3-[(1,3-Benzodioxol-6-yl)methyl­ene]-4-(pentan-3-yl­idene)tetra­hydro­furan-2,5-dione

In the structure of the title compound, C₁₇H₁₆O₅, the dihydrofuran ring adopts an envelope conformation while the methylenedioxyphenyl ring system is essentially planar. The vinyl group is inclined to the dihydrofuran ring by 30.22 (12)°. The dihedral angle between the atoms defining the planar part of the dihydrofuran ring and the aryl ring is 19.12 (8)°

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.049
• wR factor = 0.150
• Data-to-parameter ratio = 16.9

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.804     1.000
            Tmin(prime) and Tmax expected:      0.966     0.969
            RR(prime) =      0.807
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.81
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.97
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O5     -   C11     ..       5.00 su
PLAT320_ALERT_2_C Check Hybridisation of  C12    in Main Residue .          ?
PLAT362_ALERT_2_C Short  C(sp3)-C(sp2) Bond  C12    -   C13    ...       1.35 Ang.

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C12    = ...          S

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

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

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S1. Comment

Photochromic fulgides with aromatic heterocycles such as furan, thiophene, pyrrole, indole and thiazole rings have been synthesized and their spectroscopic and photochromic properties have been previously described (Liang et al., 2001; Walz et al., 1993). In order to achieve certain properties, such as absorption of the colored form at longer wavelengths and 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: Heller et al. (2000); Liang et al. (2001); Walz et al. (1993).

S2. Experimental

The 2-((benzo[d][1,3]dioxol-6-yl)methylene)-3-(pentan-3-ylidene)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°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 dichloromethane at room temperature for 10 d.

S3. Refinement

(type here to add refinement details)

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.

3-[(1,3-Benzodioxol-6-yl)methylene]-4-(pentan-3-ylidene)tetrahydrofuran- 2,5-dione

Crystal data

C17H17O5	F(000) = 1272
Mr = 301.31	Dx = 1.355 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.0914 (3) Å	Cell parameters from 2665 reflections
b = 10.4909 (2) Å	θ = 2.2–24.8°
c = 14.2684 (2) Å	µ = 0.10 mm^−1
β = 110.656 (1)°	T = 296 K
V = 2954.18 (8) Å^3	Block, orange-yellow
Z = 8	0.34 × 0.31 × 0.31 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	3397 independent reflections
Radiation source: fine-focus sealed tube	2265 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
φ and ω scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (APEX2; Bruker, 2005)	h = −27→26
Tmin = 0.804, Tmax = 1.000	k = −9→13
9328 measured reflections	l = −17→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.150	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0658P)^2 + 1.5071P] where P = (Fo^2 + 2Fc^2)/3
3397 reflections	(Δ/σ)max = 0.013
201 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.56 e Å^−3

Special details

Experimental. All H atoms were placed in geometrically calculated positions and refined using a riding model with C—H = 0.97%A (for CH₂ groups) and 0.96%A (for CH₃ groups), their isotropic displacement parameters were set to 1.2 times (1.5 times for CH₃ groups) the equivalent displacement parameter of their parent atoms.

