(E)-2-(1,3-Diphenyl­allyl­idene)malononitrile

Kang, T.-R.; Chen, L.-M.

doi:10.1107/S1600536809048338

organic compounds

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Volume 65| Part 12| December 2009| Page o3164

doi:10.1107/S1600536809048338

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(E)-2-(1,3-Diphenylallylidene)malononitrile

Tai-Ran Kang ^a ^* and Lian-Mei Chen ^a

^aCollege of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002, People's Republic of China
^*Correspondence e-mail: kangtairan@yahoo.com.cn

(Received 13 November 2009; accepted 14 November 2009; online 21 November 2009)

The title compound, C₁₈H₁₂N₂, adopts an E conformation with the benzylidenemalononitrile and phenyl groups located on opposite sides of the C=C bond. The two phenyl rings are oriented at a dihedral angle of 62.49 (7)°.

Related literature

For background to the use of malononitrile-containing compounds as building blocks in organic synthesis, see: Erian (1993 ); Liu et al. (2002 ); Sepiol & Milart. (1985 ); Zhang et al. (2003 ). For a related structure, see: Basu Baul et al. (2009 ).

Experimental

Crystal data

C₁₈H₁₂N₂
M_r = 256.30
Monoclinic, P 2₁ /c
a = 12.1658 (6) Å
b = 14.8852 (9) Å
c = 8.1959 (7) Å
β = 108.457 (6)°
V = 1407.85 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 295 K
0.50 × 0.40 × 0.40 mm

Data collection

Oxford Diffraction Gemini S Ultra diffractometer
Absorption correction: none
13329 measured reflections
2880 independent reflections
1735 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.082
S = 1.01
2880 reflections
181 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: CrysAlis Pro (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis Pro. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis Pro; data reduction: CrysAlis Pro; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809048338/xu2673sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809048338/xu2673Isup2.hkl

checkCIF report

Comment top

The chemistry of ylidene malononitrile was studied extensively in organic synthesis (Erian et al., 1993). From the ring closure reactions, the comounds containing newly formed five or six-membered rings, such as indans (Zhang et al., 2003), naphthalenes (Liu, et al., 2002), benzenes (Sepiol & Milart., 1985) were obtained. As a part of our interest in the synthesis of some complex ring systems, we investigated the title compound, (I), which is a diene reagent in the Diels–Alder reaction. We report herein the crystal structure of the title compound.

The molecular structure of (I) is shown in Fig. 1. Bond lengths and angles in (I) are normal. The title compound adopts an E conformation with respect to the C=C bond, the dihedral angle between the C1—C6 phenyl ring and C10—C15 phenyl ring is 62.49 (7)°.

Related literature top

For background to the use of malononitrile-containing compounds as building blocks in organic synthesis, see: Erian (1993); Liu et al. (2002); Sepiol & Milart. (1985); Zhang et al. (2003). For a related structure, see: Basu Baul et al. (2009).

Experimental top

2-(1-Phenylethylidene)malononitrile (0.334 g, 2.14 mmol), benzaldehyde (0.249 g, 2.35 mmol), piperidine (0.018 g, 0.214 mmol) were stirred in 2-propanol (2 ml) at 343 K for 24 h. Then the reaction was cooled to room temperature, and the solution was filtered to obtain a yellow solid. Recrystallization from hot ethanol afforded the pure compound. Single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation ethanol solvent.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009; data reduction: CrysAlis PRO (Oxford Diffraction, 2009; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms).

