2-[4-(Diethyl­amino)­benzyl­idene]malono­nitrile

Jing, Y.; Yu, L.-T.

doi:10.1107/S1600536811019295

organic compounds

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Volume 67| Part 6| June 2011| Page o1556

doi:10.1107/S1600536811019295

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2-[4-(Diethylamino)benzylidene]malononitrile

Yi Jing ^a,^b and Luo-Ting Yu ^a ^*

^aSchool of Chemical Engineering, Sichuan University, Chengdu 610065, People's Republic of China, and ^bChengdu institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, People's Republic of China
^*Correspondence e-mail: yuluot@scu.edu.cn

(Received 9 May 2011; accepted 21 May 2011; online 28 May 2011)

In the title compound, C₁₄H₁₅N₃, the diethylamino N atom, benzene ring, olefinic bond and cyano groups form an extended conjugated system, making the molecule nearly planar: the dihedral angle between the benzene ring and the best plane throught the cyano groups is 4.93 (10)°, while the dihedral angle between the benzene ring and the plane through the diethylamino N atom and the two attached ethyl C atoms is 9.51 (14)°. In the crystal, intermolecular C—H⋯π interactions stabilize the packing.

Related literature

The title compound is an intermediate in our research into anticancer agents. For general background to its chemistry, biological activity and use, see: Gazit et al. (1989 ).

Experimental

Crystal data

C₁₄H₁₅N₃
M_r = 225.29
Monoclinic, P 2₁ /n
a = 9.2187 (2) Å
b = 9.4914 (2) Å
c = 14.5384 (4) Å
β = 97.846 (2)°
V = 1260.17 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 150 K
0.30 × 0.25 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.997, T_max = 1.000
10075 measured reflections
2577 independent reflections
2151 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.095
S = 1.03
2577 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C7–C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14A⋯Cg1ⁱ	0.99	2.74	3.5154 (13)	136
Symmetry code: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811019295/vm2094sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811019295/vm2094Isup2.hkl

checkCIF report

Comment top

Cancer is a serious threat to human health. Molecular targeted therapies have created an encouraging road in the treatment of cancer in recent years. The title compound is a key intermediate in our synthetic investigations of molecular targeted anticancer agents. We report here its crystal structure.

As shown in Fig. 1, the N13 atom, benzene ring, olefinic bond and cyano-groups form an extended conjugated system, making them almost planar. The dihedral angle between the benzene plane and the best plane throught the cyano-groups is 4.93 (10)°, while the dihedral angle between the benzene plane and the plane through atoms N13, C14 and C15 being 9.51 (14)°. In the crystal, molecules are linked into a three-dimensional network by intermolecular C-H···π interactions (Fig.2, Table 1) and Van der Waals forces. Otherwise, there are no hydrogen bonds observed in the packing diagram.

Related literature top

The title compound is an intermediate in our research into anticancer agents. For general background to its chemistry, biological activity and use, see: Gazit et al. (1989).

Experimental top

To a solution of 4-(diethylamino)benzaldehyde (1.5 g, 8.463 mmol) and malononitrile (0.587 g, 8.886 mmol) in ethanol (25 ml) was added 4-methylmorpholine (0.9 ml). The reaction mixture was refluxed for 2 h. After cooled down to room temperature, the mixture was filtered and a red solid was abtained as the target product. Crystals suitable for X-ray analysis were obtained by slow evaporation from a solution of ethyl acetate.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2006); cell refinement: CrysAlis PRO (Oxford Diffraction, 2006); data reduction: CrysAlis PRO (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Crystal packing for the title compound, with C14—H14A···π interactions shown as dotted red lines (the centroid of ring C7-C12 is shown as a red dot).

2-{[4-(diethylamino)phenyl]methylidene}propanedinitrile top

Crystal data top

C₁₄H₁₅N₃	F(000) = 480
M_r = 225.29	D_x = 1.187 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.7107 Å
a = 9.2187 (2) Å	Cell parameters from 4336 reflections
b = 9.4914 (2) Å	θ = 3.1–29.2°
c = 14.5384 (4) Å	µ = 0.07 mm⁻¹
β = 97.846 (2)°	T = 150 K
V = 1260.17 (6) Å³	Block, red
Z = 4	0.30 × 0.25 × 0.20 mm

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	2577 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2151 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 16.0874 pixels mm^-1	θ_max = 26.4°, θ_min = 3.1°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)	k = −11→11
T_min = 0.997, T_max = 1.000	l = −15→18
10075 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0409P)² + 0.2819P] where P = (F_o² + 2F_c²)/3
2577 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₄H₁₅N₃	V = 1260.17 (6) Å³
M_r = 225.29	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.2187 (2) Å	µ = 0.07 mm⁻¹
b = 9.4914 (2) Å	T = 150 K
c = 14.5384 (4) Å	0.30 × 0.25 × 0.20 mm
β = 97.846 (2)°

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	2577 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)	2151 reflections with I > 2σ(I)
T_min = 0.997, T_max = 1.000	R_int = 0.022
10075 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.03	Δρ_max = 0.18 e Å⁻³
2577 reflections	Δρ_min = −0.18 e Å⁻³
156 parameters

Special details top

Experimental. CrysAlisPro, Version 1.171.34.40. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm (Oxford Diffraction, 2006).

