3,3,4,4-Tetra­fluoro-2,3,4,5-tetra­hydro-1,6-benzodioxocine-8-carbaldehyde

Zeng, Z.; Zhong, J.-W.; Wang, H.; Wang, J.; Cao, W.-W.

doi:10.1107/S1600536810014133

organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1137

https://doi.org/10.1107/S1600536810014133

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3,3,4,4-Tetrafluoro-2,3,4,5-tetrahydro-1,6-benzodioxocine-8-carbaldehyde

Zhuo Zeng,^a ^* Jun-Wen Zhong,^a Hui Wang,^a Jin Wang ^a and Wan-Wan Cao ^a

^aSchool of Chemistry and Environment, South China Normal University, Guangzhou 510006, People's Republic of China
^*Correspondence e-mail: zhuosioc@yahoo.com.cn

(Received 13 March 2010; accepted 16 April 2010; online 24 April 2010)

In the title compound, C₁₁H₈F₄O₃, the eight-membered dialkoxy ring adopts a highly puckered conformation. In the crystal, molecules are linked by weak C—H⋯O interactions.

Related literature

For the applications of fluorinated mcarocyles, see: Babudri et al. (2007 ).

Experimental

Crystal data

C₁₁H₈F₄O₃
M_r = 264.17
Monoclinic, P 2₁ /n
a = 9.142 (5) Å
b = 11.4935 (14) Å
c = 10.928 (10) Å
β = 104.109 (15)°
V = 1113.6 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 298 K
0.35 × 0.24 × 0.11 mm

Data collection

Bruker SMART CCD diffractometer
5552 measured reflections
2000 independent reflections
972 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.146
S = 0.97
2000 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O3ⁱ	0.93	2.52	3.193 (5)	130
C8—H8B⋯O3ⁱⁱ	0.97	2.43	3.343 (6)	157
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+2.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810014133/hb5362sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810014133/hb5362Isup2.hkl

checkCIF report

Comment top

Fluorinated mcarocyles play an important role in the pharmaceutical, agrochemical and advanced materials fields (Babudri et al., 2007). As part of our studies in this area, we now report the synthesis and structure of the title compound, (I).

The structure of this compound is shown in Fig. 1. The benzene ring is attached to a highly puckered eight-membered dialkoxy ring. The torsion angle at the fusion bond (O1—C8—C9—O2) is 3.27°. The C—C bond distances of the aromatic ring vary from 1.373 (3) to 1.407 (3) A, the latter being the C2—C7 fusion bond. The ring angles of the benzene ring also vary from 118.9 (8) to 120.8 (9)° indicating a slight distortion in this ring.

Related literature top

For the applications of fluorinated mcarocyles, see: Babudri et al. (2007).

Experimental top

A mixture of 3,4-dihydroxy-benzaldehyde (0.345 g, 2.5 mmol), potassium carbonate (3.453 g, 25 mmol) was refluxed in acetonitrile (20 ml) at 373 K for 45 min, then a solution of methanesulfonic acid, trifluoro-, 2,2,3,3-tetrafluoro-1,4-butanediylester in acetonitrile (5 ml) was added, the mixture was heated under reflux for 12 h. After cooling to room temperature, the inorganic salts was removed by filtration . The filtrate was concentrated under reduced pressure, The residue was purified by flash chromatography on silica gel to afford the title compound as a white solid, yield 467 mg (70.8%). Colourless blocks of (I) were grown by by slow evaporation from dichloromethane at room temperature.

Structure description top

For the applications of fluorinated mcarocyles, see: Babudri et al. (2007).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. View of (I) showing displacement ellipsoids drawn at the 50% probability level.

