Tetraethyl 2,2′-(2,3,5,6-tetrafluoro-p-phenylenedimethylene)dipropanoate

Xi, H.; Gao, Y.; Sun, X.; Meng, Q.; Jiang, Y.

doi:10.1107/S1600536808027207

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1853

doi:10.1107/S1600536808027207

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Tetraethyl 2,2′-(2,3,5,6-tetrafluoro-p-phenylenedimethylene)dipropanoate †

Haitao Xi,^a ^* Yajun Gao,^a Xiaoqiang Sun,^a Qi Meng ^a and Yan Jiang ^a

^aSchool of Chemistry and Chemical Engineering, Jiangsu Polytechnic University, Changzhou 213164, People's Republic of China
^*Correspondence e-mail: xihaitao@em.jpu.edu.cn

(Received 6 July 2008; accepted 23 August 2008; online 30 August 2008)

In the molecule of the title compound, C₂₂H₂₆F₄O₈, a crystallographic inversion centre is located at the centroid of the benzene ring. C—H⋯F and C—H⋯O intramolecular hydrogen bonds are observed as well as an intermolecular C—H⋯O interaction.

Related literature

For related literature, see: Benetti et al. (1995 ); Howard et al. (1996 ); Thalladi et al. (1998 ).

Experimental

Crystal data

C₂₂H₂₆F₄O₈
M_r = 494.43
Orthorhombic, P b c a
a = 9.833 (5) Å
b = 8.797 (4) Å
c = 27.587 (14) Å
V = 2386 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 291 (2) K
0.30 × 0.26 × 0.24 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.96, T_max = 0.97
11819 measured reflections
2343 independent reflections
1411 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.097
S = 1.02
2343 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.16 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
C4—H4A⋯F2	0.97	2.42	2.852 (3)	107
C7—H7A⋯O2	0.97	2.29	2.667 (3)	102
C8—H8C⋯O2ⁱ	0.96	2.54	3.472 (4)	162
Symmetry code: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks 271217a, I. DOI: 10.1107/S1600536808027207/gw2045sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808027207/gw2045Isup2.hkl

checkCIF report

Comment top

β-Keto esters are multicoupling reagents with electrophilic and nuclephilic sites that have proven to be valuable tools in the synthesis of a wide variety of molecular systems(Benetti et al.,1995). In the present paper, we report the crystal structure of the title compound, (I). The molecule of (I) lies on a crystallographic inversion center located at the middle of the benzene ring. Selected bond distances and angles are given in Table 1. One pair of symmetrically related ethyl groups was found to be disordered over two orientations (Fig.1) The feature of the title compound in packing is based on C-H···O intramolecular interaction and C-H···F intramolecular interaction which had been reported in related references (Howard et al., 1996; Thalladi et al., 1998)(Fig.2); the C4-H4a···F2 distance is 2.852 Å. the C7-H7a···O2 distance is 2.667 Å and the C8-H8C···O2 distance is 3.472 Å.

Related literature top

For related literature, see: Benetti et al. (1995);Howard et al.(1996); Thalladi et al. (1998).

Experimental top

A mixture of 1,4-bis(bromomethyl)-2,3,5,6-tetrafluorobenzene (1.67g,5mmol), ethyl malonate(1.53mL,10mmol),potassuium carbonate(1.38g 10mmol) and acetonitrile(25mL) was stirred and refluxed for 8h. The solvent was evaporated on a rotary evaporator and the resulting oil was chromatographed on a silica-gel column,yielding the title compound (1.78g,69%). Crystals appropriate for data collection were obtained by slow evaporation of an acetonitrile solution at 283K. (m.p. 324-326K).

Computing details top

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

Figures top

	Fig. 1. View of the molecule (I),showing the atom-labelling scheme. (thermal ellipsoids are shown at 30% probability levels).[Symmetry code:(A) -x+2, -y+1,-z]
	Fig. 2. The molecular packing diagram in the crystal for (I) (Dashed lines indicate hydrogen bonds).

Tetraethyl 2,2'-(2,3,5,6-tetrafluoro-p-phenylenedimethylene)dipropanoate top

Crystal data top

C₂₂H₂₆F₄O₈	D_x = 1.376 Mg m⁻³
M_r = 494.43	Melting point = 324–326 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3968 reflections
a = 9.833 (5) Å	θ = 5.5–26.8°
b = 8.797 (4) Å	µ = 0.12 mm⁻¹
c = 27.587 (14) Å	T = 291 K
V = 2386 (2) Å³	Block, colorless
Z = 4	0.30 × 0.26 × 0.24 mm
F(000) = 1032

Data collection top

Bruker SMART Apex CCD diffractometer	2343 independent reflections
Radiation source: sealed tube	1411 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
phi and ω scans	θ_max = 26.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→12
T_min = 0.96, T_max = 0.97	k = −10→5
11819 measured reflections	l = −34→34

