Crystal structure of 2-(4-methyl­benzyl­idene)malono­nitrile

Amiri, O.; Rakib, E.M.; Hannioui, A.; Saadi, M.; El Ammari, L.

doi:10.1107/S1600536814024660

organic compounds

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ISSN: 2056-9890

Volume 70| Part 12| December 2014| Page o1263

doi:10.1107/S1600536814024660

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Crystal structure of 2-(4-methylbenzylidene)malononitrile

Ouafa Amiri,^a ^* El Mostapha Rakib,^a Abdellah Hannioui,^a Mohamed Saadi ^b and Lahcen El Ammari ^b

^aLaboratoire de Chimie Organique et Analytique, Université Sultan Moulay Slimane, Faculté des Sciences et Techniques, Béni-Mellal, BP 523, Morocco, and ^bLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: ouafa_amiri@yahoo.fr

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 8 November 2014; accepted 10 November 2014; online 15 November 2014)

The molecule of the title compound, C₁₁H₈N₂, is approximately planar (r.m.s.deviation for all non-H atoms = 0.023 Å). The malononitrile C—C—C angle is 113.54 (13)°. In the crystal, molecules stack head-to-tail along [010]. There are no significant intermolecular interactions present.

Keywords: crystal structure; benzylidene; malononitrile; tyrphostins; benzylidenemalononitrile derivatives.

CCDC reference: 1033522

1. Related literature

For the pharmacological activity of benzylidenemalononitriles, see: Gazit et al. (1989 ); Levitzki & Mishani (2006 ). For the use of benzylidenemalononitrile derivatives in the preparation of heterocyclic compounds, see: Kolla & Lee (2011 ); Gao & Du (2012 ); Li et al. (2006 ).

2. Experimental

2.1. Crystal data

C₁₁H₈N₂
M_r = 168.19
Triclinic, $[P \overline 1]$
a = 7.0043 (5) Å
b = 7.5270 (5) Å
c = 9.5396 (6) Å
α = 106.757 (4)°
β = 96.592 (4)°
γ = 105.204 (4)°
V = 454.75 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.40 × 0.34 × 0.30 mm

2.2. Data collection

Bruker X8 APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.637, T_max = 0.746
7629 measured reflections
1923 independent reflections
1535 reflections with I > 2σ(I)
R_int = 0.022

2.3. Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.132
S = 1.06
1923 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1033522

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814024660/su5017sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814024660/su5017Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814024660/su5017Isup3.cml

checkCIF report

Comment top

Pharmacological effects of benzylidenemalononitrile (BMN) compounds have been examined since the 1990's when several of their derivatives, referred to as tyrphostins, were recognized as specific inhibitors of epidermal growth factor tyrosine kinase (Gazit, et al., 1989). Subsequent design and testing of a series of BMNs revealed new specific inhibitors of various protein tyrosine kinases (Levitzki & Mishani, 2006). It is well known that the benzylidenemalononitrile derivatives are very useful reagents for the preparation of heterocyclic compounds (Kolla & Lee, 2011; Gao & Du, 2012; Li et al., 2006).

The title molecule is almost planar, Fig. 1, with an r.m.s. devation = 0.023 Å; the maximum deviation of -0.037 (2) Å was observed for atom C5. The malononitrile angle C10–C9–C11 is 113.58 (12)°.

In the crystal, molecules stack head-to-tail along [010]. There are no significant intermolecular interactions present.

Related literature top

For the pharmacological activity of benzylidenemalononitriles, see: Gazit et al. (1989); Levitzki & Mishani (2006). For the use of benzylidenemalononitrile derivatives in the preparation of heterocyclic compounds, see: Kolla & Lee (2011); Gao & Du (2012); Li et al. (2006).

