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

Abstract

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,

• a = 7.6504 (2) Å

• b = 12.4989 (3) Å

• c = 12.7787 (3) Å

• β = 98.375 (2)°

• V = 1208.89 (5) ų

• 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 ▶) 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[F ² > 2σ(F ²)] = 0.041

• wR(F ²) = 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 ▶); 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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811035884/xu5286Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

The carbon-bound H atoms were placed in calculated positions, with C—H = 0.93–0.97 Å, and refined using a riding model, with U_iso(H) =1.5U_eq(C) for methyl H atoms and U_iso(H) = 1.2U_eq(C) for the others.

Figures

Fig. 1.

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

Crystal data

C14H11FN2	F(000) = 472
Mr = 226.25	Dx = 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

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	Rint = 0.014
Detector resolution: 15.9149 pixels mm-1	θmax = 67.1°, θmin = 5.0°
ω scans	h = −9→8
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −14→11
Tmin = 0.758, Tmax = 0.808	l = −15→13
5033 measured reflections

Refinement

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(Fo2) + (0.0672P)2 + 0.0976P] where P = (Fo2 + 2Fc2)/3
2148 reflections	(Δ/σ)max = 0.005
155 parameters	Δρmax = 0.10 e Å−3
0 restraints	Δρmin = −0.14 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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)