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Acta Cryst. (2009). E65, o761    [ doi:10.1107/S1600536809008526 ]

(E,E)-2-[3,4-Bis(4-methylbenzylidene)-5-oxotetrahydrofuran-2-ylidene]propanedinitrile

A. M. Asiri and S. W. Ng

Abstract top

In the title molecule, C23H16N2O2, the two exocyclic C=C bonds bearing the tolyl groups have an E configuration and the beznene rings are oriented at 22.1 (1) and 24.8 (1)° with respect to the mean plane of the atoms of the furan ring.

Comment top

The molecular structure of the title compound is shown in Fig. 1.

Related literature top

The compound belongs to a class of photochromic fulgicides; for similar structures, see: Asiri et al. (2000); Heller et al. (1994); Liang et al. (2003).

Experimental top

Diethylamine(0.73 g,10.0 mmol) was added dropwise E,E-3,4-bis(4-tolylmethylene) succinic anhydride (1.52 g, 5.0 mmol) and malononitrile (0.33 g, 5.0 mmol) in THF (20 ml) at 273 K. The mixture was kept at this temperature for 6 h. Diethyl ether (15 ml) was added to quench the reaction. The product was dissolved in dichloromethane (20 ml) and cyclized by acetyl chloride (10 ml) at 293 K. The reaction was kept at this temperature for 10 h. The solvent and excess acetyl chloride were removed in vacuum, and the residual was chromatographed on silica gel. Elution by a 3:7 mixture of ethyl acetate and light petroleum give the title compound as an orange compound (1.41 g, 80% yield), m.p. 478–479 K. Crystals were grown with ether/lightpetroleum ether as solvent.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.98 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellisoid plot (Barbour, 2001) of C23H16N2O2; probability levels are set at 70% and H-atoms are drawn as spheres of arbitrary radius.
(E,E)-2-[3,4-Bis(4-methylbenzylidene)-5-oxotetrahydrofuran- 2-ylidene]propanedinitrile top
Crystal data top
C23H16N2O2F(000) = 736
Mr = 352.38Dx = 1.325 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2995 reflections
a = 6.7908 (2) Åθ = 2.5–25.4°
b = 22.0814 (5) ŵ = 0.09 mm−1
c = 11.8626 (3) ÅT = 123 K
β = 96.877 (2)°Prism, orange
V = 1766.00 (8) Å30.22 × 0.12 × 0.08 mm
Z = 4
Data collection top
Bruker SMART APEX
diffractometer		2971 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.040
graphiteθmax = 27.5°, θmin = 1.8°
ω scansh = −8→8
16672 measured reflectionsk = −28→28
4051 independent reflectionsl = −15→15
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0555P)2 + 0.4567P]
where P = (Fo2 + 2Fc2)/3
4051 reflections(Δ/σ)max = 0.001
246 parametersΔρmax = 0.29 e Å−3