(E)-2-(1,3-Diphenylallylidene)malononitrile top

Crystal data top

C₁₈H₁₂N₂	F(000) = 536
M_r = 256.30	D_x = 1.209 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5219 reflections
a = 12.1658 (6) Å	θ = 3.0–29.2°
b = 14.8852 (9) Å	µ = 0.07 mm⁻¹
c = 8.1959 (7) Å	T = 295 K
β = 108.457 (6)°	Block, yellow
V = 1407.85 (16) Å³	0.50 × 0.40 × 0.40 mm
Z = 4

Data collection top

Oxford Diffraction Gemini S Ultra diffractometer	1735 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.025
Graphite monochromator	θ_max = 26.4°, θ_min = 3.0°
Detector resolution: 15.9149 pixels mm^-1	h = −15→15
ω scans	k = −12→18
13329 measured reflections	l = −10→10
2880 independent reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0388P)²] where P = (F_o² + 2F_c²)/3
2880 reflections	(Δ/σ)_max = 0.001
181 parameters	Δρ_max = 0.11 e Å⁻³
3 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₈H₁₂N₂	V = 1407.85 (16) Å³
M_r = 256.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.1658 (6) Å	µ = 0.07 mm⁻¹
b = 14.8852 (9) Å	T = 295 K
c = 8.1959 (7) Å	0.50 × 0.40 × 0.40 mm
β = 108.457 (6)°

Data collection top

Oxford Diffraction Gemini S Ultra diffractometer	1735 reflections with I > 2σ(I)
13329 measured reflections	R_int = 0.025
2880 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	3 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 1.01	Δρ_max = 0.11 e Å⁻³
2880 reflections	Δρ_min = −0.14 e Å⁻³
181 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C8	1.02337 (9)	0.42702 (8)	0.80790 (16)	0.0520 (3)
H8	0.9756	0.4731	0.7487	0.062*
C9	1.14221 (9)	0.42886 (8)	0.80802 (15)	0.0468 (3)
C16	1.17980 (10)	0.50107 (7)	0.73655 (16)	0.0492 (3)
C10	1.22053 (10)	0.35243 (7)	0.87880 (15)	0.0466 (3)
C7	0.97483 (10)	0.36634 (8)	0.88354 (15)	0.0492 (3)
H7	1.0225	0.3211	0.9464	0.059*
C4	0.76990 (10)	0.41976 (8)	0.76497 (17)	0.0578 (3)
H4	0.7914	0.4586	0.6915	0.069*
C6	0.81719 (11)	0.30629 (8)	0.98007 (17)	0.0564 (3)
H6	0.8706	0.2677	1.0531	0.068*
C5	0.85340 (9)	0.36488 (7)	0.87593 (15)	0.0461 (3)
C1	0.70315 (12)	0.30433 (9)	0.97724 (19)	0.0679 (4)
H1	0.6804	0.2649	1.0484	0.081*
C2	0.62347 (11)	0.36058 (9)	0.86948 (19)	0.0679 (4)
H2	0.5470	0.3601	0.8692	0.082*
