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 ▶); 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,

• a = 11.865 (3) Å

• b = 7.781 (2) Å

• c = 12.780 (4) Å

• β = 107.369 (5)°

• V = 1126.1 (5) ų

• 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[F ² > 2σ(F ²)] = 0.052

• wR(F ²) = 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 ▶).

Supplementary Material

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

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 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)°.

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 U_iso set to 1.2 times (1.5 for methyl) U_eq(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

C13H13FO3	F(000) = 496
Mr = 236.23	Dx = 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

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

Refinement

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(Fo2) + (0.0872P)2 + 0.1727P] where P = (Fo2 + 2Fc2)/3
2058 reflections	(Δ/σ)max < 0.001
157 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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)