organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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[Liu, Y., Shen, B., Kotora, M., Nakajima, K. & Takahashi, T. (2002). J. Org. Chem. 67, 7019-7028.]); Sepiol & Milart (1985[Sepiol, J. & Milart, P. (1985). Tetrahedron, 41, 5261-5265.]); Zhang et al. (2003[Zhang, B., Zhu, X.-Q., Lu, J.-Y., He, J., Wang, P.-G. & Cheng, J.-P. (2003). J. Org. Chem. 68, 3295-3298.]). For related structures, see: Kang & Chen (2009[Kang, T.-R. & Chen, L.-M. (2009). Acta Cryst. E65, o3164.]).

[Scheme 1]

Experimental

Crystal data
  • C14H11FN2

  • Mr = 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.]) Tmin = 0.758, Tmax = 0.808

  • 5033 measured reflections

  • 2148 independent reflections

  • 1956 reflections with I > 2σ(I)

  • Rint = 0.014

Refinement
  • R[F2 > 2σ(F2)] = 0.041

  • wR(F2) = 0.117

  • S = 1.06

  • 2148 reflections

  • 155 parameters

  • H-atom parameters constrained

  • Δρmax = 0.10 e Å−3

  • Δρmin = −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[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

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 Uiso(H) =1.5Ueq(C) for methyl H atoms and Uiso(H) = 1.2Ueq(C) for the others.

Structure description 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.

