (2)	0.56052 (13)	0.0193 (4)
C5	0.71736 (13)	0.0244 (2)	0.53203 (12)	0.0186 (4)
C6	0.65075 (13)	0.1421 (2)	0.56386 (12)	0.0184 (4)
C7	0.79551 (13)	0.0670 (2)	0.46347 (12)	0.0192 (4)
C8	0.77995 (14)	−0.0091 (2)	0.36116 (13)	0.0208 (4)
H8	0.7177	−0.0854	0.3339	0.025*
C9	0.85535 (14)	0.0266 (2)	0.29960 (13)	0.0237 (4)
H9	0.8447	−0.0247	0.2316	0.028*
C10	0.94636 (15)	0.1401 (2)	0.34182 (14)	0.0244 (4)
C11	0.96583 (14)	0.2194 (2)	0.44186 (14)	0.0240 (4)
H11	1.0281	0.2960	0.4679	0.029*
C12	0.88968 (14)	0.1817 (2)	0.50293 (13)	0.0216 (4)
H12	0.9014	0.2333	0.5710	0.026*
C13	0.53730 (14)	−0.0969 (2)	0.75301 (13)	0.0229 (4)
H13A	0.5194	−0.0014	0.7929	0.034*
H13B	0.5644	−0.1918	0.8021	0.034*
H13C	0.4676	−0.1301	0.6960	0.034*
C14	0.74870 (14)	−0.0007 (2)	0.78687 (13)	0.0224 (4)
H14A	0.8081	0.0157	0.7507	0.034*
H14B	0.7720	−0.0924	0.8391	0.034*
H14C	0.7397	0.1033	0.8241	0.034*
C15	0.63020 (15)	0.3252 (2)	0.52936 (13)	0.0220 (4)
H15A	0.6699	0.3502	0.4758	0.033*
H15B	0.6605	0.3984	0.5920	0.033*
H15C	0.5470	0.3450	0.4982	0.033*
O1	0.58727 (9)	0.09857 (15)	0.63304 (9)	0.0209 (3)
O3	0.64762 (9)	−0.18821 (14)	0.63603 (9)	0.0198 (3)
O4	0.73951 (10)	−0.27917 (15)	0.51946 (9)	0.0251 (3)
F	1.02109 (9)	0.17542 (15)	0.28148 (9)	0.0337 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.0239 (8)	0.0180 (8)	0.0181 (8)	0.0005 (6)	0.0090 (6)	0.0009 (6)
C4	0.0173 (8)	0.0235 (8)	0.0169 (7)	−0.0010 (6)	0.0046 (6)	−0.0016 (6)
C5	0.0192 (7)	0.0209 (8)	0.0152 (8)	−0.0004 (6)	0.0042 (6)	0.0001 (6)
C6	0.0175 (8)	0.0226 (8)	0.0153 (8)	−0.0019 (6)	0.0049 (6)	−0.0002 (6)
C7	0.0194 (8)	0.0195 (8)	0.0182 (8)	0.0042 (6)	0.0048 (6)	0.0034 (6)
C8	0.0215 (8)	0.0197 (8)	0.0208 (8)	0.0021 (6)	0.0056 (6)	0.0005 (6)
C9	0.0266 (8)	0.0280 (9)	0.0175 (8)	0.0073 (7)	0.0083 (6)	0.0031 (7)
C10	0.0211 (8)	0.0305 (9)	0.0246 (9)	0.0076 (6)	0.0115 (7)	0.0092 (7)
C11	0.0190 (8)	0.0264 (8)	0.0257 (9)	−0.0003 (6)	0.0051 (6)	0.0043 (7)
C12	0.0211 (8)	0.0242 (8)	0.0188 (8)	0.0021 (6)	0.0050 (6)	0.0019 (6)
C13	0.0231 (8)	0.0257 (9)	0.0222 (8)	−0.0009 (6)	0.0104 (7)	0.0022 (7)
C14	0.0253 (8)	0.0252 (9)	0.0181 (8)	−0.0027 (6)	0.0085 (6)	−0.0005 (6)
C15	0.0257 (8)	0.0210 (8)	0.0212 (8)	0.0017 (6)	0.0098 (6)	0.0010 (6)
O1	0.0231 (6)	0.0218 (6)	0.0205 (6)	0.0022 (5)	0.0106 (5)	0.0030 (5)
O3	0.0237 (6)	0.0181 (6)	0.0192 (6)	−0.0014 (4)	0.0090 (5)	−0.0014 (5)
O4	0.0313 (7)	0.0208 (6)	0.0265 (7)	0.0005 (5)	0.0140 (5)	−0.0027 (5)
F	0.0276 (6)	0.0474 (7)	0.0327 (6)	0.0013 (5)	0.0191 (5)	0.0079 (5)

