(3E,4E)-3-(1,3-Benzodioxol-5-ylmethyl­ene)-4-(1-phenyl­ethyl­idene)tetra­hydro­furan-2,5-dione

In the title compound, C₂₀H₁₄O₅, the methyl­enedioxy­phenyl ring system is essentially planar. There are short C—H...π inter­actions. The vinyl group is inclined with respect to the tetrahydrofuran ring by 21.43 (7)°. The dihedral angles made by the atoms defining the planar part of the tetrahydrofuran ring with the phenyl and methyl­ene­dioxy­phenyl rings are 35.24 (12) and 26.39 (9)°, respectively, while that between the two aryl rings is 14.43 (10)°.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.032
• wR factor = 0.086
• Data-to-parameter ratio = 8.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.52
           From the CIF: _reflns_number_total               1918
           Count of symmetry unique reflns         1921
           Completeness (_total/calc)             99.84%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Organic photochromic compounds, such as fulgides, are potential candidates for application in erasable optical information media. Attempts have been made to improve their photochromic properties (Asiri, 2003; Uchida et al., 1995). In order to achieve certain desirable properties such as absorption at longer wavelengths and thus higher fatigue resistance to coloration-bleaching cycles, improvements have been made by modifying the fulgide frame (Heller et al., 2000). We report here the crystal structure of the title compound, (I).

Related literature

For related literature, see: Asiri et al. (2003); Heller et al. (2000); Uchida et al. (1995).

S2. Experimental

The (2E,3E)-2-(1,3-benzodioxol-5-ylmethylene)-3-(1-phenylethylidene)succinic acid (0.01 mmol) was dissolved in dichloromethane (10 ml), and to this mixture was added acetyl chloride (5 ml) dropwise with stirring at 0 degree C, and the mixture was stirred at room temperature for 5 h. After removal of the excess acetyl chloride and dichloromethane, the residue was purified using flash column chromatography on silica gel (petroleum ether/ethyl acetate = 2/1; v/v) and recrystallized with ethyl acetate to give a solid (yield 76%). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of a solution of the solid in ethyl acetate at room temperature for 15 d.

S3. Refinement

H atoms were positioned geometrically (C - H = 0.93 - 0.97 A °) and refined as riding, with U_iso(H) = 1.2Ueq(C). Because of the meaningless of the absolute structure parameter, Friedel-pairs (4) were merged before final refinement.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and 50% probability displacement ellipsoids.
	Fig. 2. The view of the structure along a axis. All H atoms were omited for clarity except for those which were involve with X—H···Cg(Pi-Ring) interactions. Symmetry codes: (i) x,-1 + y,z; (ii) 0.5 - x,-1/2 + y,-1/2 + z; (iii) 1 - x,1 - y,-1/2 + z; (iv) 1 - x,2 - y,-1/2 + z; (v) 1/2 + x,1.5 - y,z.

(3E,4E)-3-(1,3-Benzodioxol-5-ylmethylene)-4-˘1-phenylethylidene)tetrahydrofuran-2,5-dione

Crystal data

C20H14O5	F(000) = 696
Mr = 334.31	Dx = 1.395 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 3450 reflections
a = 7.2201 (2) Å	θ = 3.0–26.3°
b = 18.0627 (5) Å	µ = 0.10 mm^−1
c = 12.2046 (4) Å	T = 296 K
V = 1591.66 (8) Å^3	Plate, orange–yellow
Z = 4	0.38 × 0.19 × 0.07 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	1918 independent reflections
Radiation source: fine-focus sealed tube	1606 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan APEX2 (Bruker, 2005)	h = −9→9
Tmin = 0.963, Tmax = 0.993	k = −23→23
9796 measured reflections	l = −15→5

