organic compounds
4-[(E)-Phenyliminomethyl]benzonitrile
aGovernment College University, Department of Chemistry, Lahore, Pakistan, and bUniversity of Sargodha, Department of Physics, Sargodha, Pakistan
*Correspondence e-mail: dmntahir_uos@yahoo.com
In the molecule of the title compound, C14H10N2, the two aromatic rings are oriented at a dihedral angle of 32.22 (6)°. In the intermolecular C—H⋯N hydrogen bonds link the molecules into centrosymmetric R22(10) dimers. A weak π–π interaction between the cyanobenzene rings, with a centroid–centroid distance of 3.8447 (3) Å, further stabilizes the There is also a C—H⋯π interaction between the aniline ring and a CH group of the cyanobenzene ring.
Related literature
For related structures, see: Ojala et al. (2002). For ring motif details, see: Bernstein et al. (1995); Etter (1990). For bond-length data, see: Allen et al. (1987).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell APEX2; data reduction: SAINT (Bruker, 2007); 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, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON.
Supporting information
10.1107/S1600536808008672/hk2445sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808008672/hk2445Isup2.hkl
The starting materials employed were first purified by distillation or crystallization just before use. The experiment was performed in stoppered flask at room temperature. The title compound was synthesized by using equimolecular mixture of aniline (5 mmol) and p-cyanobenzaldehyde (5 mmol) of pH = 9 in aqueous medium. The product was precipitated after a few minutes, and separated by filtration, washed with a small amount of water and dried for 2 d at room temperature in a vacuum desicator. The dried filtrate was used for X-ray analysis (yield; 53.09%, m.p. 339 K).
H atoms were located in a difference syntheses and refined [C-H = 0.949 (15)-0.999 (12) Å and Uiso(H) = 1.2Ueq(C)].
Data collection: APEX2 (Bruker, 2007); cell
APEX2 (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003)..C14H10N2 | F(000) = 432 |
Mr = 206.24 | Dx = 1.226 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2883 reflections |
a = 7.2673 (4) Å | θ = 2.4–28.7° |
b = 10.0287 (7) Å | µ = 0.07 mm−1 |
c = 15.4306 (12) Å | T = 296 K |
β = 96.177 (2)° | Prismatic, yellow |
V = 1118.08 (13) Å3 | 0.20 × 0.15 × 0.12 mm |
Z = 4 |
Bruker Kappa-APEXII CCD diffractometer | 2883 independent reflections |
Radiation source: fine-focus sealed tube | 1423 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
Detector resolution: 7.30 pixels mm-1 | θmax = 28.7°, θmin = 2.4° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −13→13 |
Tmin = 0.983, Tmax = 0.994 | l = −20→20 |
13128 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.046 | All H-atom parameters refined |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.0364P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2883 reflections | Δρmax = 0.13 e Å−3 |
