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

Asiri, A.M.; Ng, S.W.

doi:10.1107/S1600536809008526

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o761

doi:10.1107/S1600536809008526

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

Abdullah Mohamed Asiri ^a and Seik Weng Ng ^b ^*

^aChemistry Department, Faculty of Science, King Abdul Aziz University, Jeddah, Saudi Arabia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 5 March 2009; accepted 9 March 2009; online 14 March 2009)

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.

Related literature

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

Crystal data

C₂₃H₁₆N₂O₂
M_r = 352.38
Monoclinic, P 2₁ /n
a = 6.7908 (2) Å
b = 22.0814 (5) Å
c = 11.8626 (3) Å
β = 96.877 (2)°
V = 1766.00 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 123 K
0.22 × 0.12 × 0.08 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: none
16672 measured reflections
4051 independent reflections
2971 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.119
S = 1.02
4051 reflections
246 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809008526/lh2785sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809008526/lh2785Isup2.hkl

checkCIF report

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.

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

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

C₂₃H₁₆N₂O₂	F(000) = 736
M_r = 352.38	D_x = 1.325 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2995 reflections
a = 6.7908 (2) Å	θ = 2.5–25.4°
b = 22.0814 (5) Å	µ = 0.09 mm⁻¹
c = 11.8626 (3) Å	T = 123 K
β = 96.877 (2)°	Prism, orange
V = 1766.00 (8) Å³	0.22 × 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 tube	R_int = 0.040
Graphite monochromator	θ_max = 27.5°, θ_min = 1.8°
ω scans	h = −8→8
16672 measured reflections	k = −28→28
4051 independent reflections	l = −15→15

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0555P)² + 0.4567P] where P = (F_o² + 2F_c²)/3
4051 reflections	(Δ/σ)_max = 0.001
246 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₂₃H₁₆N₂O₂	V = 1766.00 (8) Å³
M_r = 352.38	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.7908 (2) Å	µ = 0.09 mm⁻¹
b = 22.0814 (5) Å	T = 123 K
c = 11.8626 (3) Å	0.22 × 0.12 × 0.08 mm
β = 96.877 (2)°