Experimental top

In a 250 ml round bottom flask, 4-methylbenzaldehyde (10 mmol), malononitrile (10 mmol) and phosphorus pentoxide (3.54 mmol) have stirred mechanically for ten minutes in 25 ml absolute ethanol. The resulting reaction mixture was heated at reflux using a water bath. The reaction mixture was poured onto crushed ice after the completion of the reaction monitored by TLC. On stirring separation of the desired product took place. The solid was filtered, washed with petroleum ether, dried and recrystallized from ethanol (yield: 68%, m.p.: 404 K), yielding block-like colourless crystals.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

2-(4-Methylbenzylidene)malononitrile top

Crystal data top

C₁₁H₈N₂	F(000) = 176
M_r = 168.19	D_x = 1.229 Mg m⁻³
Triclinic, P1	Melting point: 404 K
a = 7.0043 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.5270 (5) Å	Cell parameters from 1923 reflections
c = 9.5396 (6) Å	θ = 3.0–27.1°
α = 106.757 (4)°	µ = 0.08 mm⁻¹
β = 96.592 (4)°	T = 296 K
γ = 105.204 (4)°	Block, colourless
V = 454.75 (5) Å³	0.40 × 0.34 × 0.30 mm
Z = 2

Data collection top

Bruker X8 APEX diffractometer	1923 independent reflections
Radiation source: fine-focus sealed tube	1535 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 27.1°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
T_min = 0.637, T_max = 0.746	k = −9→9
7629 measured reflections	l = −12→12

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.132	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0567P)² + 0.1308P] where P = (F_o² + 2F_c²)/3
1923 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₁H₈N₂	γ = 105.204 (4)°
M_r = 168.19	V = 454.75 (5) Å³
Triclinic, P1	Z = 2
a = 7.0043 (5) Å	Mo Kα radiation
b = 7.5270 (5) Å	µ = 0.08 mm⁻¹
c = 9.5396 (6) Å	T = 296 K
α = 106.757 (4)°	0.40 × 0.34 × 0.30 mm
β = 96.592 (4)°

Data collection top

Bruker X8 APEX diffractometer	1923 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1535 reflections with I > 2σ(I)
T_min = 0.637, T_max = 0.746	R_int = 0.022
7629 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.132	H-atom parameters constrained
S = 1.06	Δρ_max = 0.20 e Å⁻³
1923 reflections	Δρ_min = −0.18 e Å⁻³
118 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
C1	0.3051 (2)	−0.0064 (2)	0.22452 (16)	0.0427 (4)
C2	0.1662 (3)	0.0403 (2)	0.30984 (17)	0.0488 (4)
H2	0.0285	−0.0170	0.2695	0.059*
C3	0.2306 (2)	0.1710 (2)	0.45410 (17)	0.0461 (4)
H3	0.1352	0.2004	0.5095	0.055*
C4	0.4357 (2)	0.25984 (19)	0.51829 (15)	0.0365 (3)
C5	0.5753 (2)	0.2128 (2)	0.43179 (17)	0.0448 (4)
H5	0.7131	0.2701	0.4714	0.054*
C6	0.5089 (2)	0.0816 (2)	0.28791 (17)	0.0476 (4)
H6	0.6036	0.0516	0.2321	0.057*
C7	0.2353 (3)	−0.1472 (3)	0.06642 (17)	0.0555 (4)
H7A	0.3430	−0.1963	0.0365	0.083*
H7B	0.1977	−0.0811	0.0006	0.083*
H7C	0.1209	−0.2539	0.0615	0.083*
C8	0.4888 (2)	0.3945 (2)	0.67091 (15)	0.0389 (3)
H8	0.3790	0.4133	0.7126	0.047*
C9	0.6697 (2)	0.4962 (2)	0.76167 (15)	0.0386 (3)
C10	0.6819 (2)	0.6205 (2)	0.91126 (16)	0.0435 (4)
C11	0.8637 (2)	0.4944 (2)	0.72682 (17)	0.0476 (4)
N1	0.6955 (2)	0.7184 (2)	1.03069 (15)	0.0601 (4)
N2	1.0205 (2)	0.4968 (3)	0.70532 (18)	0.0734 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0507 (9)	0.0391 (7)	0.0347 (7)	0.0136 (7)	0.0069 (7)	0.0079 (6)
C2	0.0390 (9)	0.0520 (9)	0.0436 (8)	0.0077 (7)	0.0051 (7)	0.0059 (7)
C3	0.0398 (9)	0.0523 (9)	0.0417 (8)	0.0131 (7)	0.0140 (7)	0.0080 (7)
C4	0.0388 (8)	0.0379 (7)	0.0320 (7)	0.0119 (6)	0.0091 (6)	0.0098 (6)
C5	0.0381 (9)	0.0524 (9)	0.0377 (8)	0.0135 (7)	0.0090 (6)	0.0061 (6)
C6	0.0467 (10)	0.0570 (9)	0.0368 (8)	0.0210 (8)	0.0132 (7)	0.0060 (7)
C7	0.0619 (12)	0.0541 (9)	0.0381 (8)	0.0160 (8)	0.0038 (8)	0.0012 (7)
C8	0.0406 (8)	0.0428 (7)	0.0331 (7)	0.0139 (6)	0.0128 (6)	0.0096 (6)
C9	0.0419 (9)	0.0405 (7)	0.0326 (7)	0.0146 (6)	0.0110 (6)	0.0083 (6)
C10	0.0412 (9)	0.0464 (8)	0.0384 (8)	0.0118 (7)	0.0102 (7)	0.0084 (6)
C11	0.0442 (10)	0.0522 (9)	0.0367 (8)	0.0146 (7)	0.0066 (7)	0.0014 (6)
N1	0.0602 (10)	0.0649 (9)	0.0403 (7)	0.0147 (7)	0.0136 (7)	−0.0016 (6)
N2	0.0460 (9)	0.0935 (13)	0.0613 (10)	0.0225 (9)	0.0134 (7)	−0.0043 (8)