176 parameters | Δρmin = −0.10 e Å−3 |
Primary atom site location: structure-invariant direct methods |
C14H10N2 | V = 1118.08 (13) Å3 |
Mr = 206.24 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.2673 (4) Å | µ = 0.07 mm−1 |
b = 10.0287 (7) Å | T = 296 K |
c = 15.4306 (12) Å | 0.20 × 0.15 × 0.12 mm |
β = 96.177 (2)° |
Bruker Kappa-APEXII CCD diffractometer | 2883 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1423 reflections with I > 2σ(I) |
Tmin = 0.983, Tmax = 0.994 | Rint = 0.047 |
13128 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 176 parameters |
wR(F2) = 0.118 | All H-atom parameters refined |
S = 1.03 | Δρmax = 0.13 e Å−3 |
2883 reflections | Δρmin = −0.10 e Å−3 |
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 > 2sigma(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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.70615 (14) | 0.08086 (11) | 0.10666 (8) | 0.0518 (3) | |
N2 | 0.05182 (19) | 0.57458 (14) | −0.13327 (10) | 0.0855 (5) | |
C1 | 0.57569 (17) | 0.23345 (13) | −0.00193 (9) | 0.0462 (4) | |
C2 | 0.40486 (19) | 0.23930 (15) | 0.03050 (10) | 0.0559 (4) | |
H2 | 0.3870 (17) | 0.1816 (14) | 0.0777 (9) | 0.067* | |
C3 | 0.27073 (19) | 0.32560 (16) | −0.00409 (10) | 0.0593 (4) | |
H3 | 0.1494 (18) | 0.3263 (13) | 0.0181 (9) | 0.071* | |
C4 | 0.30456 (17) | 0.40866 (13) | −0.07259 (9) | 0.0493 (4) | |
C5 | 0.4727 (2) | 0.40351 (15) | −0.10663 (10) | 0.0538 (4) | |
H5 | 0.4929 (16) | 0.4628 (13) | −0.1547 (9) | 0.065* | |
C6 | 0.60682 (19) | 0.31589 (15) | −0.07083 (10) | 0.0528 (4) | |
H6 | 0.7273 (17) | 0.3117 (13) | −0.0919 (9) | 0.063* | |
C7 | 0.72303 (19) | 0.14630 (14) | 0.03760 (10) | 0.0519 (4) | |
H7 | 0.8385 (17) | 0.1419 (12) | 0.0080 (8) | 0.062* | |
C8 | 0.1639 (2) | 0.50057 (16) | −0.10713 (10) | 0.0610 (4) | |
C9 | 0.85826 (18) | 0.00574 (13) | 0.14575 (9) | 0.0476 (4) | |
C10 | 0.8196 (2) | −0.11183 (15) | 0.18708 (10) | 0.0569 (4) | |
H10 | 0.6901 (18) | −0.1361 (13) | 0.1860 (9) | 0.068* | |
C11 | 0.9612 (2) | −0.18768 (16) | 0.22793 (10) | 0.0657 (5) | |
H11 | 0.9274 (18) | −0.2675 (15) | 0.2552 (10) | 0.079* | |
C12 | 1.1415 (2) | −0.14576 (17) | 0.22995 (11) | 0.0668 (5) | |
H12 | 1.2406 (18) | −0.1973 (15) | 0.2609 (10) | 0.080* | |
C13 | 1.1803 (2) | −0.02736 (18) | 0.19159 (11) | 0.0684 (5) | |
H13 | 1.305 (2) | 0.0051 (15) | 0.1918 (9) | 0.082* | |
C14 | 1.03990 (19) | 0.04859 (16) | 0.14922 (11) | 0.0605 (4) | |
H14 | 1.0655 (18) | 0.1354 (14) | 0.1248 (9) | 0.073* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0550 (7) | 0.0462 (7) | 0.0531 (8) | 0.0004 (5) | 0.0010 (6) | 0.0009 (6) |
N2 | 0.0759 (9) | 0.0934 (11) | 0.0861 (11) | 0.0287 (9) | 0.0031 (8) | 0.0113 (9) |
C1 | 0.0490 (8) | 0.0449 (8) | 0.0445 (9) | 0.0007 (6) | 0.0040 (7) | −0.0042 (7) |
C2 | 0.0552 (8) | 0.0586 (10) | 0.0550 (11) | −0.0002 (8) | 0.0104 (8) | 0.0092 (8) |
C3 | 0.0482 (8) | 0.0703 (11) | 0.0606 (11) | 0.0040 (8) | 0.0109 (8) | 0.0044 (9) |