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
N1	0.56613 (12)	0.33522 (13)	−0.14324 (8)	0.0415 (3)
N6	0.83063 (12)	−0.04260 (12)	−0.12289 (8)	0.0361 (3)
N13	0.92323 (11)	0.75238 (10)	0.22772 (7)	0.0252 (2)
C2	0.66785 (13)	0.27997 (13)	−0.10553 (8)	0.0270 (3)
C3	0.79456 (12)	0.20766 (12)	−0.06038 (8)	0.0235 (3)
C4	0.81521 (13)	0.06912 (13)	−0.09534 (8)	0.0265 (3)
C5	0.89198 (12)	0.25873 (12)	0.01132 (8)	0.0230 (3)
H5	0.9718	0.1975	0.0308	0.028*
C7	0.89497 (12)	0.38735 (12)	0.06192 (8)	0.0214 (3)
C8	0.78864 (12)	0.49489 (12)	0.04813 (8)	0.0224 (3)
H8	0.7087	0.4849	−0.0001	0.027*
C9	1.01290 (12)	0.40925 (13)	0.13344 (8)	0.0243 (3)
H9	1.0866	0.3390	0.1445	0.029*
C10	0.79762 (12)	0.61324 (12)	0.10229 (8)	0.0228 (3)
H10	0.7229	0.6825	0.0916	0.027*
C11	1.02484 (12)	0.52810 (12)	0.18741 (8)	0.0242 (3)
H11	1.1067	0.5391	0.2341	0.029*
C12	0.91658 (12)	0.63493 (12)	0.17440 (8)	0.0213 (3)
C14	0.79952 (13)	0.85020 (13)	0.22449 (8)	0.0289 (3)
H14A	0.7991	0.8920	0.2868	0.035*
H14B	0.7071	0.7969	0.2088	0.035*
C15	1.05037 (13)	0.78608 (14)	0.29599 (8)	0.0297 (3)
H15A	1.0639	0.8896	0.2984	0.036*
H15B	1.1390	0.7440	0.2756	0.036*
C16	0.80443 (16)	0.96798 (14)	0.15436 (10)	0.0398 (3)
H16A	0.8031	0.9276	0.0922	0.060*
H16B	0.8942	1.0230	0.1705	0.060*
H16C	0.7191	1.0294	0.1551	0.060*
C17	1.03529 (16)	0.73264 (17)	0.39255 (9)	0.0412 (4)
H17A	1.0252	0.6298	0.3911	0.062*
H17B	0.9484	0.7748	0.4135	0.062*
H17C	1.1225	0.7588	0.4354	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0354 (6)	0.0428 (7)	0.0425 (7)	0.0053 (6)	−0.0081 (5)	−0.0064 (6)
N6	0.0351 (6)	0.0291 (6)	0.0418 (7)	0.0014 (5)	−0.0031 (5)	−0.0078 (5)
N13	0.0280 (5)	0.0248 (5)	0.0219 (5)	0.0033 (4)	0.0001 (4)	−0.0032 (4)
C2	0.0278 (6)	0.0263 (6)	0.0262 (7)	−0.0020 (5)	0.0011 (5)	−0.0047 (5)
C3	0.0252 (6)	0.0226 (6)	0.0226 (6)	−0.0006 (5)	0.0034 (5)	−0.0002 (5)
C4	0.0244 (6)	0.0276 (7)	0.0263 (6)	−0.0016 (5)	−0.0012 (5)	−0.0006 (5)
C5	0.0229 (6)	0.0214 (6)	0.0246 (6)	0.0016 (5)	0.0030 (4)	0.0032 (5)
C7	0.0226 (6)	0.0220 (6)	0.0198 (6)	−0.0008 (5)	0.0033 (4)	0.0014 (4)
C8	0.0227 (5)	0.0245 (6)	0.0192 (6)	−0.0001 (5)	−0.0002 (4)	0.0017 (5)
C9	0.0232 (6)	0.0235 (6)	0.0256 (6)	0.0041 (5)	0.0016 (5)	0.0024 (5)
C10	0.0235 (6)	0.0229 (6)	0.0216 (6)	0.0050 (5)	0.0014 (4)	0.0025 (5)
C11	0.0231 (6)	0.0270 (6)	0.0211 (6)	0.0016 (5)	−0.0017 (4)	0.0004 (5)
C12	0.0256 (6)	0.0216 (6)	0.0172 (6)	−0.0004 (5)	0.0045 (4)	0.0016 (4)
C14	0.0312 (6)	0.0294 (7)	0.0265 (7)	0.0052 (5)	0.0056 (5)	−0.0055 (5)
C15	0.0307 (6)	0.0275 (7)	0.0295 (7)	−0.0017 (5)	−0.0008 (5)	−0.0071 (5)
C16	0.0435 (8)	0.0332 (8)	0.0433 (8)	0.0120 (6)	0.0081 (6)	0.0055 (6)
C17	0.0428 (8)	0.0538 (9)	0.0246 (7)	0.0058 (7)	−0.0034 (6)	−0.0062 (6)

