2-[(E)-4-(2-Bromo­phen­yl)but-3-en-2-yl­idene]malononitrile

Kang, T.-R.

doi:10.1107/S1600536810049536

organic compounds

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Volume 66| Part 12| December 2010| Page o3365

https://doi.org/10.1107/S1600536810049536

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2-[(E)-4-(2-Bromophenyl)but-3-en-2-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@yahoo.com.cn

(Received 19 November 2010; accepted 26 November 2010; online 30 November 2010)

The title compound, C₁₃H₁₉BrN₂, is planar structure except for the methyl H atoms, the maximum atomic deviation for the non-H atoms being 0.100 (1) Å. The bromophenyl and isopropanylidenemalononitrile units are located on opposite sides of the C=C bond, showing an E configuration.

Related literature

For the use of malononitrile-containing compounds as building blocks in syntheses, see: Liu et al. (2002 ); Sepiol & Milart (1985 ); Zhang et al. (2003 ). For a related structure, see: Chen & Kang (2010 ).

Experimental

Crystal data

C₁₃H₉BrN₂
M_r = 273.13
Triclinic, $[P \overline 1]$
a = 7.0353 (7) Å
b = 7.0765 (5) Å
c = 13.3229 (8) Å
α = 82.192 (6)°
β = 76.628 (8)°
γ = 66.038 (9)°
V = 589.03 (8) Å³
Z = 2
Cu Kα radiation
μ = 4.52 mm⁻¹
T = 291 K
0.36 × 0.32 × 0.24 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 = 0.293, T_max = 0.410
4500 measured reflections
2062 independent reflections
1923 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.112
S = 1.06
2062 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.55 e Å⁻³

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/S1600536810049536/xu5097sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810049536/xu5097Isup2.hkl

checkCIF report

Comment top

Malononitrile derivatives have broad application for the preparation of heterocyclic ring compounds. 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 Chen, et al., 2010). 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 molecule skeleton display an approximately planar structure except for the methyl group.

Related literature top

For the use of malononitrile-containing compounds as building blocks in syntheses, see: Liu et al. (2002); Sepiol & Milart (1985); Zhang et al. (2003). For a related structure, see: Chen & Kang (2010).

Experimental top

2-(Propan-2-ylidene)malononitrile (0.212 g, 2 mmol) and 2-bromobenzaldehyde (0.366 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 yellow solid. Recrystallization from hot ethanol afforded the pure compound. Single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation ethyl acetate solution.

Structure description top

The molecular structure of (I) is shown in Fig. 1. Bond lengths and angles in (I) are normal. The molecule skeleton display an approximately planar structure except for the methyl group.

For the use of malononitrile-containing compounds as building blocks in syntheses, see: Liu et al. (2002); Sepiol & Milart (1985); Zhang et al. (2003). For a related structure, see: Chen & Kang (2010).

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)-4-(2-Bromophenyl)but-3-en-2-ylidene]propanedinitrile top

Crystal data top

C₁₃H₉BrN₂	Z = 2
M_r = 273.13	F(000) = 272
Triclinic, P1	D_x = 1.540 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.0353 (7) Å	Cell parameters from 3664 reflections
b = 7.0765 (5) Å	θ = 6.8–71.9°
c = 13.3229 (8) Å	µ = 4.52 mm⁻¹
α = 82.192 (6)°	T = 291 K
β = 76.628 (8)°	Block, yellow
γ = 66.038 (9)°	0.36 × 0.32 × 0.24 mm
V = 589.03 (8) Å³

Data collection top

Oxford Diffraction Xcalibur Sapphire3 Gemini ultra diffractometer	2062 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	1923 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.024
Detector resolution: 7.9575 pixels mm^-1	θ_max = 67.0°, θ_min = 6.8°
ω scans	h = −8→6
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −8→8
T_min = 0.293, T_max = 0.410	l = −15→15
4500 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 = 1.06	w = 1/[σ²(F_o²) + (0.0759P)² + 0.0933P] where P = (F_o² + 2F_c²)/3
2062 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.59 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

