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ISSN: 2056-9890

Crystal structure of 2-(4-methyl­benzyl­­idene)malono­nitrile

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.

1. Related literature

For the pharmacological activity of benzyl­idenemalono­nitriles, see: Gazit et al. (1989[Gazit, A., Yaish, P., Gilon, C. & Levitzki, A. (1989). J. Med. Chem. 32, 2344-2352.]); Levitzki & Mishani (2006[Levitzki, A. & Mishani, E. (2006). Annu. Rev. Biochem. 75, 93-109.]). For the use of benzyl­idenemalono­nitrile derivatives in the preparation of heterocyclic compounds, see: Kolla & Lee (2011[Kolla, S. R. & Lee, Y. R. (2011). Tetrahedron, 67, 8271-8275.]); Gao & Du (2012[Gao, Y. & Du, D.-M. (2012). Tetrahedron Asymmetry, 23, 1343-1349.]); Li et al. (2006[Li, X., Song, L., Xing, C., Zhao, J. & Zhu, S. (2006). Tetrahedron, 62, 2255-2263.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • C11H8N2

  • Mr = 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[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.637, Tmax = 0.746

  • 7629 measured reflections

  • 1923 independent reflections

  • 1535 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.20 e Å−3

  • Δρmin = −0.18 e Å−3

Data collection: APEX2 (Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]); software used to prepare material for publication: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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.

Refinement top

H atoms were located in a difference Fourier map and treated as riding: C–H = 0.93 - 0.96 Å with Uiso(H) = 1.5Ue(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms.

