4-[(E)-Phenyl­imino­meth­yl]benzonitrile

In the mol­ecule of the title compound, C₁₄H₁₀N₂, the two aromatic rings are oriented at a dihedral angle of 32.22 (6)°. In the crystal structure, 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 crystal structure. There is also a C—H...π inter­action between the aniline ring and a CH group of the cyanobenzene ring.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.047
• wR factor = 0.119
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C4     -   C8      ..       7.05 su

Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         49 Perc.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C4     -   C8     ...       1.44 Ang.

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

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.

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).

S2. Experimental

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).

S3. Refinement

H atoms were located in a difference syntheses and refined [C-H = 0.949 (15)-0.999 (12) Å and U_iso(H) = 1.2U_eq(C)].

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: 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)..

Figures

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial packing diagram of (I), showing the formation of centro- symmetric R2^2(10) ring motifs. Hydrogen bonds are shown as dashed lines.

4-[(E)-Phenyliminomethyl]benzonitrile

Crystal data

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) Å^3	0.20 × 0.15 × 0.12 mm
Z = 4

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.046	All H-atom parameters refined
wR(F^2) = 0.118	w = 1/[σ^2(Fo^2) + (0.0364P)^2] where P = (Fo^2 + 2Fc^2)/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

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N2^i	0.980 (13)	2.616 (14)	3.473 (2)	146.1 (10)
C5—H5···Cg^ii	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.