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	0.50597 (11)	0.1433 (2)	0.09603 (19)	0.0667 (6)
H1A	0.5511	0.1470	0.1464	0.080*
H1B	0.5102	0.1303	0.0312	0.080*
C2	0.41037 (10)	0.09418 (19)	0.12185 (15)	0.0510 (5)
C3	0.41168 (9)	0.22456 (18)	0.10944 (13)	0.0464 (4)
C4	0.36026 (9)	0.30202 (17)	0.11198 (14)	0.0443 (4)
H4	0.3619	0.3897	0.1033	0.053*
C5	0.30475 (9)	0.24430 (17)	0.12824 (13)	0.0431 (4)
C6	0.30334 (10)	0.11233 (19)	0.13665 (15)	0.0529 (5)
H6	0.2656	0.0744	0.1444	0.063*
C7	0.35620 (11)	0.03484 (19)	0.13395 (17)	0.0610 (6)
H7	0.3547	−0.0533	0.1401	0.073*
C8	0.24709 (9)	0.31722 (18)	0.13190 (13)	0.0458 (4)
H8	0.2082	0.2691	0.1218	0.055*
C9	0.24012 (9)	0.44169 (18)	0.14725 (14)	0.0466 (4)
C10	0.17018 (10)	0.4924 (2)	0.11986 (15)	0.0543 (5)
C11	0.23940 (11)	0.6642 (2)	0.12756 (16)	0.0579 (5)
C12	0.28464 (9)	0.55359 (18)	0.17105 (15)	0.0492 (5)
H12	0.2982	0.5431	0.1125	0.059*
C13	0.34872 (9)	0.56812 (18)	0.23532 (14)	0.0504 (5)
C14	0.38614 (11)	0.4624 (2)	0.30374 (16)	0.0605 (6)
H14A	0.4288	0.4474	0.2940	0.073*
H14B	0.3596	0.3847	0.2860	0.073*
C15	0.40001 (14)	0.4921 (3)	0.41240 (17)	0.0838 (8)
H15A	0.4255	0.5698	0.4300	0.126*
H15B	0.4255	0.4237	0.4532	0.126*
H15C	0.3579	0.5016	0.4233	0.126*
C16	0.38779 (11)	0.6895 (2)	0.24180 (18)	0.0658 (6)
H16A	0.4253	0.6924	0.3052	0.079*
H16B	0.3586	0.7618	0.2392	0.079*
C17	0.41472 (13)	0.6982 (3)	0.1561 (2)	0.0820 (8)
H17A	0.4412	0.6238	0.1562	0.123*
H17B	0.4425	0.7729	0.1645	0.123*
H17C	0.3774	0.7034	0.0937	0.123*
O1	0.47048 (7)	0.25917 (14)	0.09591 (13)	0.0676 (4)
O2	0.46851 (8)	0.04115 (14)	0.11749 (13)	0.0715 (5)
O3	0.11796 (7)	0.44018 (16)	0.10856 (12)	0.0705 (5)
O4	0.17249 (7)	0.62320 (14)	0.10505 (11)	0.0634 (4)
O5	0.25015 (9)	0.77286 (16)	0.11528 (14)	0.0801 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0493 (12)	0.0696 (15)	0.0853 (16)	0.0149 (10)	0.0290 (11)	−0.0041 (12)
C2	0.0536 (11)	0.0480 (11)	0.0537 (12)	0.0170 (8)	0.0218 (9)	0.0052 (8)
C3	0.0421 (10)	0.0482 (11)	0.0507 (11)	0.0013 (8)	0.0187 (8)	−0.0029 (8)
C4	0.0471 (10)	0.0379 (9)	0.0511 (10)	0.0024 (7)	0.0211 (8)	−0.0017 (8)
C5	0.0428 (9)	0.0453 (10)	0.0415 (9)	0.0049 (7)	0.0154 (7)	−0.0010 (7)
C6	0.0573 (12)	0.0476 (11)	0.0610 (12)	−0.0037 (9)	0.0299 (10)	0.0008 (9)
C7	0.0740 (14)	0.0411 (11)	0.0748 (15)	0.0077 (10)	0.0349 (12)	0.0074 (9)
C8	0.0406 (9)	0.0532 (11)	0.0458 (10)	0.0015 (8)	0.0179 (8)	−0.0013 (8)
C9	0.0384 (9)	0.0549 (11)	0.0479 (11)	0.0094 (8)	0.0167 (8)	0.0004 (8)
C10	0.0458 (11)	0.0692 (14)	0.0491 (11)	0.0145 (9)	0.0183 (9)	−0.0020 (9)
C11	0.0581 (12)	0.0594 (14)	0.0594 (13)	0.0171 (10)	0.0246 (10)	0.0021 (10)
C12	0.0488 (11)	0.0499 (11)	0.0541 (11)	0.0133 (8)	0.0247 (9)	0.0003 (8)
C13	0.0469 (10)	0.0512 (11)	0.0536 (11)	0.0072 (8)	0.0186 (9)	−0.0081 (9)
C14	0.0531 (12)	0.0655 (14)	0.0554 (12)	0.0083 (10)	0.0098 (9)	−0.0047 (10)
C15	0.0821 (17)	0.102 (2)	0.0558 (14)	0.0153 (15)	0.0102 (12)	−0.0097 (13)
C16	0.0587 (12)	0.0553 (13)	0.0827 (16)	0.0017 (10)	0.0240 (11)	−0.0093 (11)
C17	0.0752 (16)	0.0712 (16)	0.111 (2)	0.0034 (13)	0.0475 (15)	0.0022 (14)
O1	0.0496 (8)	0.0570 (9)	0.1072 (13)	0.0041 (7)	0.0412 (8)	−0.0038 (8)
O2	0.0639 (9)	0.0612 (10)	0.0965 (12)	0.0269 (7)	0.0372 (9)	0.0110 (8)
O3	0.0409 (8)	0.0901 (12)	0.0817 (11)	0.0092 (7)	0.0231 (7)	−0.0024 (8)
O4	0.0519 (8)	0.0672 (10)	0.0702 (10)	0.0235 (7)	0.0204 (7)	0.0069 (7)
O5	0.0864 (12)	0.0522 (10)	0.1033 (13)	0.0185 (8)	0.0353 (10)	0.0146 (9)