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
C11H8N2F(000) = 176
Mr = 168.19Dx = 1.229 Mg m3
Triclinic, P1Melting point: 404 K
a = 7.0043 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.5270 (5) ÅCell parameters from 1923 reflections
c = 9.5396 (6) Åθ = 3.0–27.1°
α = 106.757 (4)°µ = 0.08 mm1
β = 96.592 (4)°T = 296 K
γ = 105.204 (4)°Block, colourless
V = 454.75 (5) Å30.40 × 0.34 × 0.30 mm
Z = 2
Data collection top
Bruker X8 APEX
diffractometer
1923 independent reflections
Radiation source: fine-focus sealed tube1535 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ϕ and ω scansθmax = 27.1°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
h = 88
Tmin = 0.637, Tmax = 0.746k = 99
7629 measured reflectionsl = 1212
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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0567P)2 + 0.1308P]
where P = (Fo2 + 2Fc2)/3
1923 reflections(Δ/σ)max < 0.001
118 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C11H8N2γ = 105.204 (4)°
Mr = 168.19V = 454.75 (5) Å3
Triclinic, P1Z = 2
a = 7.0043 (5) ÅMo Kα radiation
b = 7.5270 (5) ŵ = 0.08 mm1
c = 9.5396 (6) ÅT = 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)
Tmin = 0.637, Tmax = 0.746Rint = 0.022
7629 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.132H-atom parameters constrained
S = 1.06Δρmax = 0.20 e Å3
1923 reflectionsΔρmin = 0.18 e Å3
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
xyzUiso*/Ueq
C10.3051 (2)0.0064 (2)0.22452 (16)0.0427 (4)
C20.1662 (3)0.0403 (2)0.30984 (17)0.0488 (4)
H20.02850.01700.26950.059*
C30.2306 (2)0.1710 (2)0.45410 (17)0.0461 (4)
H30.13520.20040.50950.055*
C40.4357 (2)0.25984 (19)0.51829 (15)0.0365 (3)
C50.5753 (2)0.2128 (2)0.43179 (17)0.0448 (4)
H50.71310.27010.47140.054*
C60.5089 (2)0.0816 (2)0.28791 (17)0.0476 (4)
H60.60360.05160.23210.057*
C70.2353 (3)0.1472 (3)0.06642 (17)0.0555 (4)
H7A0.34300.19630.03650.083*
H7B0.19770.08110.00060.083*
H7C0.12090.25390.06150.083*
C80.4888 (2)0.3945 (2)0.67091 (15)0.0389 (3)
H80.37900.41330.71260.047*
C90.6697 (2)0.4962 (2)0.76167 (15)0.0386 (3)
C100.6819 (2)0.6205 (2)0.91126 (16)0.0435 (4)
C110.8637 (2)0.4944 (2)0.72682 (17)0.0476 (4)
N10.6955 (2)0.7184 (2)1.03069 (15)0.0601 (4)
N21.0205 (2)0.4968 (3)0.70532 (18)0.0734 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0507 (9)0.0391 (7)0.0347 (7)0.0136 (7)0.0069 (7)0.0079 (6)
C20.0390 (9)0.0520 (9)0.0436 (8)0.0077 (7)0.0051 (7)0.0059 (7)
C30.0398 (9)0.0523 (9)0.0417 (8)0.0131 (7)0.0140 (7)0.0080 (7)
C40.0388 (8)0.0379 (7)0.0320 (7)0.0119 (6)0.0091 (6)0.0098 (6)
C50.0381 (9)0.0524 (9)0.0377 (8)0.0135 (7)0.0090 (6)0.0061 (6)
C60.0467 (10)0.0570 (9)0.0368 (8)0.0210 (8)0.0132 (7)0.0060 (7)
C70.0619 (12)0.0541 (9)0.0381 (8)0.0160 (8)0.0038 (8)0.0012 (7)
C80.0406 (8)0.0428 (7)0.0331 (7)0.0139 (6)0.0128 (6)0.0096 (6)
C90.0419 (9)0.0405 (7)0.0326 (7)0.0146 (6)0.0110 (6)0.0083 (6)
C100.0412 (9)0.0464 (8)0.0384 (8)0.0118 (7)0.0102 (7)0.0084 (6)
C110.0442 (10)0.0522 (9)0.0367 (8)0.0146 (7)0.0066 (7)0.0014 (6)
N10.0602 (10)0.0649 (9)0.0403 (7)0.0147 (7)0.0136 (7)0.0016 (6)
N20.0460 (9)0.0935 (13)0.0613 (10)0.0225 (9)0.0134 (7)0.0043 (8)
Geometric parameters (Å, º) top
C1—C61.384 (2)C6—H60.9300
C1—C21.389 (2)C7—H7A0.9600
C1—C71.508 (2)C7—H7B0.9600
C2—C31.382 (2)C7—H7C0.9600
C2—H20.9300C8—C91.341 (2)
C3—C41.395 (2)C8—H80.9300
C3—H30.9300C9—C111.438 (2)
C4—C51.3998 (19)C9—C101.4419 (18)
C4—C81.4535 (18)C10—N11.1420 (19)
C5—C61.381 (2)C11—N21.137 (2)
C5—H50.9300
C6—C1—C2118.20 (14)C5—C6—H6119.1
C6—C1—C7121.04 (14)C1—C6—H6119.1
C2—C1—C7120.75 (15)C1—C7—H7A109.5
C3—C2—C1120.64 (15)C1—C7—H7B109.5
C3—C2—H2119.7H7A—C7—H7B109.5
C1—C2—H2119.7C1—C7—H7C109.5
C2—C3—C4121.29 (14)H7A—C7—H7C109.5
C2—C3—H3119.4H7B—C7—H7C109.5
C4—C3—H3119.4C9—C8—C4130.79 (13)
C3—C4—C5117.90 (13)C9—C8—H8114.6
C3—C4—C8117.33 (12)C4—C8—H8114.6
C5—C4—C8124.77 (14)C8—C9—C11126.43 (13)
C6—C5—C4120.21 (15)C8—C9—C10120.02 (13)
C6—C5—H5119.9C11—C9—C10113.54 (13)
C4—C5—H5119.9N1—C10—C9178.50 (17)
C5—C6—C1121.76 (14)N2—C11—C9177.20 (17)

Experimental details

Crystal data
Chemical formulaC11H8N2
Mr168.19
Crystal system, space groupTriclinic, 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)
V3)454.75 (5)
Z2
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.40 × 0.34 × 0.30
Data collection
DiffractometerBruker X8 APEX
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2009)
Tmin, Tmax0.637, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
7629, 1923, 1535
Rint0.022
(sin θ/λ)max1)0.641
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.132, 1.06
No. of reflections1923
No. of parameters118
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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.

References

First citationBruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationGao, Y. & Du, D.-M. (2012). Tetrahedron Asymmetry, 23, 1343–1349.  Web of Science CrossRef CAS Google Scholar
First citationGazit, A., Yaish, P., Gilon, C. & Levitzki, A. (1989). J. Med. Chem. 32, 2344–2352.  CrossRef CAS PubMed Web of Science Google Scholar
First citationKolla, S. R. & Lee, Y. R. (2011). Tetrahedron, 67, 8271–8275.  Web of Science CrossRef CAS Google Scholar
First citationLevitzki, A. & Mishani, E. (2006). Annu. Rev. Biochem. 75, 93–109.  Web of Science CrossRef PubMed CAS Google Scholar
First citationLi, X., Song, L., Xing, C., Zhao, J. & Zhu, S. (2006). Tetrahedron, 62, 2255–2263.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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