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

Kang, T.-R.

doi:10.1107/S1600536811035884

organic compounds

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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2582

https://doi.org/10.1107/S1600536811035884

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

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@sina.com

(Received 5 August 2011; accepted 2 September 2011; online 14 September 2011)

The title molecule, C₁₄H₁₁FN₂, is approximately planar except the ethyl group, the maximum atomic deviation being 0.105 (5) Å. The fluorophenyl ring and 2-propylidenemalononitrile unit are located on the opposite sides of the C=C double bond, showing an E configuration.

Related literature

The title compound is a diene reagent in Diels–Alder reactions. For the use of malononitrile-containing compounds as building blocks in organic synthesis, see: Liu et al. (2002 ); Sepiol & Milart (1985 ); Zhang et al. (2003 ). For related structures, see: Kang & Chen (2009 ).

Experimental

Crystal data

C₁₄H₁₁FN₂
M_r = 226.25
Monoclinic, P 2₁ /n
a = 7.6504 (2) Å
b = 12.4989 (3) Å
c = 12.7787 (3) Å
β = 98.375 (2)°
V = 1208.89 (5) Å³
Z = 4
Cu Kα radiation
μ = 0.70 mm⁻¹
T = 291 K
0.42 × 0.38 × 0.32 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 Gemini ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.758, T_max = 0.808
5033 measured reflections
2148 independent reflections
1956 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.117
S = 1.06
2148 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.10 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: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811035884/xu5286sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811035884/xu5286Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811035884/xu5286Isup3.cml

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 & Milart, 1985) were obtained. Some crystal structures involving ylidene malononitrile groups have been published, including a recent report from our labratory (Kang & Chen, 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 copolar.The fluorophenyl ring and 2-propylidenemalononitrile groups are located on opposite sides of the double bond, showing an E configuration.

Related literature top

The title compound is a diene reagent in Diels–Alder reactions. For the use of malononitrile-containing compounds as building blocks in organic synthesis, see: Liu et al. (2002); Sepiol & Milart (1985); Zhang et al. (2003). For related structures, see: Kang & Chen (2009).

Experimental top

2-(Butan-2-ylidene)malononitrile (0.24 g, 2 mmol) and 4-fluorobenzaldehyde (0.248 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 reaction was cooled to room temperature, and the solution was filtered to obtain a white 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

The title compound is a diene reagent in Diels–Alder reactions. For the use of malononitrile-containing compounds as building blocks in organic synthesis, see: Liu et al. (2002); Sepiol & Milart (1985); Zhang et al. (2003). For related structures, see: Kang & Chen (2009).

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: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