Geometric parameters (Å, º) top

C2—O1	1.4345 (19)	C9—H9	0.9300
C2—O3	1.4429 (19)	C10—F	1.3655 (19)
C2—C13	1.509 (2)	C10—C11	1.375 (3)
C2—C14	1.515 (2)	C11—C12	1.390 (2)
C4—O4	1.2081 (19)	C11—H11	0.9300
C4—O3	1.3691 (18)	C12—H12	0.9300
C4—C5	1.473 (2)	C13—H13A	0.9600
C5—C6	1.349 (2)	C13—H13B	0.9600
C5—C7	1.491 (2)	C13—H13C	0.9600
C6—O1	1.3643 (18)	C14—H14A	0.9600
C6—C15	1.490 (2)	C14—H14B	0.9600
C7—C8	1.397 (2)	C14—H14C	0.9600
C7—C12	1.401 (2)	C15—H15A	0.9600
C8—C9	1.385 (2)	C15—H15B	0.9600
C8—H8	0.9300	C15—H15C	0.9600
C9—C10	1.374 (3)

O1—C2—O3	108.85 (12)	C10—C11—C12	118.05 (16)
O1—C2—C13	106.44 (12)	C10—C11—H11	121.0
O3—C2—C13	106.87 (12)	C12—C11—H11	121.0
O1—C2—C14	110.59 (13)	C11—C12—C7	120.97 (15)
O3—C2—C14	110.43 (12)	C11—C12—H12	119.5
C13—C2—C14	113.46 (13)	C7—C12—H12	119.5
O4—C4—O3	117.84 (14)	C2—C13—H13A	109.5
O4—C4—C5	125.57 (15)	C2—C13—H13B	109.5
O3—C4—C5	116.51 (14)	H13A—C13—H13B	109.5
C6—C5—C4	118.14 (14)	C2—C13—H13C	109.5
C6—C5—C7	123.34 (15)	H13A—C13—H13C	109.5
C4—C5—C7	118.39 (14)	H13B—C13—H13C	109.5
C5—C6—O1	120.89 (14)	C2—C14—H14A	109.5
C5—C6—C15	128.21 (15)	C2—C14—H14B	109.5
O1—C6—C15	110.85 (13)	H14A—C14—H14B	109.5
C8—C7—C12	118.39 (14)	C2—C14—H14C	109.5
C8—C7—C5	121.63 (14)	H14A—C14—H14C	109.5
C12—C7—C5	119.94 (14)	H14B—C14—H14C	109.5
C9—C8—C7	121.29 (15)	C6—C15—H15A	109.5
C9—C8—H8	119.4	C6—C15—H15B	109.5
C7—C8—H8	119.4	H15A—C15—H15B	109.5
C10—C9—C8	118.12 (15)	C6—C15—H15C	109.5
C10—C9—H9	120.9	H15A—C15—H15C	109.5
C8—C9—H9	120.9	H15B—C15—H15C	109.5
F—C10—C9	118.29 (16)	C6—O1—C2	114.91 (12)
F—C10—C11	118.53 (15)	C4—O3—C2	117.38 (12)
C9—C10—C11	123.18 (15)

O4—C4—C5—C6	163.49 (15)	C8—C9—C10—C11	0.0 (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—C12	0.3 (3)
O3—C4—C5—C7	170.94 (12)	C10—C11—C12—C7	−0.3 (2)
C4—C5—C6—O1	8.8 (2)	C8—C7—C12—C11	0.2 (2)
C7—C5—C6—O1	−175.29 (13)	C5—C7—C12—C11	178.08 (14)
C4—C5—C6—C15	−168.39 (15)	C5—C6—O1—C2	25.3 (2)
C7—C5—C6—C15	7.5 (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—C8	55.8 (2)	C13—C2—O1—C6	−167.62 (12)
C6—C5—C7—C12	62.1 (2)	C14—C2—O1—C6	68.72 (16)
C4—C5—C7—C12	−122.05 (16)	O4—C4—O3—C2	165.97 (14)
C12—C7—C8—C9	0.1 (2)	C5—C4—O3—C2	−17.28 (18)
C5—C7—C8—C9	−177.78 (14)	O1—C2—O3—C4	48.96 (16)
C7—C8—C9—C10	−0.2 (2)	C13—C2—O3—C4	163.53 (12)
C8—C9—C10—F	179.84 (14)	C14—C2—O3—C4	−72.62 (16)

Experimental details

Crystal data
Chemical formula	C₁₃H₁₃FO₃
M_r	236.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	98
a, b, c (Å)	11.865 (3), 7.781 (2), 12.780 (4)
β (°)	107.369 (5)
V (Å³)	1126.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.20 × 0.15 × 0.08

Data collection
Diffractometer	Rigaku AFC12/SATURN724 diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.977, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	4071, 2058, 1895
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.150, 1.15
No. of reflections	2058
No. of parameters	157
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.25

Computer programs: CrystalClear (Rigaku/MSC 2005), CrystalClear (Rigaku/MSC, 2005), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), WinGX (Farrugia, 1999).

Acknowledgements

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.

References

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