2-[(E)-1-(4-Meth­oxy­phen­yl)pent-1-en-3-yl­idene]malononitrile

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

doi:10.1107/S1600536810045381

organic compounds

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Volume 66| Part 12| December 2010| Page o3148

https://doi.org/10.1107/S1600536810045381

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2-[(E)-1-(4-Methoxyphenyl)pent-1-en-3-ylidene]malononitrile

Lian-Mei Chen ^a and Tai-Ran Kang ^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 4 November 2010; accepted 5 November 2010; online 13 November 2010)

In the title compound, C₁₅H₁₄N₂O, the molecule skeleton displays an approximately planar structure except for the ethyl group [maximum deviation = 0.042 (1) Å]. The methoxyphenyl ring and butanylidenemalononitrile groups are located on opposite sides of the C=C bond, showing an E configuration. Weak intermolecular C—H⋯N hydrogen bonding is present in the crystal structure.

Related literature

For the use of malononitrile-containing compounds as building blocks in synthesis, see: Liu et al. (2002 ); Sepiol & Milart (1985 ); Zhang et al. (2003 ). For a related structure, see: Kang & Chen (2009 ).

Experimental

Crystal data

C₁₅H₁₄N₂O
M_r = 238.28
Monoclinic, P 2₁ /n
a = 12.3371 (3) Å
b = 8.8832 (2) Å
c = 12.8554 (3) Å
β = 108.050 (2)°
V = 1339.53 (5) Å³
Z = 4
Cu Kα radiation
μ = 0.60 mm⁻¹
T = 291 K
0.42 × 0.40 × 0.36 mm

Data collection

Oxford Diffraction Gemini S Ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.787, T_max = 0.813
9020 measured reflections
2456 independent reflections
2266 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.112
S = 1.05
2456 reflections
165 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯N1ⁱ	0.93	2.62	3.5285 (19)	167 (1)
Symmetry code: (i) $[-x-{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; 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: https://doi.org/10.1107/S1600536810045381/xu5082sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810045381/xu5082Isup2.hkl

checkCIF report

Comment top

The chemistry of ylidene malononitrile have been studied extensively, 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 et al.1985) were obtained. Some crystal structures involving ylidene malononitrile groups have been published, including a recent report from our labratory (Kang et al., 2009). As a part of our interest in the synthsis of some complex ring systems, we investigated the title compound (I), which is a diene reagent in 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 phenyl ring with two double bond and triple bond is co-planar. The crystal packing is stabilized by C—H···N hydrogen bonding (Table 1).

Related literature top

For the use of malononitrile-containing compounds as building blocks in synthesis, see: Liu et al. (2002); Sepiol & Milart (1985); Zhang et al. (2003). For a related structure, see: Kang & Chen (2009).

Experimental top

2-(Butan-2-ylidene)malononitrile (0.24 g 2 mmol) and 4-methoxy -benzaldehyde (0.272 g 2 mmol) were dissolved in 2-propanol (2 ml). To the solution was added piperidine (0.017 g, 0.2 mmol), the solution was stirred for 24 h at 343 K. Then the solution was cooled to room temperature, and 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.

Structure description top

For the use of malononitrile-containing compounds as building blocks in synthesis, see: Liu et al. (2002); Sepiol & Milart (1985); Zhang et al. (2003). For a related structure, see: Kang & Chen (2009).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); 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).