C4 | 0.0509 (8) | 0.0485 (9) | 0.0473 (9) | 0.0033 (7) | −0.0005 (7) | −0.0045 (7) |
C5 | 0.0621 (9) | 0.0525 (9) | 0.0470 (10) | 0.0015 (7) | 0.0070 (8) | 0.0037 (7) |
C6 | 0.0511 (8) | 0.0595 (10) | 0.0490 (10) | 0.0035 (8) | 0.0102 (7) | 0.0008 (8) |
C7 | 0.0531 (8) | 0.0507 (9) | 0.0518 (10) | 0.0023 (7) | 0.0060 (7) | −0.0034 (8) |
C8 | 0.0597 (9) | 0.0658 (11) | 0.0571 (11) | 0.0072 (9) | 0.0036 (8) | −0.0016 (9) |
C9 | 0.0559 (8) | 0.0414 (8) | 0.0447 (9) | 0.0025 (7) | 0.0024 (7) | −0.0017 (7) |
C10 | 0.0656 (9) | 0.0498 (9) | 0.0535 (10) | −0.0058 (8) | −0.0024 (8) | 0.0003 (8) |
C11 | 0.0921 (12) | 0.0461 (10) | 0.0556 (11) | −0.0021 (9) | −0.0072 (9) | 0.0045 (8) |
C12 | 0.0790 (12) | 0.0624 (11) | 0.0565 (11) | 0.0186 (9) | −0.0047 (9) | 0.0014 (9) |
C13 | 0.0580 (9) | 0.0749 (12) | 0.0718 (12) | 0.0052 (9) | 0.0051 (9) | 0.0107 (10) |
C14 | 0.0570 (9) | 0.0559 (9) | 0.0682 (12) | 0.0006 (8) | 0.0046 (8) | 0.0136 (9) |
N1—C7 | 1.2686 (17) | C6—H6 | 0.967 (12) |
N1—C9 | 1.4177 (16) | C7—H7 | 0.999 (12) |
N2—C8 | 1.1429 (17) | C9—C10 | 1.3835 (18) |
C1—C6 | 1.3845 (19) | C9—C14 | 1.3838 (18) |
C1—C2 | 1.3888 (17) | C10—C11 | 1.376 (2) |
C1—C7 | 1.4635 (18) | C10—H10 | 0.971 (12) |
C2—C3 | 1.3683 (19) | C11—C12 | 1.373 (2) |
C2—H2 | 0.950 (14) | C11—H11 | 0.949 (15) |
C3—C4 | 1.3883 (19) | C12—C13 | 1.370 (2) |
C3—H3 | 0.979 (13) | C12—H12 | 0.970 (14) |
C4—C5 | 1.3823 (19) | C13—C14 | 1.3801 (19) |
C4—C8 | 1.436 (2) | C13—H13 | 0.965 (14) |
C5—C6 | 1.3823 (19) | C14—H14 | 0.975 (14) |
C5—H5 | 0.975 (13) | ||
C7—N1—C9 | 119.40 (12) | C1—C7—H7 | 116.7 (8) |
C6—C1—C2 | 118.54 (13) | N2—C8—C4 | 178.87 (17) |
C6—C1—C7 | 120.26 (12) | C10—C9—C14 | 119.13 (13) |
C2—C1—C7 | 121.16 (13) | C10—C9—N1 | 117.48 (12) |
C3—C2—C1 | 120.87 (14) | C14—C9—N1 | 123.25 (13) |
C3—C2—H2 | 122.3 (8) | C11—C10—C9 | 120.22 (14) |
C1—C2—H2 | 116.8 (8) | C11—C10—H10 | 123.0 (8) |
C2—C3—C4 | 119.97 (14) | C9—C10—H10 | 116.8 (8) |
C2—C3—H3 | 119.9 (8) | C12—C11—C10 | 120.37 (16) |
C4—C3—H3 | 120.1 (8) | C12—C11—H11 | 122.7 (9) |
C5—C4—C3 | 120.20 (13) | C10—C11—H11 | 116.9 (9) |
C5—C4—C8 | 120.42 (13) | C13—C12—C11 | 119.72 (16) |
C3—C4—C8 | 119.37 (13) | C13—C12—H12 | 119.9 (8) |
C6—C5—C4 | 119.08 (14) | C11—C12—H12 | 120.3 (8) |
C6—C5—H5 | 122.3 (7) | C12—C13—C14 | 120.48 (16) |
C4—C5—H5 | 118.6 (7) | C12—C13—H13 | 121.9 (9) |
C5—C6—C1 | 121.34 (14) | C14—C13—H13 | 117.6 (9) |
C5—C6—H6 | 121.2 (8) | C13—C14—C9 | 120.02 (14) |
C1—C6—H6 | 117.5 (8) | C13—C14—H14 | 121.0 (8) |
N1—C7—C1 | 121.76 (13) | C9—C14—H14 | 118.9 (8) |
N1—C7—H7 | 121.6 (7) | ||
C6—C1—C2—C3 | −0.7 (2) | C2—C1—C7—N1 | −5.6 (2) |
C7—C1—C2—C3 | 176.87 (14) | C7—N1—C9—C10 | −146.46 (13) |
C1—C2—C3—C4 | 0.1 (2) | C7—N1—C9—C14 | 37.8 (2) |
C2—C3—C4—C5 | 0.7 (2) | C14—C9—C10—C11 | −2.7 (2) |
C2—C3—C4—C8 | −178.79 (13) | N1—C9—C10—C11 | −178.56 (14) |
C3—C4—C5—C6 | −0.8 (2) | C9—C10—C11—C12 | 1.6 (2) |