C₁₃H₉BrN₂	γ = 66.038 (9)°
M_r = 273.13	V = 589.03 (8) Å³
Triclinic, P1	Z = 2
a = 7.0353 (7) Å	Cu Kα radiation
b = 7.0765 (5) Å	µ = 4.52 mm⁻¹
c = 13.3229 (8) Å	T = 291 K
α = 82.192 (6)°	0.36 × 0.32 × 0.24 mm
β = 76.628 (8)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 Gemini ultra diffractometer	2062 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	1923 reflections with I > 2σ(I)
T_min = 0.293, T_max = 0.410	R_int = 0.024
4500 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.06	Δρ_max = 0.59 e Å⁻³
2062 reflections	Δρ_min = −0.55 e Å⁻³
146 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
Br1	0.67339 (5)	0.15902 (4)	0.54256 (2)	0.06643 (19)
C8	0.8775 (4)	−0.3609 (4)	0.7789 (2)	0.0493 (6)
H8	0.8557	−0.3515	0.8499	0.059*
N2	1.2571 (5)	−1.0939 (4)	0.7188 (2)	0.0735 (8)
C11	1.0519 (4)	−0.7373 (4)	0.7984 (2)	0.0455 (5)
C4	0.5298 (5)	0.2647 (5)	0.8955 (2)	0.0598 (7)
H4	0.4994	0.2887	0.9655	0.072*
C13	1.0087 (4)	−0.7342 (4)	0.9092 (2)	0.0527 (6)
C5	0.6402 (5)	0.0655 (4)	0.8620 (2)	0.0563 (6)
H5	0.6835	−0.0433	0.9103	0.068*
C9	0.9905 (4)	−0.5636 (4)	0.7362 (2)	0.0461 (5)
C7	0.8037 (4)	−0.1879 (4)	0.7217 (2)	0.0516 (6)
H7	0.8277	−0.2024	0.6510	0.062*
C2	0.5107 (4)	0.3937 (4)	0.7208 (3)	0.0563 (7)
H2	0.4684	0.5041	0.6732	0.068*
C10	1.0389 (5)	−0.5797 (5)	0.6211 (2)	0.0584 (7)
H10A	1.1160	−0.7222	0.6044	0.088*
H10B	1.1228	−0.5013	0.5895	0.088*
H10C	0.9087	−0.5260	0.5958	0.088*
C6	0.6889 (4)	0.0226 (4)	0.7573 (2)	0.0478 (6)
N1	0.9737 (5)	−0.7329 (5)	0.9974 (2)	0.0749 (8)
C3	0.4644 (4)	0.4289 (4)	0.8242 (3)	0.0604 (7)
H3	0.3891	0.5629	0.8466	0.072*
C12	1.1667 (4)	−0.9376 (4)	0.7555 (2)	0.0532 (6)
C1	0.6206 (4)	0.1936 (4)	0.6873 (2)	0.0496 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0880 (3)	0.0444 (2)	0.0549 (3)	−0.01383 (17)	−0.01666 (17)	0.00310 (15)
C8	0.0616 (14)	0.0331 (13)	0.0509 (14)	−0.0141 (11)	−0.0134 (11)	−0.0042 (10)
N2	0.0868 (17)	0.0364 (14)	0.0813 (19)	−0.0086 (12)	−0.0094 (14)	−0.0120 (13)
C11	0.0542 (12)	0.0334 (12)	0.0467 (13)	−0.0140 (10)	−0.0109 (10)	−0.0024 (10)
C4	0.0712 (16)	0.0478 (15)	0.0555 (16)	−0.0208 (13)	−0.0032 (13)	−0.0105 (12)
C13	0.0673 (15)	0.0354 (13)	0.0519 (17)	−0.0138 (11)	−0.0196 (12)	0.0028 (11)
C5	0.0706 (16)	0.0384 (14)	0.0559 (16)	−0.0179 (12)	−0.0128 (12)	0.0009 (12)
C9	0.0549 (12)	0.0336 (12)	0.0481 (14)	−0.0145 (10)	−0.0117 (10)	−0.0024 (10)
C7	0.0654 (14)	0.0336 (13)	0.0522 (15)	−0.0145 (11)	−0.0141 (11)	−0.0015 (11)
C2	0.0583 (14)	0.0329 (13)	0.0699 (19)	−0.0105 (11)	−0.0140 (13)	0.0022 (12)
C10	0.0780 (17)	0.0425 (15)	0.0469 (15)	−0.0169 (13)	−0.0093 (13)	−0.0031 (11)
C6	0.0539 (13)	0.0318 (12)	0.0551 (15)	−0.0140 (10)	−0.0119 (11)	0.0003 (10)
N1	0.105 (2)	0.0617 (17)	0.0521 (17)	−0.0232 (15)	−0.0236 (14)	0.0012 (12)
C3	0.0602 (15)	0.0371 (14)	0.076 (2)	−0.0120 (11)	−0.0060 (13)	−0.0109 (13)
C12	0.0629 (15)	0.0354 (14)	0.0566 (16)	−0.0150 (12)	−0.0122 (12)	0.0011 (12)
C1	0.0508 (12)	0.0359 (13)	0.0575 (15)	−0.0125 (10)	−0.0116 (11)	0.0009 (11)