0 restraintsΔρmin = −0.24 e Å−3
Crystal data top
C23H16N2O2V = 1766.00 (8) Å3
Mr = 352.38Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.7908 (2) ŵ = 0.09 mm−1
b = 22.0814 (5) ÅT = 123 K
c = 11.8626 (3) Å0.22 × 0.12 × 0.08 mm
β = 96.877 (2)°
Data collection top
Bruker SMART APEX
diffractometer		2971 reflections with I > 2σ(I)
16672 measured reflectionsRint = 0.040
4051 independent reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.119Δρmax = 0.29 e Å−3
S = 1.02Δρmin = −0.24 e Å−3
4051 reflectionsAbsolute structure: ?
246 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.81235 (17)0.53159 (5)0.60804 (9)0.0311 (3)
O20.8934 (2)0.56246 (6)0.78870 (10)0.0434 (3)
N10.7342 (2)0.40469 (7)0.44380 (13)0.0404 (4)
N20.5427 (3)0.55698 (7)0.22059 (13)0.0419 (4)
C10.8373 (2)0.57691 (7)0.69372 (14)0.0311 (4)
C20.7782 (2)0.63512 (7)0.64023 (13)0.0255 (3)
C30.7583 (2)0.62428 (7)0.51673 (13)0.0239 (3)
C40.7526 (2)0.55846 (7)0.50622 (13)0.0257 (3)
C50.6993 (2)0.52050 (7)0.41733 (14)0.0279 (3)
C60.7187 (2)0.45625 (7)0.43229 (14)0.0309 (4)
C70.6140 (3)0.54142 (7)0.30845 (15)0.0310 (4)
C80.7414 (2)0.68084 (7)0.71076 (13)0.0269 (3)
H80.77470.67240.78920.032*
C90.6596 (2)0.74052 (7)0.68603 (12)0.0242 (3)
C100.5317 (2)0.75352 (7)0.58741 (12)0.0250 (3)
H100.48490.72160.53740.030*
C110.4733 (2)0.81213 (7)0.56248 (13)0.0276 (3)
H110.38630.82010.49530.033*
C120.5393 (2)0.86024 (7)0.63392 (14)0.0306 (4)
C130.6552 (2)0.84664 (8)0.73535 (14)0.0317 (4)
H130.69550.87830.78730.038*
C140.7129 (2)0.78790 (7)0.76190 (13)0.0283 (4)
H140.78970.77950.83250.034*
C150.4873 (3)0.92448 (8)0.60006 (17)0.0445 (5)
H15A0.54590.95210.65950.067*
H15B0.34280.92930.59020.067*
H15C0.53940.93390.52850.067*
C160.7738 (2)0.66042 (7)0.42565 (13)0.0246 (3)
H160.75190.64080.35400.030*
C170.8187 (2)0.72444 (7)0.42155 (12)0.0223 (3)
C180.7433 (2)0.75755 (7)0.32513 (12)0.0252 (3)
H180.67200.73720.26240.030*
C190.7713 (2)0.81920 (7)0.32030 (13)0.0274 (3)
H190.71570.84100.25510.033*
C200.8803 (2)0.85031 (7)0.40968 (13)0.0273 (3)
C210.9648 (2)0.81676 (7)0.50266 (13)0.0261 (3)
H211.04410.83670.56290.031*
C220.9353 (2)0.75505 (7)0.50862 (12)0.0242 (3)
H220.99490.73310.57270.029*
C230.9098 (3)0.91778 (8)0.40462 (16)0.0382 (4)
H23A0.93120.93420.48190.057*
H23B0.79180.93650.36320.057*
H23C1.02570.92660.36540.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0370 (7)0.0231 (6)0.0326 (6)0.0003 (5)0.0017 (5)0.0047 (5)
O20.0597 (9)0.0357 (7)0.0323 (7)−0.0004 (6)−0.0051 (6)0.0116 (5)
N10.0444 (9)0.0266 (8)0.0501 (10)0.0001 (6)0.0057 (8)−0.0024 (7)