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

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

Crystal data top

C₁₄H₁₁FN₂	F(000) = 472
M_r = 226.25	D_x = 1.243 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 3458 reflections
a = 7.6504 (2) Å	θ = 3.5–71.8°
b = 12.4989 (3) Å	µ = 0.70 mm⁻¹
c = 12.7787 (3) Å	T = 291 K
β = 98.375 (2)°	Block, yellow
V = 1208.89 (5) Å³	0.42 × 0.38 × 0.32 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Sapphire3 Gemini ultra diffractometer	2148 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	1956 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.014
Detector resolution: 15.9149 pixels mm^-1	θ_max = 67.1°, θ_min = 5.0°
ω scans	h = −9→8
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −14→11
T_min = 0.758, T_max = 0.808	l = −15→13
5033 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0672P)² + 0.0976P] where P = (F_o² + 2F_c²)/3
2148 reflections	(Δ/σ)_max = 0.005
155 parameters	Δρ_max = 0.10 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₄H₁₁FN₂	V = 1208.89 (5) Å³
M_r = 226.25	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 7.6504 (2) Å	µ = 0.70 mm⁻¹
b = 12.4989 (3) Å	T = 291 K
c = 12.7787 (3) Å	0.42 × 0.38 × 0.32 mm
β = 98.375 (2)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 Gemini ultra diffractometer	2148 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	1956 reflections with I > 2σ(I)
T_min = 0.758, T_max = 0.808	R_int = 0.014
5033 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.06	Δρ_max = 0.10 e Å⁻³
2148 reflections	Δρ_min = −0.14 e Å⁻³
155 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
C11	0.29662 (18)	−0.17966 (10)	0.91075 (11)	0.0583 (3)
F1	0.17654 (14)	0.52071 (7)	0.95680 (10)	0.0992 (4)
C9	0.49407 (15)	−0.06063 (10)	0.82906 (9)	0.0500 (3)
C4	0.36822 (15)	0.23270 (9)	0.86946 (9)	0.0483 (3)
N1	0.18077 (18)	−0.19553 (12)	0.95555 (12)	0.0819 (4)
C5	0.45722 (17)	0.32820 (10)	0.85718 (11)	0.0595 (3)
H5	0.5624	0.3264	0.8288	0.071*
C13	0.65462 (17)	−0.04859 (10)	0.77465 (10)	0.0571 (3)
H13A	0.6384	0.0122	0.7270	0.069*
H13B	0.6677	−0.1120	0.7327	0.069*
C3	0.21017 (16)	0.23790 (10)	0.91178 (9)	0.0515 (3)
H3	0.1477	0.1754	0.9201	0.062*
C14	0.82131 (18)	−0.03252 (13)	0.85331 (12)	0.0704 (4)
H14A	0.8075	0.0290	0.8964	0.106*
H14B	0.9199	−0.0217	0.8158	0.106*
H14C	0.8420	−0.0947	0.8975	0.106*
C12	0.53656 (19)	−0.25427 (10)	0.83029 (11)	0.0611 (4)
C7	0.44770 (16)	0.13350 (9)	0.83921 (10)	0.0520 (3)
H7	0.5433	0.1410	0.8024	0.062*
C10	0.44336 (16)	−0.16038 (9)	0.85528 (10)	0.0523 (3)
C2	0.14552 (18)	0.33429 (10)	0.94140 (11)	0.0593 (3)
H2	0.0406	0.3374	0.9700	0.071*
C1	0.23896 (19)	0.42570 (10)	0.92788 (12)	0.0633 (4)
C8	0.40019 (15)	0.03307 (9)	0.85783 (9)	0.0509 (3)
H8	0.3012	0.0228	0.8912	0.061*
C6	0.39336 (19)	0.42521 (10)	0.88608 (12)	0.0658 (4)
H6	0.4536	0.4885	0.8774	0.079*
N2	0.6121 (2)	−0.32851 (10)	0.81089 (12)	0.0867 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C11	0.0574 (7)	0.0436 (6)	0.0741 (8)	−0.0017 (5)	0.0100 (6)	0.0036 (5)
F1	0.1059 (7)	0.0510 (5)	0.1490 (10)	0.0130 (5)	0.0465 (7)	−0.0189 (5)
C9	0.0499 (6)	0.0461 (6)	0.0545 (6)	0.0027 (5)	0.0096 (5)	−0.0024 (5)
C4	0.0484 (6)	0.0419 (6)	0.0560 (6)	0.0011 (5)	0.0119 (5)	0.0056 (5)
N1	0.0709 (8)	0.0697 (8)	0.1101 (10)	−0.0068 (6)	0.0300 (7)	0.0134 (7)
C5	0.0540 (7)	0.0479 (7)	0.0808 (9)	−0.0026 (5)	0.0244 (6)	0.0060 (6)
C13	0.0607 (7)	0.0498 (7)	0.0650 (7)	0.0045 (5)	0.0232 (6)	−0.0012 (5)
C3	0.0504 (6)	0.0452 (6)	0.0602 (7)	−0.0003 (5)	0.0131 (5)	0.0067 (5)
C14	0.0541 (7)	0.0799 (10)	0.0803 (9)	0.0043 (6)	0.0203 (6)	0.0063 (7)
C12	0.0687 (8)	0.0465 (7)	0.0672 (8)	0.0053 (6)	0.0064 (6)	−0.0044 (6)
C7	0.0501 (6)	0.0472 (7)	0.0617 (7)	0.0028 (5)	0.0179 (5)	0.0031 (5)
C10	0.0539 (7)	0.0426 (6)	0.0606 (7)	0.0020 (5)	0.0091 (5)	−0.0019 (5)
C2	0.0557 (7)	0.0562 (8)	0.0694 (8)	0.0066 (5)	0.0203 (6)	0.0020 (6)
C1	0.0691 (8)	0.0453 (7)	0.0774 (8)	0.0094 (6)	0.0166 (6)	−0.0048 (6)
C8	0.0503 (6)	0.0436 (6)	0.0615 (7)	0.0018 (5)	0.0170 (5)	0.0013 (5)
C6	0.0701 (8)	0.0417 (7)	0.0878 (9)	−0.0069 (6)	0.0190 (7)	0.0015 (6)
N2	0.1048 (11)	0.0568 (8)	0.0969 (10)	0.0233 (7)	0.0096 (8)	−0.0131 (6)