C11	1.32866 (10)	0.36506 (8)	0.99982 (17)	0.0572 (3)
H11	1.3530	0.4227	1.0384	0.069*
C3	0.65660 (11)	0.41749 (9)	0.76217 (18)	0.0651 (4)
H3	0.6021	0.4547	0.6873	0.078*
C17	1.29300 (11)	0.50807 (8)	0.71970 (17)	0.0578 (3)
C14	1.25937 (13)	0.19431 (9)	0.8861 (2)	0.0751 (4)
H14	1.2363	0.1364	0.8474	0.090*
C15	1.18644 (11)	0.26573 (8)	0.82240 (18)	0.0604 (4)
H15	1.1142	0.2559	0.7414	0.073*
C13	1.36577 (13)	0.20804 (10)	1.0064 (2)	0.0778 (5)
H13	1.4144	0.1595	1.0492	0.093*
C12	1.40048 (12)	0.29275 (10)	1.06346 (19)	0.0707 (4)
H12	1.4726	0.3018	1.1453	0.085*
C18	1.10284 (11)	0.57361 (9)	0.66242 (17)	0.0544 (3)
N2	1.03886 (10)	0.62944 (8)	0.60031 (16)	0.0742 (4)
N1	1.38156 (11)	0.51654 (8)	0.70138 (18)	0.0851 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C8	0.0442 (7)	0.0488 (7)	0.0631 (8)	0.0040 (5)	0.0171 (6)	0.0015 (6)
C9	0.0427 (7)	0.0482 (7)	0.0495 (8)	−0.0006 (5)	0.0144 (5)	−0.0057 (6)
C16	0.0458 (6)	0.0452 (7)	0.0570 (8)	−0.0010 (5)	0.0169 (6)	−0.0030 (6)
C10	0.0433 (7)	0.0475 (7)	0.0530 (8)	0.0017 (5)	0.0208 (6)	0.0013 (6)
C7	0.0462 (7)	0.0503 (7)	0.0505 (8)	0.0049 (5)	0.0146 (6)	0.0000 (6)
C4	0.0474 (7)	0.0592 (8)	0.0668 (9)	0.0011 (6)	0.0178 (6)	0.0085 (7)
C6	0.0566 (8)	0.0565 (7)	0.0588 (9)	0.0020 (6)	0.0222 (7)	0.0023 (7)
C5	0.0440 (7)	0.0458 (7)	0.0508 (8)	0.0001 (5)	0.0182 (6)	−0.0039 (6)
C1	0.0608 (9)	0.0757 (9)	0.0755 (11)	−0.0076 (7)	0.0335 (8)	0.0056 (8)
C2	0.0465 (8)	0.0847 (10)	0.0779 (10)	−0.0075 (7)	0.0272 (7)	−0.0097 (9)
C11	0.0486 (7)	0.0614 (8)	0.0613 (9)	−0.0012 (6)	0.0168 (6)	0.0034 (7)
C3	0.0436 (8)	0.0732 (9)	0.0757 (10)	0.0054 (6)	0.0149 (7)	0.0012 (8)
C17	0.0549 (7)	0.0536 (8)	0.0690 (9)	−0.0005 (6)	0.0253 (7)	0.0041 (7)
C14	0.0774 (11)	0.0503 (8)	0.1059 (13)	0.0079 (7)	0.0408 (10)	0.0020 (8)
C15	0.0530 (8)	0.0548 (8)	0.0753 (10)	0.0018 (6)	0.0229 (7)	−0.0052 (7)
C13	0.0682 (10)	0.0724 (11)	0.0999 (13)	0.0228 (8)	0.0365 (10)	0.0281 (9)
C12	0.0509 (8)	0.0846 (11)	0.0754 (11)	0.0103 (7)	0.0181 (7)	0.0199 (9)
C18	0.0528 (7)	0.0489 (7)	0.0626 (9)	−0.0029 (5)	0.0199 (6)	0.0020 (6)
N2	0.0721 (8)	0.0606 (7)	0.0865 (10)	0.0055 (6)	0.0202 (7)	0.0097 (7)
N1	0.0661 (8)	0.0863 (9)	0.1148 (11)	0.0025 (6)	0.0457 (8)	0.0183 (8)