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.086	w = 1/[σ^2(Fo^2) + (0.053P)^2 + 0.0276P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
1918 reflections	Δρmax = 0.11 e Å^−3
227 parameters	Δρmin = −0.12 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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
C1	0.4507 (4)	1.08850 (14)	0.6981 (3)	0.0766 (8)
H1	0.4852	1.1381	0.6987	0.092*
C2	0.3315 (4)	1.06286 (14)	0.6196 (3)	0.0746 (8)
H2	0.2857	1.0950	0.5666	0.090*
C3	0.2793 (3)	0.98960 (13)	0.6188 (2)	0.0590 (6)
H3	0.2008	0.9723	0.5641	0.071*
C4	0.3435 (3)	0.94086 (11)	0.69979 (17)	0.0459 (4)
C5	0.4666 (3)	0.96742 (11)	0.77765 (19)	0.0501 (5)
H5	0.5136	0.9357	0.8309	0.060*
C6	0.5196 (4)	1.04076 (13)	0.7763 (3)	0.0678 (7)
H6	0.6025	1.0582	0.8287	0.081*
C7	0.2848 (3)	0.86249 (11)	0.69894 (19)	0.0451 (4)
C8	0.2857 (4)	0.82596 (15)	0.5875 (2)	0.0653 (6)
H8A	0.3729	0.7858	0.5874	0.098*
H8B	0.3207	0.8616	0.5329	0.098*
H8C	0.1642	0.8073	0.5714	0.098*
C9	0.2416 (3)	0.82442 (11)	0.79118 (19)	0.0448 (4)
C10	0.2277 (3)	0.74232 (13)	0.7893 (2)	0.0579 (6)
C11	0.2485 (3)	0.77359 (13)	0.9690 (2)	0.0578 (6)
C12	0.2296 (3)	0.84388 (11)	0.90818 (18)	0.0444 (4)
C13	0.1956 (3)	0.90390 (11)	0.97086 (17)	0.0473 (5)
H13	0.2022	0.8946	1.0457	0.057*
C14	0.1507 (3)	0.98016 (11)	0.94437 (16)	0.0438 (4)
C15	0.0488 (2)	1.00096 (11)	0.85107 (17)	0.0429 (4)
H15	−0.0007	0.9658	0.8037	0.052*
C16	0.0257 (2)	1.07498 (12)	0.83316 (17)	0.0445 (4)
C17	0.1013 (3)	1.12780 (11)	0.9026 (2)	0.0522 (5)
C18	0.1941 (3)	1.10943 (12)	0.9952 (2)	0.0618 (6)
H18	0.2411	1.1453	1.0423	0.074*
C19	0.2157 (3)	1.03414 (12)	1.01647 (19)	0.0544 (5)
H19	0.2751	1.0195	1.0805	0.065*
C20	−0.0455 (4)	1.18660 (13)	0.7682 (2)	0.0692 (7)
H20A	0.0160	1.2098	0.7063	0.083*
H20B	−0.1664	1.2092	0.7767	0.083*
O1	−0.0653 (2)	1.10928 (8)	0.74889 (14)	0.0585 (4)
O2	0.0608 (3)	1.19719 (8)	0.86474 (16)	0.0709 (5)
O3	0.2660 (3)	0.76142 (11)	1.06471 (17)	0.0809 (6)
O4	0.2406 (3)	0.71527 (9)	0.89574 (18)	0.0691 (5)