C8—C4—C5—C6 | 178.69 (13) | C10—C11—C12—C13 | 0.5 (3) |
C4—C5—C6—C1 | 0.1 (2) | C11—C12—C13—C14 | −1.5 (3) |
C2—C1—C6—C5 | 0.6 (2) | C12—C13—C14—C9 | 0.4 (3) |
C7—C1—C6—C5 | −176.99 (12) | C10—C9—C14—C13 | 1.6 (2) |
C9—N1—C7—C1 | −175.33 (11) | N1—C9—C14—C13 | 177.28 (14) |
C6—C1—C7—N1 | 172.00 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N2i | 0.980 (13) | 2.616 (14) | 3.473 (2) | 146.1 (10) |
C5—H5···Cgii | 0.975 (13) | 2.650 (14) | 3.5970 (17) | 163.9 (11) |
Symmetry codes: (i) −x, −y+1, −z; (ii) x−1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C14H10N2 |
Mr | 206.24 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 7.2673 (4), 10.0287 (7), 15.4306 (12) |
β (°) | 96.177 (2) |
V (Å3) | 1118.08 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.20 × 0.15 × 0.12 |
Data collection | |
Diffractometer | Bruker Kappa-APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.983, 0.994 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13128, 2883, 1423 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.676 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.118, 1.03 |
No. of reflections | 2883 |
No. of parameters | 176 |
No. of restraints | ? |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.13, −0.10 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Farrugia, 1999) and PLATON (Spek, 2003)..
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N2i | 0.980 (13) | 2.616 (14) | 3.473 (2) | 146.1 (10) |
C5—H5···Cgii | 0.975 (13) | 2.650 (14) | 3.5970 (17) | 163.9 (11) |
Symmetry codes: (i) −x, −y+1, −z; (ii) x−1/2, −y+1/2, z−1/2. |
Acknowledgements
The authors acknowledge the Higher Education Commision, Islamabad, Pakistan, for funding the purchase of the diffractometer.
References
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The crystal structures of p-halo-N-(p-cyanobenzylidene)- aniline and p-cyano-N-(p-halobenzylidene)aniline, (halo = bromo and chloro) (Ojala et al., 2002) have been reported, previously. The title compound, (I), differs due to no attachment of halogen atoms. It is prepared in aqueous medium and we report herein its crystal structure.
The molecule of (I), (Fig. 1), is a Schiff base ligand of aniline and p-cyanobenzaldehyde. The bond lengths (Allen et al., 1987) and angles are generally within normal ranges. Rings A (C1-C6) and B (C9-C14) are, of course, planar, and they are oriented at a dihedral angle of 32.22 (6)°.
In the crystal structure, intermolecular C-H···N hydrogen bonds (Table 1) link the molecules into centrosymmetric R22(10) dimers (Fig. 2) (Bernstein et al., 1995; Etter, 1990), in which they may be effective in the stabilization of the structure. A weak π···π interaction between the A rings, at x, y, z and 1 - x, 1 - y, -z, further stabilizes the structure, with a centroid-centroid distance of 3.8447 (3) Å. There is also a C—H···π interaction between the ring B at x - 1/2, 1/2 -y, z - 1/2 and C5-H5, with H5-centroid distance of 2.650 (14) Å.