Geometric parameters (Å, º)

C1—O1	1.427 (2)	C10—O4	1.392 (3)
C1—O2	1.427 (3)	C11—O5	1.187 (3)
C1—H1A	0.9700	C11—O4	1.400 (3)
C1—H1B	0.9700	C11—C12	1.492 (3)
C2—C7	1.364 (3)	C12—C13	1.348 (3)
C2—O2	1.368 (2)	C12—H12	0.9800
C2—C3	1.381 (3)	C13—C16	1.502 (3)
C3—C4	1.366 (2)	C13—C14	1.504 (3)
C3—O1	1.369 (2)	C14—C15	1.505 (3)
C4—C5	1.408 (2)	C14—H14A	0.9700
C4—H4	0.9300	C14—H14B	0.9700
C5—C6	1.391 (3)	C15—H15A	0.9600
C5—C8	1.453 (2)	C15—H15B	0.9600
C6—C7	1.391 (3)	C15—H15C	0.9600
C6—H6	0.9300	C16—C17	1.521 (3)
C7—H7	0.9300	C16—H16A	0.9700
C8—C9	1.341 (3)	C16—H16B	0.9700
C8—H8	0.9300	C17—H17A	0.9600
C9—C12	1.466 (3)	C17—H17B	0.9600
C9—C10	1.485 (2)	C17—H17C	0.9600
C10—O3	1.189 (2)
O1—C1—O2	108.05 (15)	C13—C12—C9	130.89 (18)
O1—C1—H1A	110.1	C13—C12—C11	122.39 (18)
O2—C1—H1A	110.1	C9—C12—C11	105.27 (16)
O1—C1—H1B	110.1	C13—C12—H12	93.9
O2—C1—H1B	110.1	C9—C12—H12	93.9
H1A—C1—H1B	108.4	C11—C12—H12	93.9
C7—C2—O2	128.63 (18)	C12—C13—C16	122.31 (18)
C7—C2—C3	121.59 (17)	C12—C13—C14	121.92 (18)
O2—C2—C3	109.76 (17)	C16—C13—C14	115.75 (17)
C4—C3—O1	127.80 (17)	C13—C14—C15	112.49 (19)
C4—C3—C2	122.26 (17)	C13—C14—H14A	109.1
O1—C3—C2	109.93 (16)	C15—C14—H14A	109.1
C3—C4—C5	117.56 (17)	C13—C14—H14B	109.1
C3—C4—H4	121.2	C15—C14—H14B	109.1
C5—C4—H4	121.2	H14A—C14—H14B	107.8
C6—C5—C4	119.11 (16)	C14—C15—H15A	109.5
C6—C5—C8	118.51 (16)	C14—C15—H15B	109.5
C4—C5—C8	122.32 (16)	H15A—C15—H15B	109.5
C5—C6—C7	122.52 (18)	C14—C15—H15C	109.5
C5—C6—H6	118.7	H15A—C15—H15C	109.5
C7—C6—H6	118.7	H15B—C15—H15C	109.5
C2—C7—C6	116.86 (18)	C13—C16—C17	110.73 (18)
C2—C7—H7	121.6	C13—C16—H16A	109.5
C6—C7—H7	121.6	C17—C16—H16A	109.5