Geometric parameters (Å, º) top

C11—N1	1.1404 (18)	C3—C2	1.3762 (17)
C11—C10	1.4326 (19)	C3—H3	0.9300
F1—C1	1.3514 (15)	C14—H14A	0.9600
C9—C10	1.3620 (17)	C14—H14B	0.9600
C9—C8	1.4489 (16)	C14—H14C	0.9600
C9—C13	1.5045 (17)	C12—N2	1.1393 (18)
C4—C5	1.3943 (16)	C12—C10	1.4331 (17)
C4—C3	1.3961 (16)	C7—C8	1.3378 (16)
C4—C7	1.4577 (16)	C7—H7	0.9300
C5—C6	1.3777 (18)	C2—C1	1.372 (2)
C5—H5	0.9300	C2—H2	0.9300
C13—C14	1.518 (2)	C1—C6	1.365 (2)
C13—H13A	0.9700	C8—H8	0.9300
C13—H13B	0.9700	C6—H6	0.9300

N1—C11—C10	179.39 (16)	C13—C14—H14C	109.5
C10—C9—C8	120.53 (11)	H14A—C14—H14C	109.5
C10—C9—C13	119.09 (11)	H14B—C14—H14C	109.5
C8—C9—C13	120.31 (10)	N2—C12—C10	179.37 (16)
C5—C4—C3	117.93 (11)	C8—C7—C4	128.05 (11)
C5—C4—C7	117.97 (11)	C8—C7—H7	116.0
C3—C4—C7	124.09 (10)	C4—C7—H7	116.0
C6—C5—C4	121.68 (12)	C9—C10—C11	123.19 (11)
C6—C5—H5	119.2	C9—C10—C12	121.73 (12)
C4—C5—H5	119.2	C11—C10—C12	115.07 (11)
C9—C13—C14	111.77 (11)	C1—C2—C3	118.66 (12)
C9—C13—H13A	109.3	C1—C2—H2	120.7
C14—C13—H13A	109.3	C3—C2—H2	120.7
C9—C13—H13B	109.3	F1—C1—C6	118.11 (12)
C14—C13—H13B	109.3	F1—C1—C2	119.08 (12)
H13A—C13—H13B	107.9	C6—C1—C2	122.81 (11)
C2—C3—C4	120.90 (11)	C7—C8—C9	123.76 (11)
C2—C3—H3	119.5	C7—C8—H8	118.1
C4—C3—H3	119.5	C9—C8—H8	118.1
C13—C14—H14A	109.5	C1—C6—C5	118.00 (12)
C13—C14—H14B	109.5	C1—C6—H6	121.0
H14A—C14—H14B	109.5	C5—C6—H6	121.0

C3—C4—C5—C6	0.4 (2)	C13—C9—C10—C12	−1.42 (19)
C7—C4—C5—C6	−178.49 (13)	C4—C3—C2—C1	0.4 (2)
C10—C9—C13—C14	−91.40 (14)	C3—C2—C1—F1	−179.96 (13)
C8—C9—C13—C14	85.53 (14)	C3—C2—C1—C6	0.1 (2)
C5—C4—C3—C2	−0.66 (19)	C4—C7—C8—C9	−176.65 (12)
C7—C4—C3—C2	178.11 (12)	C10—C9—C8—C7	176.67 (12)
C5—C4—C7—C8	169.58 (13)	C13—C9—C8—C7	−0.22 (19)
C3—C4—C7—C8	−9.2 (2)	F1—C1—C6—C5	179.66 (14)
C8—C9—C10—C11	0.61 (19)	C2—C1—C6—C5	−0.4 (2)
C13—C9—C10—C11	177.53 (12)	C4—C5—C6—C1	0.2 (2)
C8—C9—C10—C12	−178.34 (11)

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁FN₂
M_r	226.25
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	7.6504 (2), 12.4989 (3), 12.7787 (3)
β (°)	98.375 (2)
V (Å³)	1208.89 (5)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.70
Crystal size (mm)	0.42 × 0.38 × 0.32

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3 Gemini ultra
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.758, 0.808
No. of measured, independent and observed [I > 2σ(I)] reflections	5033, 2148, 1956
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.117, 1.06
No. of reflections	2148
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.10, −0.14

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXTL (Sheldrick, 2008).

Acknowledgements

The author thanks the Testing Centre of Sichuan University for the diffraction measurements. This work was supported by China West Normal University (No. 10ZB016).

References

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