Geometric parameters (Å, º) top

N1—C2	1.1465 (16)	C10—H10	0.9500
N6—C4	1.1491 (16)	C10—C12	1.4248 (16)
N13—C12	1.3543 (15)	C11—H11	0.9500
N13—C14	1.4663 (15)	C11—C12	1.4172 (16)
N13—C15	1.4642 (15)	C14—H14A	0.9900
C2—C3	1.4343 (16)	C14—H14B	0.9900
C3—C4	1.4318 (17)	C14—C16	1.5178 (18)
C3—C5	1.3685 (16)	C15—H15A	0.9900
C5—H5	0.9500	C15—H15B	0.9900
C5—C7	1.4235 (16)	C15—C17	1.5168 (19)
C7—C8	1.4104 (16)	C16—H16A	0.9800
C7—C9	1.4134 (16)	C16—H16B	0.9800
C8—H8	0.9500	C16—H16C	0.9800
C8—C10	1.3678 (16)	C17—H17A	0.9800
C9—H9	0.9500	C17—H17B	0.9800
C9—C11	1.3700 (16)	C17—H17C	0.9800

C12—N13—C14	121.91 (10)	N13—C12—C11	122.45 (10)
C12—N13—C15	122.50 (10)	C11—C12—C10	116.87 (10)
C15—N13—C14	115.50 (9)	N13—C14—H14A	108.9
N1—C2—C3	178.32 (13)	N13—C14—H14B	108.9
C4—C3—C2	114.61 (10)	N13—C14—C16	113.17 (10)
C5—C3—C2	126.01 (11)	H14A—C14—H14B	107.8
C5—C3—C4	119.37 (10)	C16—C14—H14A	108.9
N6—C4—C3	179.26 (14)	C16—C14—H14B	108.9
C3—C5—H5	114.3	N13—C15—H15A	109.0
C3—C5—C7	131.43 (11)	N13—C15—H15B	109.0
C7—C5—H5	114.3	N13—C15—C17	112.85 (11)
C8—C7—C5	125.67 (10)	H15A—C15—H15B	107.8
C8—C7—C9	116.62 (10)	C17—C15—H15A	109.0
C9—C7—C5	117.71 (10)	C17—C15—H15B	109.0
C7—C8—H8	119.1	C14—C16—H16A	109.5
C10—C8—C7	121.75 (10)	C14—C16—H16B	109.5
C10—C8—H8	119.1	C14—C16—H16C	109.5
C7—C9—H9	118.8	H16A—C16—H16B	109.5
C11—C9—C7	122.42 (11)	H16A—C16—H16C	109.5
C11—C9—H9	118.8	H16B—C16—H16C	109.5
C8—C10—H10	119.3	C15—C17—H17A	109.5
C8—C10—C12	121.49 (10)	C15—C17—H17B	109.5
C12—C10—H10	119.3	C15—C17—H17C	109.5
C9—C11—H11	119.6	H17A—C17—H17B	109.5
C9—C11—C12	120.84 (10)	H17A—C17—H17C	109.5
C12—C11—H11	119.6	H17B—C17—H17C	109.5
N13—C12—C10	120.68 (10)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C7–C12 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14A···Cg1ⁱ	0.99	2.74	3.5154 (13)	136

Symmetry code: (i) −x+3/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₅N₃
M_r	225.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	9.2187 (2), 9.4914 (2), 14.5384 (4)
β (°)	97.846 (2)
V (Å³)	1260.17 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)
T_min, T_max	0.997, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10075, 2577, 2151
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.095, 1.03
No. of reflections	2577
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.18

Computer programs: CrysAlis PRO (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2006), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C7–C12 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14A···Cg1ⁱ	0.99	2.74	3.5154 (13)	136

Symmetry code: (i) −x+3/2, y+1/2, −z+1/2.

Acknowledgements

We thank the Analytical and Testing Center of Sichuan University for the X-ray measurements.

References

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gazit, A., Yaish, P., Gilon, C. & Levitzki, A. (1989). J. Med. Chem. 32, 2344–2352. CrossRef CAS PubMed Web of Science Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Oxford Diffraction (2006). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1556

doi:10.1107/S1600536811019295

Open

access