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.03P)² + 0.22P] where P = (F_o² + 2F_c²)/3
2343 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₂₂H₂₆F₄O₈	V = 2386 (2) Å³
M_r = 494.43	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 9.833 (5) Å	µ = 0.12 mm⁻¹
b = 8.797 (4) Å	T = 291 K
c = 27.587 (14) Å	0.30 × 0.26 × 0.24 mm

Data collection top

Bruker SMART Apex CCD diffractometer	2343 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1411 reflections with I > 2σ(I)
T_min = 0.96, T_max = 0.97	R_int = 0.059
11819 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.02	Δρ_max = 0.16 e Å⁻³
2343 reflections	Δρ_min = −0.15 e Å⁻³
156 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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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
C1	0.9879 (2)	0.6145 (3)	0.03274 (8)	0.0390 (6)
C2	0.9112 (2)	0.4839 (3)	0.04088 (8)	0.0355 (5)
C3	0.9249 (2)	0.3719 (3)	0.00603 (8)	0.0389 (6)
C4	0.8172 (2)	0.4682 (3)	0.08408 (8)	0.0454 (7)
H4A	0.7622	0.3774	0.0803	0.054*
H4B	0.7565	0.5550	0.0853	0.054*
C5	0.8979 (2)	0.4582 (3)	0.13216 (8)	0.0419 (6)
H5	0.9305	0.5599	0.1409	0.050*
C6	0.8013 (3)	0.4001 (3)	0.17246 (8)	0.0499 (7)
C7	0.7966 (3)	0.3238 (3)	0.25401 (9)	0.0570 (7)
H7A	0.7203	0.2646	0.2422	0.068*
H7B	0.7619	0.4028	0.2752	0.068*
C8	0.8912 (3)	0.2252 (3)	0.28077 (11)	0.0633 (8)
H8A	0.9243	0.1468	0.2596	0.095*
H8B	0.8448	0.1799	0.3078	0.095*
H8C	0.9664	0.2846	0.2924	0.095*
C9	1.0178 (2)	0.3515 (3)	0.12940 (8)	0.0448 (7)
C10	1.0781 (3)	0.0853 (3)	0.11522 (9)	0.0538 (7)
H10A	1.0372	−0.0112	0.1239	0.065*
H10B	1.1521	0.1054	0.1376	0.065*
C11	1.1313 (3)	0.0783 (3)	0.06437 (9)	0.0568 (7)
H11A	1.0590	0.0505	0.0427	0.085*
H11B	1.2026	0.0039	0.0625	0.085*
H11C	1.1666	0.1760	0.0553	0.085*
F1	0.98045 (14)	0.72947 (17)	0.06482 (5)	0.0522 (4)
F2	0.85239 (14)	0.24185 (19)	0.01115 (5)	0.0546 (4)
O1	0.87007 (16)	0.3924 (2)	0.21311 (5)	0.0495 (5)
O2	0.68696 (19)	0.3633 (2)	0.16648 (7)	0.0587 (5)
O3	0.97511 (17)	0.2082 (2)	0.11861 (6)	0.0545 (5)
O4	1.13167 (17)	0.3861 (2)	0.13604 (6)	0.0526 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0430 (13)	0.0427 (15)	0.0313 (11)	0.0002 (12)	−0.0017 (10)	−0.0024 (11)
C2	0.0358 (12)	0.0442 (14)	0.0266 (10)	0.0010 (11)	0.0017 (9)	0.0088 (11)
C3	0.0432 (13)	0.0455 (15)	0.0280 (11)	−0.0024 (13)	−0.0063 (10)	0.0057 (11)
C4	0.0443 (13)	0.0598 (18)	0.0322 (11)	0.0021 (13)	0.0061 (11)	0.0094 (12)
C5	0.0462 (14)	0.0537 (17)	0.0258 (10)	−0.0021 (13)	0.0034 (10)	0.0042 (11)
C6	0.0569 (17)	0.0594 (19)	0.0335 (12)	0.0139 (15)	0.0119 (12)	0.0100 (13)
C7	0.0707 (18)	0.0593 (18)	0.0411 (13)	0.0087 (15)	0.0088 (13)	0.0088 (14)
C8	0.0652 (19)	0.0536 (18)	0.0712 (19)	0.0072 (16)	0.0121 (15)	0.0161 (16)
C9	0.0354 (14)	0.071 (2)	0.0284 (12)	−0.0039 (13)	−0.0018 (10)	0.0072 (13)
C10	0.0566 (16)	0.0553 (18)	0.0494 (14)	0.0151 (15)	0.0027 (13)	0.0066 (14)
C11	0.0589 (17)	0.0521 (16)	0.0594 (16)	0.0145 (14)	0.0128 (14)	−0.0038 (15)
F1	0.0598 (9)	0.0513 (9)	0.0457 (7)	−0.0051 (8)	0.0158 (7)	−0.0146 (7)
F2	0.0615 (9)	0.0584 (10)	0.0439 (8)	−0.0110 (8)	0.0038 (7)	0.0030 (8)
O1	0.0582 (10)	0.0578 (12)	0.0324 (8)	0.0049 (9)	0.0083 (8)	0.0063 (8)
O2	0.0526 (11)	0.0613 (14)	0.0621 (12)	−0.0012 (10)	0.0191 (9)	0.0198 (10)
O3	0.0466 (10)	0.0574 (13)	0.0596 (11)	0.0119 (10)	−0.0048 (9)	−0.0020 (10)
O4	0.0399 (10)	0.0566 (12)	0.0612 (11)	−0.0093 (9)	−0.0100 (8)	−0.0039 (10)