N20.0523 (10)0.0350 (8)0.0375 (9)0.0054 (7)0.0009 (7)−0.0061 (7)
C10.0314 (9)0.0286 (9)0.0327 (9)−0.0034 (7)0.0014 (7)0.0057 (7)
C20.0258 (8)0.0245 (8)0.0256 (8)−0.0029 (6)0.0010 (6)0.0040 (6)
C30.0219 (7)0.0238 (8)0.0261 (8)−0.0003 (6)0.0034 (6)−0.0005 (6)
C40.0229 (8)0.0246 (8)0.0300 (8)0.0009 (6)0.0051 (6)0.0029 (6)
C50.0262 (8)0.0228 (8)0.0355 (9)0.0012 (6)0.0068 (7)−0.0006 (6)
C60.0276 (9)0.0271 (9)0.0384 (9)0.0003 (6)0.0054 (7)−0.0031 (7)
C70.0345 (9)0.0215 (8)0.0378 (10)0.0016 (6)0.0076 (8)−0.0067 (7)
C80.0284 (8)0.0313 (9)0.0208 (7)−0.0053 (6)0.0023 (6)0.0033 (6)
C90.0237 (8)0.0274 (8)0.0224 (7)−0.0032 (6)0.0066 (6)−0.0014 (6)
C100.0230 (8)0.0295 (8)0.0233 (7)−0.0020 (6)0.0059 (6)−0.0060 (6)
C110.0229 (8)0.0338 (9)0.0262 (8)0.0029 (6)0.0038 (6)−0.0012 (6)
C120.0280 (8)0.0277 (9)0.0384 (9)0.0007 (6)0.0132 (7)−0.0027 (7)
C130.0314 (9)0.0323 (9)0.0327 (9)−0.0066 (7)0.0094 (7)−0.0113 (7)
C140.0269 (8)0.0356 (9)0.0227 (8)−0.0043 (7)0.0047 (6)−0.0046 (6)
C150.0500 (12)0.0306 (10)0.0552 (12)0.0064 (8)0.0152 (10)−0.0012 (8)
C160.0229 (8)0.0260 (8)0.0252 (7)0.0011 (6)0.0044 (6)−0.0022 (6)
C170.0215 (7)0.0237 (8)0.0226 (7)0.0008 (6)0.0067 (6)0.0011 (6)
C180.0251 (8)0.0298 (8)0.0212 (7)−0.0005 (6)0.0046 (6)0.0005 (6)
C190.0287 (8)0.0284 (8)0.0255 (8)0.0030 (6)0.0047 (6)0.0071 (6)
C200.0254 (8)0.0256 (8)0.0323 (8)−0.0014 (6)0.0091 (7)0.0035 (6)
C210.0229 (8)0.0295 (8)0.0264 (8)−0.0040 (6)0.0046 (6)−0.0012 (6)
C220.0225 (8)0.0269 (8)0.0233 (7)0.0000 (6)0.0033 (6)0.0035 (6)
C230.0431 (10)0.0278 (9)0.0436 (10)−0.0045 (7)0.0055 (8)0.0057 (8)
Geometric parameters (Å, °) top
O1—C41.3631 (19)C13—C141.381 (2)
O1—C11.422 (2)C13—H130.9500
O2—C11.1890 (19)C14—H140.9500
N1—C61.150 (2)C15—H15A0.9800
N2—C71.148 (2)C15—H15B0.9800
C1—C21.468 (2)C15—H15C0.9800
C2—C81.353 (2)C16—C171.448 (2)
C2—C31.475 (2)C16—H160.9500
C3—C161.357 (2)C17—C221.398 (2)
C3—C41.459 (2)C17—C181.402 (2)
C4—C51.361 (2)C18—C191.377 (2)
C5—C71.428 (2)C18—H180.9500
C5—C61.434 (2)C19—C201.399 (2)
C8—C91.446 (2)C19—H190.9500
C8—H80.9500C20—C211.394 (2)
C9—C141.399 (2)C20—C231.505 (2)
C9—C101.401 (2)C21—C221.380 (2)
C10—C111.375 (2)C21—H210.9500
C10—H100.9500C22—H220.9500
C11—C121.399 (2)C23—H23A0.9800
C11—H110.9500C23—H23B0.9800
C12—C131.390 (2)C23—H23C0.9800
C12—C151.505 (2)
C4—O1—C1108.93 (12)C13—C14—C9120.75 (15)
O2—C1—O1119.06 (15)C13—C14—H14119.6
O2—C1—C2133.21 (16)C9—C14—H14119.6
O1—C1—C2107.71 (13)C12—C15—H15A109.5
C8—C2—C1116.55 (14)C12—C15—H15B109.5
C8—C2—C3137.18 (14)H15A—C15—H15B109.5
C1—C2—C3105.97 (13)C12—C15—H15C109.5