Data collection top

Bruker SMART APEX diffractometer	2971 reflections with I > 2σ(I)
16672 measured reflections	R_int = 0.040
4051 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.02	Δρ_max = 0.29 e Å⁻³
4051 reflections	Δρ_min = −0.24 e Å⁻³
246 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.81235 (17)	0.53159 (5)	0.60804 (9)	0.0311 (3)
O2	0.8934 (2)	0.56246 (6)	0.78870 (10)	0.0434 (3)
N1	0.7342 (2)	0.40469 (7)	0.44380 (13)	0.0404 (4)
N2	0.5427 (3)	0.55698 (7)	0.22059 (13)	0.0419 (4)
C1	0.8373 (2)	0.57691 (7)	0.69372 (14)	0.0311 (4)
C2	0.7782 (2)	0.63512 (7)	0.64023 (13)	0.0255 (3)
C3	0.7583 (2)	0.62428 (7)	0.51673 (13)	0.0239 (3)
C4	0.7526 (2)	0.55846 (7)	0.50622 (13)	0.0257 (3)
C5	0.6993 (2)	0.52050 (7)	0.41733 (14)	0.0279 (3)
C6	0.7187 (2)	0.45625 (7)	0.43229 (14)	0.0309 (4)
C7	0.6140 (3)	0.54142 (7)	0.30845 (15)	0.0310 (4)
C8	0.7414 (2)	0.68084 (7)	0.71076 (13)	0.0269 (3)
H8	0.7747	0.6724	0.7892	0.032*
C9	0.6596 (2)	0.74052 (7)	0.68603 (12)	0.0242 (3)
C10	0.5317 (2)	0.75352 (7)	0.58741 (12)	0.0250 (3)
H10	0.4849	0.7216	0.5374	0.030*
C11	0.4733 (2)	0.81213 (7)	0.56248 (13)	0.0276 (3)
H11	0.3863	0.8201	0.4953	0.033*
C12	0.5393 (2)	0.86024 (7)	0.63392 (14)	0.0306 (4)
C13	0.6552 (2)	0.84664 (8)	0.73535 (14)	0.0317 (4)
H13	0.6955	0.8783	0.7873	0.038*
C14	0.7129 (2)	0.78790 (7)	0.76190 (13)	0.0283 (4)
H14	0.7897	0.7795	0.8325	0.034*
C15	0.4873 (3)	0.92448 (8)	0.60006 (17)	0.0445 (5)
H15A	0.5459	0.9521	0.6595	0.067*
H15B	0.3428	0.9293	0.5902	0.067*
H15C	0.5394	0.9339	0.5285	0.067*
C16	0.7738 (2)	0.66042 (7)	0.42565 (13)	0.0246 (3)
H16	0.7519	0.6408	0.3540	0.030*
C17	0.8187 (2)	0.72444 (7)	0.42155 (12)	0.0223 (3)
C18	0.7433 (2)	0.75755 (7)	0.32513 (12)	0.0252 (3)
H18	0.6720	0.7372	0.2624	0.030*
C19	0.7713 (2)	0.81920 (7)	0.32030 (13)	0.0274 (3)
H19	0.7157	0.8410	0.2551	0.033*
C20	0.8803 (2)	0.85031 (7)	0.40968 (13)	0.0273 (3)
C21	0.9648 (2)	0.81676 (7)	0.50266 (13)	0.0261 (3)
H21	1.0441	0.8367	0.5629	0.031*
C22	0.9353 (2)	0.75505 (7)	0.50862 (12)	0.0242 (3)
H22	0.9949	0.7331	0.5727	0.029*
C23	0.9098 (3)	0.91778 (8)	0.40462 (16)	0.0382 (4)
H23A	0.9312	0.9342	0.4819	0.057*
H23B	0.7918	0.9365	0.3632	0.057*
H23C	1.0257	0.9266	0.3654	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0370 (7)	0.0231 (6)	0.0326 (6)	0.0003 (5)	0.0017 (5)	0.0047 (5)
O2	0.0597 (9)	0.0357 (7)	0.0323 (7)	−0.0004 (6)	−0.0051 (6)	0.0116 (5)
N1	0.0444 (9)	0.0266 (8)	0.0501 (10)	0.0001 (6)	0.0057 (8)	−0.0024 (7)
N2	0.0523 (10)	0.0350 (8)	0.0375 (9)	0.0054 (7)	0.0009 (7)	−0.0061 (7)
C1	0.0314 (9)	0.0286 (9)	0.0327 (9)	−0.0034 (7)	0.0014 (7)	0.0057 (7)
C2	0.0258 (8)	0.0245 (8)	0.0256 (8)	−0.0029 (6)	0.0010 (6)	0.0040 (6)
C3	0.0219 (7)	0.0238 (8)	0.0261 (8)	−0.0003 (6)	0.0034 (6)	−0.0005 (6)
C4	0.0229 (8)	0.0246 (8)	0.0300 (8)	0.0009 (6)	0.0051 (6)	0.0029 (6)
C5	0.0262 (8)	0.0228 (8)	0.0355 (9)	0.0012 (6)	0.0068 (7)	−0.0006 (6)
C6	0.0276 (9)	0.0271 (9)	0.0384 (9)	0.0003 (6)	0.0054 (7)	−0.0031 (7)
C7	0.0345 (9)	0.0215 (8)	0.0378 (10)	0.0016 (6)	0.0076 (8)	−0.0067 (7)
C8	0.0284 (8)	0.0313 (9)	0.0208 (7)	−0.0053 (6)	0.0023 (6)	0.0033 (6)
C9	0.0237 (8)	0.0274 (8)	0.0224 (7)	−0.0032 (6)	0.0066 (6)	−0.0014 (6)
C10	0.0230 (8)	0.0295 (8)	0.0233 (7)	−0.0020 (6)	0.0059 (6)	−0.0060 (6)
C11	0.0229 (8)	0.0338 (9)	0.0262 (8)	0.0029 (6)	0.0038 (6)	−0.0012 (6)
C12	0.0280 (8)	0.0277 (9)	0.0384 (9)	0.0007 (6)	0.0132 (7)	−0.0027 (7)
C13	0.0314 (9)	0.0323 (9)	0.0327 (9)	−0.0066 (7)	0.0094 (7)	−0.0113 (7)
C14	0.0269 (8)	0.0356 (9)	0.0227 (8)	−0.0043 (7)	0.0047 (6)	−0.0046 (6)
C15	0.0500 (12)	0.0306 (10)	0.0552 (12)	0.0064 (8)	0.0152 (10)	−0.0012 (8)
C16	0.0229 (8)	0.0260 (8)	0.0252 (7)	0.0011 (6)	0.0044 (6)	−0.0022 (6)
C17	0.0215 (7)	0.0237 (8)	0.0226 (7)	0.0008 (6)	0.0067 (6)	0.0011 (6)
C18	0.0251 (8)	0.0298 (8)	0.0212 (7)	−0.0005 (6)	0.0046 (6)	0.0005 (6)
C19	0.0287 (8)	0.0284 (8)	0.0255 (8)	0.0030 (6)	0.0047 (6)	0.0071 (6)
C20	0.0254 (8)	0.0256 (8)	0.0323 (8)	−0.0014 (6)	0.0091 (7)	0.0035 (6)
C21	0.0229 (8)	0.0295 (8)	0.0264 (8)	−0.0040 (6)	0.0046 (6)	−0.0012 (6)
C22	0.0225 (8)	0.0269 (8)	0.0233 (7)	0.0000 (6)	0.0033 (6)	0.0035 (6)
C23	0.0431 (10)	0.0278 (9)	0.0436 (10)	−0.0045 (7)	0.0055 (8)	0.0057 (8)