Geometric parameters (Å, º) top

C1—C6	1.384 (2)	C6—H6	0.9300
C1—C2	1.389 (2)	C7—H7A	0.9600
C1—C7	1.508 (2)	C7—H7B	0.9600
C2—C3	1.382 (2)	C7—H7C	0.9600
C2—H2	0.9300	C8—C9	1.341 (2)
C3—C4	1.395 (2)	C8—H8	0.9300
C3—H3	0.9300	C9—C11	1.438 (2)
C4—C5	1.3998 (19)	C9—C10	1.4419 (18)
C4—C8	1.4535 (18)	C10—N1	1.1420 (19)
C5—C6	1.381 (2)	C11—N2	1.137 (2)
C5—H5	0.9300

C6—C1—C2	118.20 (14)	C5—C6—H6	119.1
C6—C1—C7	121.04 (14)	C1—C6—H6	119.1
C2—C1—C7	120.75 (15)	C1—C7—H7A	109.5
C3—C2—C1	120.64 (15)	C1—C7—H7B	109.5
C3—C2—H2	119.7	H7A—C7—H7B	109.5
C1—C2—H2	119.7	C1—C7—H7C	109.5
C2—C3—C4	121.29 (14)	H7A—C7—H7C	109.5
C2—C3—H3	119.4	H7B—C7—H7C	109.5
C4—C3—H3	119.4	C9—C8—C4	130.79 (13)
C3—C4—C5	117.90 (13)	C9—C8—H8	114.6
C3—C4—C8	117.33 (12)	C4—C8—H8	114.6
C5—C4—C8	124.77 (14)	C8—C9—C11	126.43 (13)
C6—C5—C4	120.21 (15)	C8—C9—C10	120.02 (13)
C6—C5—H5	119.9	C11—C9—C10	113.54 (13)
C4—C5—H5	119.9	N1—C10—C9	178.50 (17)
C5—C6—C1	121.76 (14)	N2—C11—C9	177.20 (17)

Experimental details

Crystal data
Chemical formula	C₁₁H₈N₂
M_r	168.19
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.0043 (5), 7.5270 (5), 9.5396 (6)
α, β, γ (°)	106.757 (4), 96.592 (4), 105.204 (4)
V (Å³)	454.75 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.40 × 0.34 × 0.30

Data collection
Diffractometer	Bruker X8 APEX diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.637, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	7629, 1923, 1535
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.132, 1.06
No. of reflections	1923
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.18

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements, and the University Sultan Moulay Slimane, Beni-Mellal, Morocco, for financial support.

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