Geometric parameters (Å, º) top

C1—F1	1.346 (3)	C7—C8	1.471 (3)
C1—C3ⁱ	1.376 (3)	C7—H7A	0.9700
C1—C2	1.393 (3)	C7—H7B	0.9700
C2—C3	1.383 (3)	C8—H8A	0.9600
C2—C4	1.514 (3)	C8—H8B	0.9600
C3—F2	1.355 (3)	C8—H8C	0.9600
C3—C1ⁱ	1.376 (3)	C9—O4	1.174 (3)
C4—C5	1.548 (3)	C9—O3	1.361 (3)
C4—H4A	0.9700	C10—O3	1.484 (3)
C4—H4B	0.9700	C10—C11	1.499 (3)
C5—C9	1.509 (3)	C10—H10A	0.9700
C5—C6	1.549 (3)	C10—H10B	0.9700
C5—H5	0.9800	C11—H11A	0.9600
C6—O2	1.182 (3)	C11—H11B	0.9600
C6—O1	1.311 (3)	C11—H11C	0.9600
C7—O1	1.469 (3)

F1—C1—C3ⁱ	118.6 (2)	O1—C7—H7B	110.0
F1—C1—C2	119.0 (2)	C8—C7—H7B	110.0
C3ⁱ—C1—C2	122.3 (2)	H7A—C7—H7B	108.4
C3—C2—C1	115.0 (2)	C7—C8—H8A	109.5
C3—C2—C4	122.8 (2)	C7—C8—H8B	109.5
C1—C2—C4	122.2 (2)	H8A—C8—H8B	109.5
F2—C3—C1ⁱ	118.8 (2)	C7—C8—H8C	109.5
F2—C3—C2	118.5 (2)	H8A—C8—H8C	109.5
C1ⁱ—C3—C2	122.6 (2)	H8B—C8—H8C	109.5
C2—C4—C5	111.52 (19)	O4—C9—O3	124.7 (3)
C2—C4—H4A	109.3	O4—C9—C5	125.1 (3)
C5—C4—H4A	109.3	O3—C9—C5	110.2 (2)
C2—C4—H4B	109.3	O3—C10—C11	109.1 (2)
C5—C4—H4B	109.3	O3—C10—H10A	109.9
H4A—C4—H4B	108.0	C11—C10—H10A	109.9
C9—C5—C4	113.1 (2)	O3—C10—H10B	109.9
C9—C5—C6	108.1 (2)	C11—C10—H10B	109.9
C4—C5—C6	108.6 (2)	H10A—C10—H10B	108.3
C9—C5—H5	109.0	C10—C11—H11A	109.5
C4—C5—H5	109.0	C10—C11—H11B	109.5
C6—C5—H5	109.0	H11A—C11—H11B	109.5
O2—C6—O1	126.6 (2)	C10—C11—H11C	109.5
O2—C6—C5	125.0 (2)	H11A—C11—H11C	109.5
O1—C6—C5	108.3 (2)	H11B—C11—H11C	109.5
O1—C7—C8	108.5 (2)	C6—O1—C7	115.1 (2)
O1—C7—H7A	110.0	C9—O3—C10	118.5 (2)
C8—C7—H7A	110.0

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···F2	0.97	2.42	2.852 (3)	107
C7—H7A···O2	0.97	2.29	2.667 (3)	102
C8—H8C···O2ⁱⁱ	0.96	2.54	3.472 (4)	162

Symmetry code: (ii) x+1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₆F₄O₈
M_r	494.43
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	291
a, b, c (Å)	9.833 (5), 8.797 (4), 27.587 (14)
V (Å³)	2386 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.30 × 0.26 × 0.24

Data collection
Diffractometer	Bruker SMART Apex CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.96, 0.97
No. of measured, independent and observed [I > 2σ(I)] reflections	11819, 2343, 1411
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.097, 1.02
No. of reflections	2343
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.15

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···F2	0.97	2.42	2.852 (3)	107
C7—H7A···O2	0.97	2.29	2.667 (3)	102
C8—H8C···O2ⁱ	0.96	2.54	3.472 (4)	162

Symmetry code: (i) x+1/2, y, −z+1/2.

Footnotes

†Contribution No. 20272019.

Acknowledgements

The authors are grateful to Jiangsu Polytechnic University, the Natural Science Foundation of China (No.20272019) and the Key Laboratory of Fine Petrochemical Engineering of Jiangsu Province (KF0503) for finanical support.

References

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