O5	0.2125 (3)	0.69889 (10)	0.71649 (18)	0.0878 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0858 (17)	0.0437 (12)	0.100 (2)	−0.0096 (11)	0.0383 (18)	−0.0003 (16)
C2	0.0857 (17)	0.0588 (14)	0.0794 (19)	0.0115 (13)	0.0310 (16)	0.0223 (15)
C3	0.0655 (12)	0.0621 (13)	0.0495 (12)	0.0050 (10)	0.0081 (11)	0.0086 (12)
C4	0.0498 (10)	0.0477 (10)	0.0401 (10)	0.0006 (8)	0.0098 (9)	−0.0006 (9)
C5	0.0456 (10)	0.0530 (11)	0.0518 (12)	−0.0043 (8)	0.0075 (10)	−0.0038 (10)
C6	0.0630 (14)	0.0603 (14)	0.0801 (19)	−0.0166 (11)	0.0202 (14)	−0.0152 (14)
C7	0.0472 (9)	0.0465 (10)	0.0416 (10)	−0.0012 (8)	0.0001 (9)	−0.0047 (10)
C8	0.0885 (16)	0.0634 (14)	0.0439 (12)	−0.0034 (12)	0.0010 (12)	−0.0127 (12)
C9	0.0478 (10)	0.0408 (10)	0.0458 (11)	−0.0037 (7)	0.0021 (9)	−0.0055 (10)
C10	0.0686 (13)	0.0465 (12)	0.0585 (14)	−0.0100 (10)	0.0083 (12)	−0.0055 (13)
C11	0.0696 (13)	0.0483 (13)	0.0556 (15)	0.0053 (10)	0.0036 (11)	0.0049 (12)
C12	0.0491 (9)	0.0416 (10)	0.0427 (11)	−0.0008 (8)	0.0009 (9)	0.0026 (10)
C13	0.0548 (10)	0.0505 (11)	0.0365 (10)	0.0022 (9)	0.0004 (9)	0.0017 (9)
C14	0.0483 (10)	0.0455 (10)	0.0375 (10)	0.0044 (8)	0.0027 (9)	−0.0041 (9)
C15	0.0426 (9)	0.0468 (10)	0.0394 (10)	−0.0012 (8)	0.0018 (8)	−0.0067 (9)
C16	0.0420 (8)	0.0501 (11)	0.0414 (10)	0.0040 (8)	0.0024 (9)	−0.0010 (9)
C17	0.0579 (11)	0.0434 (11)	0.0555 (13)	0.0052 (9)	0.0014 (10)	−0.0075 (11)
C18	0.0766 (13)	0.0503 (12)	0.0586 (15)	0.0054 (10)	−0.0152 (12)	−0.0211 (12)
C19	0.0667 (12)	0.0574 (13)	0.0391 (11)	0.0113 (10)	−0.0107 (10)	−0.0108 (11)
C20	0.0816 (16)	0.0540 (13)	0.0719 (17)	0.0067 (11)	−0.0073 (14)	0.0106 (13)
O1	0.0640 (9)	0.0567 (8)	0.0549 (9)	0.0022 (7)	−0.0134 (7)	0.0073 (7)
O2	0.0881 (11)	0.0445 (8)	0.0802 (13)	0.0049 (8)	−0.0127 (10)	−0.0021 (9)
O3	0.1243 (16)	0.0638 (10)	0.0544 (11)	0.0120 (10)	−0.0018 (11)	0.0152 (10)
O4	0.1004 (12)	0.0409 (8)	0.0660 (12)	−0.0016 (8)	0.0077 (10)	0.0034 (8)
O5	0.1352 (17)	0.0545 (10)	0.0737 (14)	−0.0265 (10)	0.0139 (12)	−0.0191 (11)