2-[(E)-1-(4-Methoxyphenyl)pent-1-en-3-ylidene]propanedinitrile top

Crystal data top

C₁₅H₁₄N₂O	F(000) = 504
M_r = 238.28	D_x = 1.182 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 6882 reflections
a = 12.3371 (3) Å	θ = 3.6–69.4°
b = 8.8832 (2) Å	µ = 0.60 mm⁻¹
c = 12.8554 (3) Å	T = 291 K
β = 108.050 (2)°	Block, yellow
V = 1339.53 (5) Å³	0.42 × 0.40 × 0.36 mm
Z = 4

Data collection top

Oxford Diffraction Gemini S Ultra diffractometer	2456 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	2266 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.014
Detector resolution: 15.9149 pixels mm^-1	θ_max = 69.6°, θ_min = 4.3°
ω scans	h = −14→14
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −10→10
T_min = 0.787, T_max = 0.813	l = −15→8
9020 measured 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0607P)² + 0.1456P] where P = (F_o² + 2F_c²)/3
2456 reflections	(Δ/σ)_max < 0.001
165 parameters	Δρ_max = 0.11 e Å⁻³
3 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₅H₁₄N₂O	V = 1339.53 (5) Å³
M_r = 238.28	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 12.3371 (3) Å	µ = 0.60 mm⁻¹
b = 8.8832 (2) Å	T = 291 K
c = 12.8554 (3) Å	0.42 × 0.40 × 0.36 mm
β = 108.050 (2)°

Data collection top

Oxford Diffraction Gemini S Ultra diffractometer	2456 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	2266 reflections with I > 2σ(I)
T_min = 0.787, T_max = 0.813	R_int = 0.014
9020 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	3 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.05	Δρ_max = 0.11 e Å⁻³
2456 reflections	Δρ_min = −0.14 e Å⁻³
165 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
O1	0.09486 (7)	−0.22305 (10)	0.03379 (7)	0.0668 (3)
C14	−0.13644 (11)	0.27243 (16)	0.51588 (10)	0.0646 (3)
C7	0.13090 (9)	0.13033 (12)	0.40443 (8)	0.0486 (3)
H7	0.2053	0.1581	0.4428	0.058*
C2	−0.00061 (9)	−0.10045 (13)	0.15020 (9)	0.0534 (3)
H2	−0.0720	−0.1348	0.1083	0.064*
C8	0.04916 (9)	0.17842 (13)	0.44506 (8)	0.0505 (3)
H8	−0.0254	0.1492	0.4090	0.061*
C4	0.11576 (9)	0.03969 (11)	0.30705 (8)	0.0464 (3)
C5	0.21124 (9)	0.00232 (14)	0.27569 (10)	0.0559 (3)
H5	0.2828	0.0364	0.3174	0.067*
C1	0.09578 (9)	−0.13673 (12)	0.12143 (9)	0.0512 (3)