C16—C3—C4121.42 (14)H15A—C15—H15C109.5
C16—C3—C2133.53 (14)H15B—C15—H15C109.5
C4—C3—C2104.18 (12)C3—C16—C17129.59 (14)
C5—C4—O1116.21 (14)C3—C16—H16115.2
C5—C4—C3132.95 (15)C17—C16—H16115.2
O1—C4—C3110.84 (13)C22—C17—C18118.03 (14)
C4—C5—C7122.89 (15)C22—C17—C16123.37 (13)
C4—C5—C6120.09 (15)C18—C17—C16118.59 (13)
C7—C5—C6116.96 (14)C19—C18—C17120.72 (14)
N1—C6—C5179.72 (18)C19—C18—H18119.6
N2—C7—C5178.35 (18)C17—C18—H18119.6
C2—C8—C9130.47 (14)C18—C19—C20121.15 (14)
C2—C8—H8114.8C18—C19—H19119.4
C9—C8—H8114.8C20—C19—H19119.4
C14—C9—C10118.09 (14)C21—C20—C19117.99 (14)
C14—C9—C8119.16 (14)C21—C20—C23120.89 (15)
C10—C9—C8122.74 (14)C19—C20—C23121.11 (14)
C11—C10—C9120.42 (14)C22—C21—C20121.10 (14)
C11—C10—H10119.8C22—C21—H21119.5
C9—C10—H10119.8C20—C21—H21119.5
C10—C11—C12121.42 (15)C21—C22—C17120.82 (14)
C10—C11—H11119.3C21—C22—H22119.6
C12—C11—H11119.3C17—C22—H22119.6
C13—C12—C11117.88 (15)C20—C23—H23A109.5
C13—C12—C15121.69 (15)C20—C23—H23B109.5
C11—C12—C15120.43 (16)H23A—C23—H23B109.5
C14—C13—C12121.09 (15)C20—C23—H23C109.5
C14—C13—H13119.5H23A—C23—H23C109.5
C12—C13—H13119.5H23B—C23—H23C109.5
C4—O1—C1—O2−178.40 (16)C2—C8—C9—C14−151.98 (17)
C4—O1—C1—C23.07 (17)C2—C8—C9—C1026.5 (3)
O2—C1—C2—C8−15.0 (3)C14—C9—C10—C114.9 (2)
O1—C1—C2—C8163.23 (14)C8—C9—C10—C11−173.64 (14)
O2—C1—C2—C3170.13 (19)C9—C10—C11—C120.1 (2)
O1—C1—C2—C3−11.63 (17)C10—C11—C12—C13−4.4 (2)
C8—C2—C3—C1632.8 (3)C10—C11—C12—C15174.86 (15)
C1—C2—C3—C16−153.94 (17)C11—C12—C13—C143.6 (2)
C8—C2—C3—C4−158.09 (19)C15—C12—C13—C14−175.61 (16)
C1—C2—C3—C415.13 (16)C12—C13—C14—C91.4 (2)
C1—O1—C4—C5−172.45 (14)C10—C9—C14—C13−5.6 (2)
C1—O1—C4—C37.04 (16)C8—C9—C14—C13172.93 (14)
C16—C3—C4—C5−23.9 (3)C4—C3—C16—C17−167.02 (14)
C2—C3—C4—C5165.36 (17)C2—C3—C16—C170.5 (3)
C16—C3—C4—O1156.70 (14)C3—C16—C17—C2228.9 (2)
C2—C3—C4—O1−14.02 (16)C3—C16—C17—C18−151.66 (16)
O1—C4—C5—C7173.23 (14)C22—C17—C18—C19−4.7 (2)
C3—C4—C5—C7−6.1 (3)C16—C17—C18—C19175.85 (14)
O1—C4—C5—C6−3.6 (2)C17—C18—C19—C201.8 (2)
C3—C4—C5—C6177.04 (15)C18—C19—C20—C211.8 (2)
C4—C5—C6—N1−164 (100)C18—C19—C20—C23−179.62 (15)
C7—C5—C6—N119 (40)C19—C20—C21—C22−2.6 (2)
C4—C5—C7—N2−147 (6)C23—C20—C21—C22178.83 (15)
C6—C5—C7—N230 (7)C20—C21—C22—C17−0.3 (2)
C1—C2—C8—C9−171.89 (15)C18—C17—C22—C213.9 (2)
C3—C2—C8—C90.8 (3)C16—C17—C22—C21−176.66 (14)
Acknowledgements top

We thank King Abdul Aziz University (grant No. 171/428) and the University of Malaya for supporting this study.

references
References top

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Westrip, S. P. (2009). publCIF. In preparation.