3,3,4,4-Tetrafluoro-2,3,4,5-tetrahydro-1,6-benzodioxocine-8-carbaldehyde top

Crystal data top

C₁₁H₈F₄O₃	F(000) = 536.0
M_r = 264.17	D_x = 1.576 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 733 reflections
a = 9.142 (5) Å	θ = 3.2–20.1°
b = 11.4935 (14) Å	µ = 0.16 mm⁻¹
c = 10.928 (10) Å	T = 298 K
β = 104.109 (15)°	Block, colourless
V = 1113.6 (12) Å³	0.35 × 0.24 × 0.11 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	972 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.044
Graphite monochromator	θ_max = 25.2°, θ_min = 2.6°
ω scans	h = −6→10
5552 measured reflections	k = −13→13
2000 independent reflections	l = −13→11

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.146	w = 1/[σ²(F_o²) + (0.049P)² + 0.4913P] where P = (F_o² + 2F_c²)/3
S = 0.97	(Δ/σ)_max < 0.001
2000 reflections	Δρ_max = 0.15 e Å⁻³
164 parameters	Δρ_min = −0.15 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0047 (12)

Crystal data top

C₁₁H₈F₄O₃	V = 1113.6 (12) Å³
M_r = 264.17	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.142 (5) Å	µ = 0.16 mm⁻¹
b = 11.4935 (14) Å	T = 298 K
c = 10.928 (10) Å	0.35 × 0.24 × 0.11 mm
β = 104.109 (15)°

Data collection top

Bruker SMART CCD diffractometer	972 reflections with I > 2σ(I)
5552 measured reflections	R_int = 0.044
2000 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 0.97	Δρ_max = 0.15 e Å⁻³
2000 reflections	Δρ_min = −0.15 e Å⁻³
164 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
F2	0.5814 (2)	0.90137 (19)	0.9443 (2)	0.0901 (8)
F4	0.9709 (3)	0.8853 (2)	1.0613 (2)	0.1040 (9)
F1	0.7668 (3)	0.9585 (2)	0.8674 (2)	0.1008 (9)
F3	0.7960 (3)	0.9756 (2)	1.1293 (3)	0.1194 (10)
C4	0.8950 (4)	0.4731 (3)	1.1272 (3)	0.0599 (10)
H4	0.9789	0.4745	1.1953	0.072*
C7	0.6454 (3)	0.4699 (3)	0.9227 (3)	0.0545 (9)
H7	0.5614	0.4689	0.8547	0.065*
C6	0.7048 (3)	0.5746 (3)	0.9715 (3)	0.0535 (9)
C5	0.8301 (3)	0.5770 (3)	1.0754 (3)	0.0552 (9)
C2	0.7096 (3)	0.3650 (3)	0.9738 (3)	0.0549 (9)