C3	0.01045 (9)	−0.01297 (13)	0.24151 (9)	0.0525 (3)
H3	−0.0546	0.0117	0.2599	0.063*
C6	0.20146 (9)	−0.08369 (14)	0.18453 (10)	0.0611 (3)
H6	0.2661	−0.1066	0.1649	0.073*
C9	0.06860 (9)	0.27216 (12)	0.54059 (9)	0.0507 (3)
N1	−0.22774 (11)	0.23824 (19)	0.46897 (11)	0.0962 (5)
C12	−0.02183 (10)	0.31596 (13)	0.57378 (9)	0.0552 (3)
N2	−0.00312 (13)	0.48196 (17)	0.74197 (12)	0.0955 (4)
C10	0.18745 (10)	0.31909 (15)	0.60535 (10)	0.0640 (3)
H10A	0.1837	0.4087	0.6472	0.077*
H10B	0.2297	0.3441	0.5554	0.077*
C15	−0.01196 (12)	−0.28321 (15)	−0.03201 (11)	0.0687 (4)
H15A	−0.0445	−0.3435	0.0128	0.103*
H15B	−0.0002	−0.3444	−0.0891	0.103*
H15C	−0.0629	−0.2022	−0.0638	0.103*
C13	−0.00959 (11)	0.40823 (15)	0.66777 (11)	0.0670 (3)
C11	0.25010 (13)	0.1964 (2)	0.68261 (12)	0.0890 (5)
H11A	0.2143	0.1807	0.7382	0.133*
H11B	0.3280	0.2260	0.7161	0.133*
H11C	0.2477	0.1047	0.6424	0.133*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0564 (5)	0.0802 (6)	0.0658 (5)	0.0005 (4)	0.0219 (4)	−0.0264 (4)
C14	0.0545 (6)	0.0853 (9)	0.0560 (7)	0.0201 (5)	0.0199 (5)	0.0060 (5)
C7	0.0477 (5)	0.0515 (6)	0.0483 (5)	−0.0039 (4)	0.0173 (4)	−0.0007 (4)
C2	0.0417 (5)	0.0614 (6)	0.0569 (6)	−0.0034 (5)	0.0150 (4)	−0.0094 (5)
C8	0.0483 (6)	0.0564 (6)	0.0481 (6)	0.0002 (4)	0.0167 (4)	−0.0022 (5)
C4	0.0451 (5)	0.0490 (5)	0.0476 (5)	−0.0006 (4)	0.0179 (4)	0.0000 (4)
C5	0.0405 (5)	0.0666 (7)	0.0609 (6)	−0.0030 (5)	0.0163 (5)	−0.0113 (5)
C1	0.0505 (6)	0.0527 (6)	0.0526 (6)	0.0020 (5)	0.0194 (5)	−0.0070 (5)
C3	0.0426 (5)	0.0620 (6)	0.0576 (6)	−0.0014 (5)	0.0225 (5)	−0.0076 (5)
C6	0.0444 (6)	0.0742 (8)	0.0697 (7)	0.0008 (5)	0.0250 (5)	−0.0176 (6)
C9	0.0556 (6)	0.0511 (6)	0.0487 (6)	0.0024 (4)	0.0209 (5)	0.0016 (4)
N1	0.0536 (7)	0.1471 (13)	0.0840 (8)	0.0179 (7)	0.0154 (6)	0.0044 (8)
C12	0.0588 (6)	0.0598 (6)	0.0503 (6)	0.0116 (5)	0.0215 (5)	0.0034 (4)
N2	0.1005 (10)	0.1055 (10)	0.0906 (9)	0.0068 (8)	0.0443 (8)	−0.0336 (8)
C10	0.0619 (7)	0.0708 (7)	0.0652 (7)	−0.0132 (6)	0.0284 (6)	−0.0197 (6)
C15	0.0699 (8)	0.0710 (8)	0.0633 (7)	−0.0060 (6)	0.0179 (6)	−0.0210 (6)
C13	0.0705 (8)	0.0706 (8)	0.0664 (7)	0.0122 (6)	0.0308 (6)	−0.0064 (6)
C11	0.0617 (8)	0.1201 (13)	0.0720 (9)	−0.0096 (8)	0.0015 (7)	−0.0004 (9)