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
[Figure 1] 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
C14H11FN2F(000) = 472
Mr = 226.25Dx = 1.243 Mg m3
Monoclinic, P21/nCu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ynCell parameters from 3458 reflections
a = 7.6504 (2) Åθ = 3.5–71.8°
b = 12.4989 (3) ŵ = 0.70 mm1
c = 12.7787 (3) ÅT = 291 K
β = 98.375 (2)°Block, yellow
V = 1208.89 (5) Å30.42 × 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 Source1956 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.014
Detector resolution: 15.9149 pixels mm-1θmax = 67.1°, θmin = 5.0°
ω scansh = 98
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
k = 1411
Tmin = 0.758, Tmax = 0.808l = 1513
5033 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117H-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 parametersΔρmax = 0.10 e Å3
0 restraintsΔρmin = 0.14 e Å3
Crystal data top
C14H11FN2V = 1208.89 (5) Å3
Mr = 226.25Z = 4
Monoclinic, P21/nCu Kα radiation
a = 7.6504 (2) ŵ = 0.70 mm1
b = 12.4989 (3) ÅT = 291 K
c = 12.7787 (3) Å0.42 × 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)
Tmin = 0.758, Tmax = 0.808Rint = 0.014
5033 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.117H-atom parameters constrained
S = 1.06Δρmax = 0.10 e Å3
2148 reflectionsΔρmin = 0.14 e Å3
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
xyzUiso*/Ueq
C110.29662 (18)0.17966 (10)0.91075 (11)0.0583 (3)
F10.17654 (14)0.52071 (7)0.95680 (10)0.0992 (4)
C90.49407 (15)0.06063 (10)0.82906 (9)0.0500 (3)
C40.36822 (15)0.23270 (9)0.86946 (9)0.0483 (3)
N10.18077 (18)0.19553 (12)0.95555 (12)0.0819 (4)
C50.45722 (17)0.32820 (10)0.85718 (11)0.0595 (3)
H50.56240.32640.82880.071*
C130.65462 (17)0.04859 (10)0.77465 (10)0.0571 (3)
H13A0.63840.01220.72700.069*
H13B0.66770.11200.73270.069*
C30.21017 (16)0.23790 (10)0.91178 (9)0.0515 (3)
H30.14770.17540.92010.062*
C140.82131 (18)0.03252 (13)0.85331 (12)0.0704 (4)
H14A0.80750.02900.89640.106*
H14B0.91990.02170.81580.106*
H14C0.84200.09470.89750.106*
C120.53656 (19)0.25427 (10)0.83029 (11)0.0611 (4)
C70.44770 (16)0.13350 (9)0.83921 (10)0.0520 (3)
H70.54330.14100.80240.062*
C100.44336 (16)0.16038 (9)0.85528 (10)0.0523 (3)
C20.14552 (18)0.33429 (10)0.94140 (11)0.0593 (3)
H20.04060.33740.97000.071*
C10.23896 (19)0.42570 (10)0.92788 (12)0.0633 (4)
C80.40019 (15)0.03307 (9)0.85783 (9)0.0509 (3)
H80.30120.02280.89120.061*
C60.39336 (19)0.42521 (10)0.88608 (12)0.0658 (4)
H60.45360.48850.87740.079*
N20.6121 (2)0.32851 (10)0.81089 (12)0.0867 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C110.0574 (7)0.0436 (6)0.0741 (8)0.0017 (5)0.0100 (6)0.0036 (5)
F10.1059 (7)0.0510 (5)0.1490 (10)0.0130 (5)0.0465 (7)0.0189 (5)
C90.0499 (6)0.0461 (6)0.0545 (6)0.0027 (5)0.0096 (5)0.0024 (5)
C40.0484 (6)0.0419 (6)0.0560 (6)0.0011 (5)0.0119 (5)0.0056 (5)
N10.0709 (8)0.0697 (8)0.1101 (10)0.0068 (6)0.0300 (7)0.0134 (7)
C50.0540 (7)0.0479 (7)0.0808 (9)0.0026 (5)0.0244 (6)0.0060 (6)
C130.0607 (7)0.0498 (7)0.0650 (7)0.0045 (5)0.0232 (6)0.0012 (5)
C30.0504 (6)0.0452 (6)0.0602 (7)0.0003 (5)0.0131 (5)0.0067 (5)
C140.0541 (7)0.0799 (10)0.0803 (9)0.0043 (6)0.0203 (6)0.0063 (7)
C120.0687 (8)0.0465 (7)0.0672 (8)0.0053 (6)0.0064 (6)0.0044 (6)
C70.0501 (6)0.0472 (7)0.0617 (7)0.0028 (5)0.0179 (5)0.0031 (5)
C100.0539 (7)0.0426 (6)0.0606 (7)0.0020 (5)0.0091 (5)0.0019 (5)
C20.0557 (7)0.0562 (8)0.0694 (8)0.0066 (5)0.0203 (6)0.0020 (6)
C10.0691 (8)0.0453 (7)0.0774 (8)0.0094 (6)0.0166 (6)0.0048 (6)
C80.0503 (6)0.0436 (6)0.0615 (7)0.0018 (5)0.0170 (5)0.0013 (5)
C60.0701 (8)0.0417 (7)0.0878 (9)0.0069 (6)0.0190 (7)0.0015 (6)
N20.1048 (11)0.0568 (8)0.0969 (10)0.0233 (7)0.0096 (8)0.0131 (6)
Geometric parameters (Å, º) top
C11—N11.1404 (18)C3—C21.3762 (17)
C11—C101.4326 (19)C3—H30.9300
F1—C11.3514 (15)C14—H14A0.9600
C9—C101.3620 (17)C14—H14B0.9600
C9—C81.4489 (16)C14—H14C0.9600
C9—C131.5045 (17)C12—N21.1393 (18)
C4—C51.3943 (16)C12—C101.4331 (17)
C4—C31.3961 (16)C7—C81.3378 (16)
C4—C71.4577 (16)C7—H70.9300
C5—C61.3777 (18)C2—C11.372 (2)
C5—H50.9300C2—H20.9300
C13—C141.518 (2)C1—C61.365 (2)
C13—H13A0.9700C8—H80.9300
C13—H13B0.9700C6—H60.9300
N1—C11—C10179.39 (16)C13—C14—H14C109.5
C10—C9—C8120.53 (11)H14A—C14—H14C109.5
C10—C9—C13119.09 (11)H14B—C14—H14C109.5
C8—C9—C13120.31 (10)N2—C12—C10179.37 (16)
C5—C4—C3117.93 (11)C8—C7—C4128.05 (11)
C5—C4—C7117.97 (11)C8—C7—H7116.0
C3—C4—C7124.09 (10)C4—C7—H7116.0
C6—C5—C4121.68 (12)C9—C10—C11123.19 (11)
C6—C5—H5119.2C9—C10—C12121.73 (12)
C4—C5—H5119.2C11—C10—C12115.07 (11)
C9—C13—C14111.77 (11)C1—C2—C3118.66 (12)
C9—C13—H13A109.3C1—C2—H2120.7
C14—C13—H13A109.3C3—C2—H2120.7
C9—C13—H13B109.3F1—C1—C6118.11 (12)
C14—C13—H13B109.3F1—C1—C2119.08 (12)
H13A—C13—H13B107.9C6—C1—C2122.81 (11)
C2—C3—C4120.90 (11)C7—C8—C9123.76 (11)
C2—C3—H3119.5C7—C8—H8118.1
C4—C3—H3119.5C9—C8—H8118.1
C13—C14—H14A109.5C1—C6—C5118.00 (12)
C13—C14—H14B109.5C1—C6—H6121.0
H14A—C14—H14B109.5C5—C6—H6121.0
C3—C4—C5—C60.4 (2)C13—C9—C10—C121.42 (19)
C7—C4—C5—C6178.49 (13)C4—C3—C2—C10.4 (2)
C10—C9—C13—C1491.40 (14)C3—C2—C1—F1179.96 (13)
C8—C9—C13—C1485.53 (14)C3—C2—C1—C60.1 (2)
C5—C4—C3—C20.66 (19)C4—C7—C8—C9176.65 (12)
C7—C4—C3—C2178.11 (12)C10—C9—C8—C7176.67 (12)
C5—C4—C7—C8169.58 (13)C13—C9—C8—C70.22 (19)
C3—C4—C7—C89.2 (2)F1—C1—C6—C5179.66 (14)
C8—C9—C10—C110.61 (19)C2—C1—C6—C50.4 (2)
C13—C9—C10—C11177.53 (12)C4—C5—C6—C10.2 (2)
C8—C9—C10—C12178.34 (11)