C3	0.8354 (3)	0.3678 (3)	1.0779 (3)	0.0590 (10)
H3	0.8785	0.2986	1.1136	0.071*
C10	0.7221 (4)	0.8729 (4)	0.9373 (4)	0.0685 (11)
C8	0.8155 (4)	0.7738 (3)	1.1564 (3)	0.0669 (11)
H8A	0.8542	0.7957	1.2441	0.080*
H8B	0.7108	0.7509	1.1445	0.080*
C1	0.6488 (4)	0.2520 (4)	0.9223 (4)	0.0664 (11)
H1	0.6927	0.1853	0.9636	0.080*
C11	0.8265 (4)	0.8762 (4)	1.0718 (4)	0.0741 (11)
C9	0.7179 (4)	0.7596 (3)	0.8678 (3)	0.0657 (10)
H9A	0.6716	0.7710	0.7788	0.079*
H9B	0.8197	0.7310	0.8761	0.079*
O2	0.9011 (2)	0.6785 (2)	1.1261 (2)	0.0670 (7)
O1	0.6327 (2)	0.6767 (2)	0.9195 (2)	0.0622 (7)
O3	0.5453 (3)	0.2397 (2)	0.8295 (3)	0.0825 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F2	0.0728 (15)	0.0924 (18)	0.0987 (18)	0.0255 (13)	0.0085 (12)	0.0057 (14)
F4	0.0709 (15)	0.112 (2)	0.116 (2)	−0.0292 (14)	−0.0040 (13)	0.0202 (16)
F1	0.1117 (19)	0.0856 (18)	0.0951 (19)	−0.0162 (14)	0.0061 (14)	0.0252 (14)
F3	0.157 (2)	0.0757 (18)	0.103 (2)	0.0154 (16)	−0.0126 (17)	−0.0179 (16)
C4	0.049 (2)	0.073 (3)	0.046 (2)	−0.0005 (19)	−0.0088 (15)	0.0038 (19)
C7	0.0456 (19)	0.070 (3)	0.0410 (19)	−0.0046 (18)	−0.0020 (15)	0.0014 (18)
C6	0.0420 (19)	0.067 (3)	0.046 (2)	0.0014 (17)	0.0012 (16)	0.0051 (18)
C5	0.0449 (19)	0.065 (3)	0.049 (2)	−0.0042 (17)	−0.0011 (16)	−0.0010 (18)
C2	0.049 (2)	0.065 (2)	0.047 (2)	−0.0067 (17)	0.0062 (16)	−0.0003 (18)
C3	0.056 (2)	0.065 (3)	0.049 (2)	0.0014 (18)	0.0010 (17)	0.0049 (18)
C10	0.065 (2)	0.070 (3)	0.068 (3)	−0.003 (2)	0.010 (2)	0.013 (2)
C8	0.063 (2)	0.079 (3)	0.052 (2)	−0.001 (2)	0.0015 (17)	−0.009 (2)
C1	0.064 (2)	0.071 (3)	0.063 (2)	−0.010 (2)	0.012 (2)	−0.003 (2)
C11	0.070 (3)	0.071 (3)	0.074 (3)	0.000 (2)	0.004 (2)	−0.009 (2)
C9	0.058 (2)	0.084 (3)	0.049 (2)	0.000 (2)	0.0007 (16)	0.011 (2)
O2	0.0481 (13)	0.0678 (17)	0.0733 (18)	−0.0011 (12)	−0.0077 (12)	−0.0091 (13)
O1	0.0472 (13)	0.0663 (17)	0.0647 (16)	0.0009 (12)	−0.0025 (11)	0.0115 (13)
O3	0.0749 (17)	0.096 (2)	0.0663 (18)	−0.0205 (16)	−0.0032 (14)	−0.0142 (15)