Geometric parameters (Å, º) top

O1—C1	1.3600 (13)	C1—C6	1.3873 (15)
O1—C15	1.4308 (15)	C3—H3	0.9300
C14—N1	1.1417 (18)	C6—H6	0.9300
C14—C12	1.4321 (18)	C9—C12	1.3686 (15)
C7—C8	1.3412 (15)	C9—C10	1.5035 (16)
C7—C4	1.4510 (14)	C12—C13	1.4289 (16)
C7—H7	0.9300	N2—C13	1.1393 (17)
C2—C3	1.3788 (15)	C10—C11	1.516 (2)
C2—C1	1.3883 (14)	C10—H10A	0.9700
C2—H2	0.9300	C10—H10B	0.9700
C8—C9	1.4410 (15)	C15—H15A	0.9600
C8—H8	0.9300	C15—H15B	0.9600
C4—C3	1.3923 (15)	C15—H15C	0.9600
C4—C5	1.3980 (15)	C11—H11A	0.9600
C5—C6	1.3727 (16)	C11—H11B	0.9600
C5—H5	0.9300	C11—H11C	0.9600

C1—O1—C15	118.04 (9)	C12—C9—C8	119.57 (10)
N1—C14—C12	179.45 (15)	C12—C9—C10	119.86 (10)
C8—C7—C4	126.97 (10)	C8—C9—C10	120.56 (9)
C8—C7—H7	116.5	C9—C12—C13	122.96 (11)
C4—C7—H7	116.5	C9—C12—C14	122.01 (11)
C3—C2—C1	119.38 (10)	C13—C12—C14	115.03 (10)
C3—C2—H2	120.3	C9—C10—C11	112.04 (11)
C1—C2—H2	120.3	C9—C10—H10A	109.2
C7—C8—C9	124.70 (10)	C11—C10—H10A	109.2
C7—C8—H8	117.7	C9—C10—H10B	109.2
C9—C8—H8	117.7	C11—C10—H10B	109.2
C3—C4—C5	117.22 (10)	H10A—C10—H10B	107.9
C3—C4—C7	123.72 (9)	O1—C15—H15A	109.5
C5—C4—C7	119.06 (10)	O1—C15—H15B	109.5
C6—C5—C4	121.29 (10)	H15A—C15—H15B	109.5
C6—C5—H5	119.4	O1—C15—H15C	109.5
C4—C5—H5	119.4	H15A—C15—H15C	109.5
O1—C1—C6	116.17 (9)	H15B—C15—H15C	109.5
O1—C1—C2	124.31 (10)	N2—C13—C12	178.06 (14)
C6—C1—C2	119.53 (10)	C10—C11—H11A	109.5
C2—C3—C4	122.15 (9)	C10—C11—H11B	109.5
C2—C3—H3	118.9	H11A—C11—H11B	109.5
C4—C3—H3	118.9	C10—C11—H11C	109.5
C5—C6—C1	120.42 (10)	H11A—C11—H11C	109.5
C5—C6—H6	119.8	H11B—C11—H11C	109.5
C1—C6—H6	119.8

C4—C7—C8—C9	−178.09 (10)	C4—C5—C6—C1	−0.5 (2)
C8—C7—C4—C3	−1.00 (18)	O1—C1—C6—C5	−178.94 (11)
C8—C7—C4—C5	178.78 (11)	C2—C1—C6—C5	0.91 (19)
C3—C4—C5—C6	−0.49 (18)	C7—C8—C9—C12	179.18 (11)
C7—C4—C5—C6	179.72 (10)	C7—C8—C9—C10	−2.24 (17)
C15—O1—C1—C6	178.49 (11)	C8—C9—C12—C13	179.74 (10)
C15—O1—C1—C2	−1.35 (17)	C10—C9—C12—C13	1.14 (18)
C3—C2—C1—O1	179.44 (10)	C8—C9—C12—C14	−0.48 (18)
C3—C2—C1—C6	−0.40 (18)	C10—C9—C12—C14	−179.08 (11)
C1—C2—C3—C4	−0.58 (18)	C12—C9—C10—C11	98.07 (14)
C5—C4—C3—C2	1.01 (17)	C8—C9—C10—C11	−80.51 (14)
C7—C4—C3—C2	−179.20 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N1ⁱ	0.93	2.62	3.5285 (19)	167 (1)

Symmetry code: (i) −x−1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄N₂O
M_r	238.28
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	12.3371 (3), 8.8832 (2), 12.8554 (3)
β (°)	108.050 (2)
V (Å³)	1339.53 (5)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.60
Crystal size (mm)	0.42 × 0.40 × 0.36

Data collection
Diffractometer	Oxford Diffraction Gemini S Ultra
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.787, 0.813
No. of measured, independent and observed [I > 2σ(I)] reflections	9020, 2456, 2266
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.112, 1.05
No. of reflections	2456
No. of parameters	165
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 CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N1ⁱ	0.93	2.62	3.5285 (19)	167.1 (5)

Symmetry code: (i) −x−1/2, y−1/2, −z+1/2.

Acknowledgements

The authors thank the Testing Centre of Sichuan University for the diffraction measurements. We are grateful for financial support from China West Normal University (No. 412374).

References

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