Geometric parameters (Å, º)

C1—C2	1.369 (4)	C11—O4	1.383 (3)
C1—C6	1.379 (4)	C11—C12	1.477 (3)
C1—H1	0.9300	C12—C13	1.349 (3)
C2—C3	1.376 (4)	C13—C14	1.451 (3)
C2—H2	0.9300	C13—H13	0.9300
C3—C4	1.403 (3)	C14—C19	1.395 (3)
C3—H3	0.9300	C14—C15	1.407 (3)
C4—C5	1.387 (3)	C15—C16	1.365 (3)
C4—C7	1.478 (3)	C15—H15	0.9300
C5—C6	1.379 (3)	C16—O1	1.369 (3)
C5—H5	0.9300	C16—C17	1.388 (3)
C6—H6	0.9300	C19—H19	0.9300
C7—C9	1.356 (3)	C17—C18	1.355 (3)
C7—C8	1.512 (3)	C17—O2	1.368 (3)
C8—H8A	0.9600	C18—C19	1.393 (3)
C8—H8B	0.9600	C18—H18	0.9300
C8—H8C	0.9600	C19—H19	0.9300
C9—C12	1.473 (3)	C20—O2	1.419 (3)
C9—C10	1.487 (3)	C20—O1	1.424 (3)
C10—O5	1.191 (3)	C20—H20A	0.9700
C10—O4	1.391 (3)	C20—H20B	0.9700
C11—O3	1.195 (3)
C2—C1—C6	120.0 (2)	O4—C11—C12	109.0 (2)
C2—C1—H1	120.0	C13—C12—C9	138.8 (2)
C6—C1—H1	120.0	C13—C12—C11	115.0 (2)
C1—C2—C3	120.2 (3)	C9—C12—C11	106.07 (19)
C1—C2—H2	119.9	C12—C13—C14	132.6 (2)
C3—C2—H2	119.9	C12—C13—H13	113.7
C2—C3—C4	120.5 (3)	C14—C13—H13	113.7
C2—C3—H3	119.7	C19—C14—C15	120.00 (18)
C4—C3—H3	119.7	C19—C14—C13	116.60 (19)
C5—C4—C3	118.5 (2)	C15—C14—C13	123.40 (18)
C5—C4—C7	121.34 (19)	C16—C15—C14	117.07 (18)
C3—C4—C7	120.1 (2)	C16—C15—H15	121.5
C6—C5—C4	120.1 (2)	C14—C15—H15	121.5
C6—C5—H5	119.9	C15—C16—O1	128.48 (19)
C4—C5—H5	119.9	C15—C16—C17	121.83 (19)
C5—C6—C1	120.6 (3)	O1—C16—C17	109.68 (18)
C5—C6—H6	119.7	C18—C17—O2	127.7 (2)
C1—C6—H6	119.7	C18—C17—C16	122.4 (2)
C9—C7—C4	123.10 (19)	O2—C17—C16	109.8 (2)
C9—C7—C8	121.79 (18)	C17—C18—C19	116.7 (2)
C4—C7—C8	115.0 (2)	C17—C18—H18	121.6
C7—C8—H8A	109.5	C19—C18—H18	121.6
C7—C8—H8B	109.5	C18—C19—C14	121.8 (2)
H8A—C8—H8B	109.5	C18—C19—H19	119.1
C7—C8—H8C	109.5	C14—C19—H19	119.1
H8A—C8—H8C	109.5	O2—C20—O1	108.90 (19)
H8B—C8—H8C	109.5	O2—C20—H20A	109.9
C7—C9—C12	134.23 (18)	O1—C20—H20A	109.9
C7—C9—C10	120.60 (19)	O2—C20—H20B	109.9
C12—C9—C10	104.40 (18)	O1—C20—H20B	109.9
O5—C10—O4	118.2 (2)	H20A—C20—H20B	108.3
O5—C10—C9	132.4 (2)	C16—O1—C20	105.74 (18)
O4—C10—C9	109.39 (19)	C17—O2—C20	105.82 (17)
O3—C11—O4	119.7 (2)	C11—O4—C10	109.81 (17)
O3—C11—C12	131.2 (3)
C6—C1—C2—C3	0.4 (4)	C9—C12—C13—C14	1.0 (4)
C1—C2—C3—C4	1.7 (4)	C11—C12—C13—C14	−173.1 (2)
C2—C3—C4—C5	−2.7 (3)	C12—C13—C14—C19	−147.5 (2)
C2—C3—C4—C7	179.3 (2)	C12—C13—C14—C15	31.9 (3)
C3—C4—C5—C6	1.8 (3)	C19—C14—C15—C16	3.0 (3)
C7—C4—C5—C6	179.78 (19)	C13—C14—C15—C16	−176.44 (18)
C4—C5—C6—C1	0.2 (3)	C14—C15—C16—O1	179.41 (18)
C2—C1—C6—C5	−1.3 (4)	C14—C15—C16—C17	0.9 (3)
C5—C4—C7—C9	42.2 (3)	C15—C16—C17—C18	−3.5 (3)
C3—C4—C7—C9	−139.8 (2)	O1—C16—C17—C18	177.8 (2)
C5—C4—C7—C8	−134.7 (2)	C15—C16—C17—O2	178.71 (18)
C3—C4—C7—C8	43.2 (3)	O1—C16—C17—O2	0.0 (2)
C4—C7—C9—C12	3.0 (4)	O2—C17—C18—C19	179.3 (2)
C8—C7—C9—C12	179.7 (2)	C16—C17—C18—C19	1.9 (3)
C4—C7—C9—C10	−165.19 (19)	C17—C18—C19—C14	2.1 (4)
C8—C7—C9—C10	11.5 (3)	C15—C14—C19—C18	−4.6 (3)
C7—C9—C10—O5	−16.8 (4)	C13—C14—C19—C18	174.8 (2)
C12—C9—C10—O5	171.9 (3)	C15—C16—O1—C20	−179.0 (2)
C7—C9—C10—O4	161.4 (2)	C17—C16—O1—C20	−0.4 (2)
C12—C9—C10—O4	−9.9 (2)	O2—C20—O1—C16	0.7 (3)
C7—C9—C12—C13	27.4 (4)	C18—C17—O2—C20	−177.2 (2)
C10—C9—C12—C13	−163.0 (3)	C16—C17—O2—C20	0.4 (2)
C7—C9—C12—C11	−158.1 (2)	O1—C20—O2—C17	−0.7 (3)
C10—C9—C12—C11	11.4 (2)	O3—C11—O4—C10	−177.6 (3)
O3—C11—C12—C13	−12.5 (4)	C12—C11—O4—C10	3.2 (3)
O4—C11—C12—C13	166.54 (19)	O5—C10—O4—C11	−177.2 (2)
O3—C11—C12—C9	171.5 (3)	C9—C10—O4—C11	4.3 (2)
O4—C11—C12—C9	−9.4 (2)