Geometric parameters (Å, º) top

O1—C4	1.3631 (19)	C13—C14	1.381 (2)
O1—C1	1.422 (2)	C13—H13	0.9500
O2—C1	1.1890 (19)	C14—H14	0.9500
N1—C6	1.150 (2)	C15—H15A	0.9800
N2—C7	1.148 (2)	C15—H15B	0.9800
C1—C2	1.468 (2)	C15—H15C	0.9800
C2—C8	1.353 (2)	C16—C17	1.448 (2)
C2—C3	1.475 (2)	C16—H16	0.9500
C3—C16	1.357 (2)	C17—C22	1.398 (2)
C3—C4	1.459 (2)	C17—C18	1.402 (2)
C4—C5	1.361 (2)	C18—C19	1.377 (2)
C5—C7	1.428 (2)	C18—H18	0.9500
C5—C6	1.434 (2)	C19—C20	1.399 (2)
C8—C9	1.446 (2)	C19—H19	0.9500
C8—H8	0.9500	C20—C21	1.394 (2)
C9—C14	1.399 (2)	C20—C23	1.505 (2)
C9—C10	1.401 (2)	C21—C22	1.380 (2)
C10—C11	1.375 (2)	C21—H21	0.9500
C10—H10	0.9500	C22—H22	0.9500
C11—C12	1.399 (2)	C23—H23A	0.9800
C11—H11	0.9500	C23—H23B	0.9800
C12—C13	1.390 (2)	C23—H23C	0.9800
C12—C15	1.505 (2)

C4—O1—C1	108.93 (12)	C13—C14—C9	120.75 (15)
O2—C1—O1	119.06 (15)	C13—C14—H14	119.6
O2—C1—C2	133.21 (16)	C9—C14—H14	119.6
O1—C1—C2	107.71 (13)	C12—C15—H15A	109.5
C8—C2—C1	116.55 (14)	C12—C15—H15B	109.5
C8—C2—C3	137.18 (14)	H15A—C15—H15B	109.5
C1—C2—C3	105.97 (13)	C12—C15—H15C	109.5
C16—C3—C4	121.42 (14)	H15A—C15—H15C	109.5
C16—C3—C2	133.53 (14)	H15B—C15—H15C	109.5
C4—C3—C2	104.18 (12)	C3—C16—C17	129.59 (14)
C5—C4—O1	116.21 (14)	C3—C16—H16	115.2
C5—C4—C3	132.95 (15)	C17—C16—H16	115.2
O1—C4—C3	110.84 (13)	C22—C17—C18	118.03 (14)
C4—C5—C7	122.89 (15)	C22—C17—C16	123.37 (13)
C4—C5—C6	120.09 (15)	C18—C17—C16	118.59 (13)
C7—C5—C6	116.96 (14)	C19—C18—C17	120.72 (14)
N1—C6—C5	179.72 (18)	C19—C18—H18	119.6
N2—C7—C5	178.35 (18)	C17—C18—H18	119.6
C2—C8—C9	130.47 (14)	C18—C19—C20	121.15 (14)
C2—C8—H8	114.8	C18—C19—H19	119.4
C9—C8—H8	114.8	C20—C19—H19	119.4
C14—C9—C10	118.09 (14)	C21—C20—C19	117.99 (14)
C14—C9—C8	119.16 (14)	C21—C20—C23	120.89 (15)
C10—C9—C8	122.74 (14)	C19—C20—C23	121.11 (14)
C11—C10—C9	120.42 (14)	C22—C21—C20	121.10 (14)
C11—C10—H10	119.8	C22—C21—H21	119.5
C9—C10—H10	119.8	C20—C21—H21	119.5
C10—C11—C12	121.42 (15)	C21—C22—C17	120.82 (14)
C10—C11—H11	119.3	C21—C22—H22	119.6
C12—C11—H11	119.3	C17—C22—H22	119.6
C13—C12—C11	117.88 (15)	C20—C23—H23A	109.5
C13—C12—C15	121.69 (15)	C20—C23—H23B	109.5
C11—C12—C15	120.43 (16)	H23A—C23—H23B	109.5
C14—C13—C12	121.09 (15)	C20—C23—H23C	109.5
C14—C13—H13	119.5	H23A—C23—H23C	109.5
C12—C13—H13	119.5	H23B—C23—H23C	109.5