Geometric parameters (Å, º) top

C8—C7	1.3344 (15)	C1—C2	1.3706 (19)
C8—C9	1.4457 (14)	C1—H1	0.9300
C8—H8	0.9300	C2—C3	1.3703 (18)
C9—C16	1.3701 (15)	C2—H2	0.9300
C9—C10	1.4795 (15)	C11—C12	1.3804 (17)
C16—C17	1.4308 (16)	C11—H11	0.9300
C16—C18	1.4323 (18)	C3—H3	0.9300
C10—C11	1.3869 (16)	C17—N1	1.1409 (14)
C10—C15	1.3892 (16)	C14—C13	1.372 (2)
C7—C5	1.4590 (15)	C14—C15	1.3773 (18)
C7—H7	0.9300	C14—H14	0.9300
C4—C3	1.3718 (16)	C15—H15	0.9300
C4—C5	1.3932 (16)	C13—C12	1.364 (2)
C4—H4	0.9300	C13—H13	0.9300
C6—C1	1.3805 (16)	C12—H12	0.9300
C6—C5	1.3861 (15)	C18—N2	1.1423 (15)
C6—H6	0.9300

C7—C8—C9	127.01 (11)	C2—C1—H1	120.0
C7—C8—H8	116.5	C6—C1—H1	120.0
C9—C8—H8	116.5	C3—C2—C1	119.97 (12)
C16—C9—C8	118.92 (10)	C3—C2—H2	120.0
C16—C9—C10	120.68 (10)	C1—C2—H2	120.0
C8—C9—C10	120.36 (10)	C12—C11—C10	120.54 (12)
C9—C16—C17	124.07 (10)	C12—C11—H11	119.7
C9—C16—C18	120.73 (10)	C10—C11—H11	119.7
C17—C16—C18	115.09 (10)	C2—C3—C4	120.18 (12)
C11—C10—C15	118.66 (11)	C2—C3—H3	119.9
C11—C10—C9	121.57 (11)	C4—C3—H3	119.9
C15—C10—C9	119.77 (11)	N1—C17—C16	177.09 (14)
C8—C7—C5	125.53 (11)	C13—C14—C15	120.38 (13)
C8—C7—H7	117.2	C13—C14—H14	119.8
C5—C7—H7	117.2	C15—C14—H14	119.8
C3—C4—C5	121.17 (12)	C14—C15—C10	120.15 (13)
C3—C4—H4	119.4	C14—C15—H15	119.9
C5—C4—H4	119.4	C10—C15—H15	119.9
C1—C6—C5	121.10 (12)	C12—C13—C14	120.22 (13)
C1—C6—H6	119.5	C12—C13—H13	119.9
C5—C6—H6	119.5	C14—C13—H13	119.9
C6—C5—C4	117.56 (10)	C13—C12—C11	120.06 (14)
C6—C5—C7	119.86 (11)	C13—C12—H12	120.0
C4—C5—C7	122.57 (11)	C11—C12—H12	120.0
C2—C1—C6	119.99 (12)	N2—C18—C16	177.74 (14)

C7—C8—C9—C16	−174.10 (11)	C8—C7—C5—C6	−170.60 (11)
C7—C8—C9—C10	8.02 (18)	C8—C7—C5—C4	10.37 (18)
C8—C9—C16—C17	−176.08 (12)	C5—C6—C1—C2	0.38 (19)
C10—C9—C16—C17	1.80 (17)	C6—C1—C2—C3	1.3 (2)
C8—C9—C16—C18	−0.14 (17)	C15—C10—C11—C12	−0.38 (18)
C10—C9—C16—C18	177.74 (12)	C9—C10—C11—C12	−179.70 (11)
C16—C9—C10—C11	53.38 (16)	C1—C2—C3—C4	−1.44 (19)
C8—C9—C10—C11	−128.77 (12)	C5—C4—C3—C2	−0.05 (19)
C16—C9—C10—C15	−125.93 (12)	C13—C14—C15—C10	0.4 (2)
C8—C9—C10—C15	51.92 (15)	C11—C10—C15—C14	−0.09 (18)
C9—C8—C7—C5	−177.82 (12)	C9—C10—C15—C14	179.25 (11)
C1—C6—C5—C4	−1.80 (17)	C15—C14—C13—C12	−0.3 (2)
C1—C6—C5—C7	179.11 (12)	C14—C13—C12—C11	−0.2 (2)
C3—C4—C5—C6	1.64 (17)	C10—C11—C12—C13	0.5 (2)
C3—C4—C5—C7	−179.30 (12)

Experimental details

Crystal data
Chemical formula	C₁₈H₁₂N₂
M_r	256.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	12.1658 (6), 14.8852 (9), 8.1959 (7)
β (°)	108.457 (6)
V (Å³)	1407.85 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.50 × 0.40 × 0.40

Data collection
Diffractometer	Oxford Diffraction Gemini S Ultra diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	13329, 2880, 1735
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.082, 1.01
No. of reflections	2880
No. of parameters	181
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.14

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), CrysAlis PRO (Oxford Diffraction, 2009, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Acknowledgements

The diffraction data were collected at the Centre for Testing and Analysis, Sichuan University. We acknowledge financial support from China West Normal University (No 412374).

References

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