Geometric parameters (Å, º) top

Br1—C1	1.908 (3)	C5—H5	0.9300
C8—C7	1.327 (4)	C9—C10	1.502 (4)
C8—C9	1.449 (4)	C7—C6	1.461 (4)
C8—H8	0.9300	C7—H7	0.9300
N2—C12	1.140 (4)	C2—C3	1.373 (5)
C11—C9	1.358 (4)	C2—C1	1.387 (4)
C11—C12	1.437 (4)	C2—H2	0.9300
C11—C13	1.438 (4)	C10—H10A	0.9600
C4—C5	1.383 (4)	C10—H10B	0.9600
C4—C3	1.390 (5)	C10—H10C	0.9600
C4—H4	0.9300	C6—C1	1.412 (4)
C13—N1	1.144 (4)	C3—H3	0.9300
C5—C6	1.401 (4)

C7—C8—C9	123.3 (3)	C3—C2—C1	120.0 (3)
C7—C8—H8	118.4	C3—C2—H2	120.0
C9—C8—H8	118.4	C1—C2—H2	120.0
C9—C11—C12	120.8 (2)	C9—C10—H10A	109.5
C9—C11—C13	123.1 (2)	C9—C10—H10B	109.5
C12—C11—C13	116.1 (2)	H10A—C10—H10B	109.5
C5—C4—C3	119.7 (3)	C9—C10—H10C	109.5
C5—C4—H4	120.2	H10A—C10—H10C	109.5
C3—C4—H4	120.2	H10B—C10—H10C	109.5
N1—C13—C11	179.5 (3)	C5—C6—C1	116.6 (2)
C4—C5—C6	121.9 (3)	C5—C6—C7	122.1 (2)
C4—C5—H5	119.0	C1—C6—C7	121.3 (3)
C6—C5—H5	119.0	C2—C3—C4	120.2 (3)
C11—C9—C8	121.1 (2)	C2—C3—H3	119.9
C11—C9—C10	120.0 (2)	C4—C3—H3	119.9
C8—C9—C10	119.0 (2)	N2—C12—C11	178.1 (3)
C8—C7—C6	127.4 (3)	C2—C1—C6	121.5 (3)
C8—C7—H7	116.3	C2—C1—Br1	117.1 (2)
C6—C7—H7	116.3	C6—C1—Br1	121.4 (2)

C9—C11—C13—N1	131 (44)	C8—C7—C6—C5	−0.8 (5)
C12—C11—C13—N1	−49 (45)	C8—C7—C6—C1	179.5 (3)
C3—C4—C5—C6	−0.1 (5)	C1—C2—C3—C4	0.9 (4)
C12—C11—C9—C8	−179.0 (2)	C5—C4—C3—C2	−0.5 (5)
C13—C11—C9—C8	0.7 (4)	C9—C11—C12—N2	−6 (10)
C12—C11—C9—C10	1.1 (4)	C13—C11—C12—N2	175 (10)
C13—C11—C9—C10	−179.1 (3)	C3—C2—C1—C6	−0.6 (4)
C7—C8—C9—C11	−176.0 (3)	C3—C2—C1—Br1	178.9 (2)
C7—C8—C9—C10	3.8 (4)	C5—C6—C1—C2	0.0 (4)
C9—C8—C7—C6	−179.9 (3)	C7—C6—C1—C2	179.7 (3)
C4—C5—C6—C1	0.4 (4)	C5—C6—C1—Br1	−179.5 (2)
C4—C5—C6—C7	−179.4 (3)	C7—C6—C1—Br1	0.2 (3)

Experimental details

Crystal data
Chemical formula	C₁₃H₉BrN₂
M_r	273.13
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	7.0353 (7), 7.0765 (5), 13.3229 (8)
α, β, γ (°)	82.192 (6), 76.628 (8), 66.038 (9)
V (Å³)	589.03 (8)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	4.52
Crystal size (mm)	0.36 × 0.32 × 0.24

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3 Gemini ultra
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.293, 0.410
No. of measured, independent and observed [I > 2σ(I)] reflections	4500, 2062, 1923
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.112, 1.06
No. of reflections	2062
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.55

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

Acknowledgements

The author thanks the Testing Centre of Sichuan University for the diffraction measurements and is grateful for financial support from China West Normal University (No. 412374).

References

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