C4—O1—C1—O2	−178.40 (16)	C2—C8—C9—C14	−151.98 (17)
C4—O1—C1—C2	3.07 (17)	C2—C8—C9—C10	26.5 (3)
O2—C1—C2—C8	−15.0 (3)	C14—C9—C10—C11	4.9 (2)
O1—C1—C2—C8	163.23 (14)	C8—C9—C10—C11	−173.64 (14)
O2—C1—C2—C3	170.13 (19)	C9—C10—C11—C12	0.1 (2)
O1—C1—C2—C3	−11.63 (17)	C10—C11—C12—C13	−4.4 (2)
C8—C2—C3—C16	32.8 (3)	C10—C11—C12—C15	174.86 (15)
C1—C2—C3—C16	−153.94 (17)	C11—C12—C13—C14	3.6 (2)
C8—C2—C3—C4	−158.09 (19)	C15—C12—C13—C14	−175.61 (16)
C1—C2—C3—C4	15.13 (16)	C12—C13—C14—C9	1.4 (2)
C1—O1—C4—C5	−172.45 (14)	C10—C9—C14—C13	−5.6 (2)
C1—O1—C4—C3	7.04 (16)	C8—C9—C14—C13	172.93 (14)
C16—C3—C4—C5	−23.9 (3)	C4—C3—C16—C17	−167.02 (14)
C2—C3—C4—C5	165.36 (17)	C2—C3—C16—C17	0.5 (3)
C16—C3—C4—O1	156.70 (14)	C3—C16—C17—C22	28.9 (2)
C2—C3—C4—O1	−14.02 (16)	C3—C16—C17—C18	−151.66 (16)
O1—C4—C5—C7	173.23 (14)	C22—C17—C18—C19	−4.7 (2)
C3—C4—C5—C7	−6.1 (3)	C16—C17—C18—C19	175.85 (14)
O1—C4—C5—C6	−3.6 (2)	C17—C18—C19—C20	1.8 (2)
C3—C4—C5—C6	177.04 (15)	C18—C19—C20—C21	1.8 (2)
C4—C5—C6—N1	−164 (100)	C18—C19—C20—C23	−179.62 (15)
C7—C5—C6—N1	19 (40)	C19—C20—C21—C22	−2.6 (2)
C4—C5—C7—N2	−147 (6)	C23—C20—C21—C22	178.83 (15)
C6—C5—C7—N2	30 (7)	C20—C21—C22—C17	−0.3 (2)
C1—C2—C8—C9	−171.89 (15)	C18—C17—C22—C21	3.9 (2)
C3—C2—C8—C9	0.8 (3)	C16—C17—C22—C21	−176.66 (14)

Experimental details

Crystal data
Chemical formula	C₂₃H₁₆N₂O₂
M_r	352.38
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	123
a, b, c (Å)	6.7908 (2), 22.0814 (5), 11.8626 (3)
β (°)	96.877 (2)
V (Å³)	1766.00 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.22 × 0.12 × 0.08

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	16672, 4051, 2971
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.119, 1.02
No. of reflections	4051
No. of parameters	246
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.24

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Acknowledgements

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

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