C9—C8—C5	131.29 (18)	C13—C16—H16B	109.5
C9—C8—H8	114.4	C17—C16—H16B	109.5
C5—C8—H8	114.4	H16A—C16—H16B	108.1
C8—C9—C12	136.01 (17)	C16—C17—H17A	109.5
C8—C9—C10	117.51 (18)	C16—C17—H17B	109.5
C12—C9—C10	105.64 (16)	H17A—C17—H17B	109.5
O3—C10—O4	120.93 (18)	C16—C17—H17C	109.5
O3—C10—C9	131.1 (2)	H17A—C17—H17C	109.5
O4—C10—C9	107.97 (17)	H17B—C17—H17C	109.5
O5—C11—O4	119.41 (19)	C3—O1—C1	105.95 (15)
O5—C11—C12	132.9 (2)	C2—O2—C1	106.10 (15)
O4—C11—C12	107.52 (18)	C10—O4—C11	110.78 (15)
C7—C2—C3—C4	2.3 (3)	C10—C9—C12—C11	−16.76 (19)
O2—C2—C3—C4	−179.03 (17)	O5—C11—C12—C13	22.6 (4)
C7—C2—C3—O1	−178.17 (19)	O4—C11—C12—C13	−152.96 (18)
O2—C2—C3—O1	0.5 (2)	O5—C11—C12—C9	−169.8 (2)
O1—C3—C4—C5	−179.23 (18)	O4—C11—C12—C9	14.7 (2)
C2—C3—C4—C5	0.2 (3)	C9—C12—C13—C16	174.36 (18)
C3—C4—C5—C6	−2.7 (3)	C11—C12—C13—C16	−21.5 (3)
C3—C4—C5—C8	−179.70 (17)	C9—C12—C13—C14	−4.3 (3)
C4—C5—C6—C7	2.8 (3)	C11—C12—C13—C14	159.83 (18)
C8—C5—C6—C7	179.99 (19)	C12—C13—C14—C15	−113.0 (2)
O2—C2—C7—C6	179.5 (2)	C16—C13—C14—C15	68.3 (2)
C3—C2—C7—C6	−2.2 (3)	C12—C13—C16—C17	−78.3 (2)
C5—C6—C7—C2	−0.4 (3)	C14—C13—C16—C17	100.4 (2)
C6—C5—C8—C9	163.7 (2)	C4—C3—O1—C1	−178.1 (2)
C4—C5—C8—C9	−19.3 (3)	C2—C3—O1—C1	2.4 (2)
C5—C8—C9—C12	−3.8 (4)	O2—C1—O1—C3	−4.3 (2)
C5—C8—C9—C10	164.00 (18)	C7—C2—O2—C1	175.4 (2)
C8—C9—C10—O3	20.8 (3)	C3—C2—O2—C1	−3.1 (2)
C12—C9—C10—O3	−168.0 (2)	O1—C1—O2—C2	4.6 (2)
C8—C9—C10—O4	−157.82 (17)	O3—C10—O4—C11	176.97 (18)
C12—C9—C10—O4	13.4 (2)	C9—C10—O4—C11	−4.2 (2)
C8—C9—C12—C13	−41.9 (4)	O5—C11—O4—C10	177.19 (19)
C10—C9—C12—C13	149.4 (2)	C12—C11—O4—C10	−6.6 (2)
C8—C9—C12—C11	152.0 (2)