Experimental details

Crystal data
Chemical formulaC14H11FN2
Mr226.25
Crystal system, space groupMonoclinic, P21/n
Temperature (K)291
a, b, c (Å)7.6504 (2), 12.4989 (3), 12.7787 (3)
β (°) 98.375 (2)
V3)1208.89 (5)
Z4
Radiation typeCu Kα
µ (mm1)0.70
Crystal size (mm)0.42 × 0.38 × 0.32
Data collection
DiffractometerOxford Diffraction Xcalibur Sapphire3 Gemini ultra
Absorption correctionMulti-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Tmin, Tmax0.758, 0.808
No. of measured, independent and
observed [I > 2σ(I)] reflections
5033, 2148, 1956
Rint0.014
(sin θ/λ)max1)0.597
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.117, 1.06
No. of reflections2148
No. of parameters155
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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

First citationKang, T.-R. & Chen, L.-M. (2009). Acta Cryst. E65, o3164.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationLiu, Y., Shen, B., Kotora, M., Nakajima, K. & Takahashi, T. (2002). J. Org. Chem. 67, 7019–7028.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationOxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.  Google Scholar
First citationSepiol, J. & Milart, P. (1985). Tetrahedron, 41, 5261–5265.  CrossRef CAS Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZhang, B., Zhu, X.-Q., Lu, J.-Y., He, J., Wang, P.-G. & Cheng, J.-P. (2003). J. Org. Chem. 68, 3295–3298.  Web of Science CrossRef PubMed CAS Google Scholar

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ISSN: 2056-9890
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