Geometric parameters (Å, º) top

F2—C10	1.347 (4)	C2—C1	1.469 (5)
F4—C11	1.357 (4)	C3—H3	0.9300
F1—C10	1.368 (4)	C10—C9	1.504 (5)
F3—C11	1.365 (4)	C10—C11	1.545 (6)
C4—C3	1.381 (4)	C8—O2	1.432 (4)
C4—C5	1.392 (4)	C8—C11	1.515 (5)
C4—H4	0.9300	C8—H8A	0.9700
C7—C6	1.374 (4)	C8—H8B	0.9700
C7—C2	1.397 (4)	C1—O3	1.215 (4)
C7—H7	0.9300	C1—H1	0.9300
C6—O1	1.398 (4)	C9—O1	1.430 (4)
C6—C5	1.402 (4)	C9—H9A	0.9700
C5—O2	1.383 (4)	C9—H9B	0.9700
C2—C3	1.407 (4)

C3—C4—C5	120.3 (3)	O2—C8—C11	109.4 (3)
C3—C4—H4	119.8	O2—C8—H8A	109.8
C5—C4—H4	119.8	C11—C8—H8A	109.8
C6—C7—C2	120.9 (3)	O2—C8—H8B	109.8
C6—C7—H7	119.6	C11—C8—H8B	109.8
C2—C7—H7	119.6	H8A—C8—H8B	108.3
C7—C6—O1	118.4 (3)	O3—C1—C2	124.6 (4)
C7—C6—C5	119.9 (3)	O3—C1—H1	117.7
O1—C6—C5	121.6 (3)	C2—C1—H1	117.7
O2—C5—C4	116.7 (3)	F4—C11—F3	106.6 (3)
O2—C5—C6	123.5 (3)	F4—C11—C8	108.8 (3)
C4—C5—C6	119.7 (3)	F3—C11—C8	108.5 (4)
C7—C2—C3	119.0 (3)	F4—C11—C10	108.1 (4)
C7—C2—C1	121.8 (3)	F3—C11—C10	108.1 (3)
C3—C2—C1	119.2 (3)	C8—C11—C10	116.4 (3)
C4—C3—C2	120.1 (3)	O1—C9—C10	109.0 (3)
C4—C3—H3	119.9	O1—C9—H9A	109.9
C2—C3—H3	119.9	C10—C9—H9A	109.9
F2—C10—F1	106.1 (3)	O1—C9—H9B	109.9
F2—C10—C9	109.4 (3)	C10—C9—H9B	109.9
F1—C10—C9	108.4 (3)	H9A—C9—H9B	108.3
F2—C10—C11	108.5 (4)	C5—O2—C8	120.5 (2)
F1—C10—C11	108.3 (3)	C6—O1—C9	118.1 (2)
C9—C10—C11	115.8 (3)

C2—C7—C6—O1	−177.7 (3)	F2—C10—C11—F4	−160.5 (3)
C2—C7—C6—C5	−1.1 (5)	F1—C10—C11—F4	−45.8 (4)
C3—C4—C5—O2	−176.8 (3)	C9—C10—C11—F4	76.1 (4)
C3—C4—C5—C6	−0.9 (5)	F2—C10—C11—F3	−45.4 (5)
C7—C6—C5—O2	176.6 (3)	F1—C10—C11—F3	69.2 (4)
O1—C6—C5—O2	−6.8 (5)	C9—C10—C11—F3	−168.8 (3)
C7—C6—C5—C4	1.0 (5)	F2—C10—C11—C8	76.9 (4)
O1—C6—C5—C4	177.6 (3)	F1—C10—C11—C8	−168.5 (3)
C6—C7—C2—C3	0.9 (5)	C9—C10—C11—C8	−46.5 (5)
C6—C7—C2—C1	−179.4 (3)	F2—C10—C9—O1	−48.7 (4)
C5—C4—C3—C2	0.8 (5)	F1—C10—C9—O1	−163.9 (2)
C7—C2—C3—C4	−0.8 (5)	C11—C10—C9—O1	74.2 (4)
C1—C2—C3—C4	179.5 (3)	C4—C5—O2—C8	−134.3 (3)
C7—C2—C1—O3	3.8 (6)	C6—C5—O2—C8	49.9 (5)
C3—C2—C1—O3	−176.6 (4)	C11—C8—O2—C5	−114.5 (3)
O2—C8—C11—F4	−41.8 (4)	C7—C6—O1—C9	−121.7 (3)
O2—C8—C11—F3	−157.5 (3)	C5—C6—O1—C9	61.7 (4)
O2—C8—C11—C10	80.4 (4)	C10—C9—O1—C6	−120.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O3ⁱ	0.93	2.52	3.193 (5)	130
C8—H8B···O3ⁱⁱ	0.97	2.43	3.343 (6)	157

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

Experimental details

Crystal data
Chemical formula	C₁₁H₈F₄O₃
M_r	264.17
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	9.142 (5), 11.4935 (14), 10.928 (10)
β (°)	104.109 (15)
V (Å³)	1113.6 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.35 × 0.24 × 0.11

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5552, 2000, 972
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.146, 0.97
No. of reflections	2000
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.15

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O3ⁱ	0.93	2.52	3.193 (5)	130
C8—H8B···O3ⁱⁱ	0.97	2.43	3.343 (6)	157

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

Acknowledgements

We are grateful to the Doctoral Program Foundation of the Natural Science Foundation of Guangdong Province, China (No. 5100430) and South China Normal University Grants (524002, 523467) for financial support.

References

Babudri, F., Farinola, G. M., Naso, F. & Ragni, R. (2007). Chem. Commun. pp. 1003–1022 CrossRef Google Scholar
Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar