Acta Cryst. (2009). E65, o371 [ doi:10.1107/S1600536809002244 ]
The molecule of the title compound, C17H10N4O, has crystallographically imposed C2 symmetry. The urea group and the benzene ring are nearly coplanar, the dihedral angle between them being 4.15 (7)°. The crystal packing is stabilized by aromatic ![[pi]](/logos/entities/pi_rmgif.gif)
- stacking interactions, with a centroid-to-centroid separation of 3.833 (4) Å.
A mixture of 4-cyanobenzaldehyde (0.53 g, 4 mmol), urea (0.36 g, 6 mmol) and NH4Cl (0.10 g, 1.6 mmol) was heated with stirring at 100°C in 5 ml acetic acid for 5 h. After cooling, the reaction mixture was washed with cold water (3 × 50 ml) and the residue recrystallized from ethyl acetate/n-hexane (1:2 v/v) to afford the title compound (0.57 g, 50%). Single crystals suitable for X-ray structure analysis were obtained by the slow evaporation of an ethyl acetate solution in air.
All H atoms were placed in calculated positions and refined using a riding model aproximation, with C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(C).
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./rz2289fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Unlabelled atoms are related to the labelled atoms by (-x, y, 1/2 - z). |
| C17H10N4O | F(000) = 592 |
| Mr = 286.29 | Dx = 1.283 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 1587 reflections |
| a = 10.552 (4) Å | θ = 2.6–27.4° |
| b = 11.687 (5) Å | µ = 0.08 mm−1 |
| c = 12.198 (3) Å | T = 291 K |
| β = 99.94 (4)° | Block, yellow |
| V = 1481.7 (9) Å3 | 0.36 × 0.30 × 0.28 mm |
| Z = 4 |
| Rigaku Mercury2 diffractometer | 1423 independent reflections |
| Radiation source: fine-focus sealed tube | 1107 reflections with I > 2σ(I) |
| graphite | Rint = 0.041 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 26.0°, θmin = 2.9° |
| CCD profile fitting scans | h = −12→12 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −14→14 |
| Tmin = 0.96, Tmax = 0.98 | l = −15→15 |
| 6461 measured reflections |
| 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)] = 0.072 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.164 | H-atom parameters constrained |
| S = 1.06 | w = 1/[σ2(Fo2) + (0.0535P)2 + 1.99P] where P = (Fo2 + 2Fc2)/3 |
| 1423 reflections | (Δ/σ)max < 0.001 |
| 102 parameters | Δρmax = 0.43 e Å−3 |
| 1 restraint | Δρmin = −0.27 e Å−3 |
| C17H10N4O | V = 1481.7 (9) Å3 |
| Mr = 286.29 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 10.552 (4) Å | µ = 0.08 mm−1 |
| b = 11.687 (5) Å | T = 291 K |
| c = 12.198 (3) Å | 0.36 × 0.30 × 0.28 mm |
| β = 99.94 (4)° |
| Rigaku Mercury2 diffractometer | 1423 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1107 reflections with I > 2σ(I) |
| Tmin = 0.96, Tmax = 0.98 | Rint = 0.041 |
| 6461 measured reflections | θmax = 26.0° |
| R[F2 > 2σ(F2)] = 0.072 | H-atom parameters constrained |
| wR(F2) = 0.164 | Δρmax = 0.43 e Å−3 |
| S = 1.06 | Δρmin = −0.27 e Å−3 |
| 1423 reflections | Absolute structure: ? |
| 102 parameters | Flack parameter: ? |
| 1 restraint | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.0000 | 0.1727 (3) | 0.2500 | 0.0459 (8) | |
| C2 | 0.0655 (2) | 0.1864 (2) | 0.45184 (18) | 0.0476 (6) | |
| H2A | 0.0645 | 0.1068 | 0.4491 | 0.057* | |
| C3 | 0.1028 (2) | 0.2366 (2) | 0.56187 (18) | 0.0419 (6) | |
| C4 | 0.1265 (2) | 0.1659 (2) | 0.65419 (19) | 0.0505 (6) | |
| H4A | 0.1174 | 0.0872 | 0.6445 | 0.061* | |
| C5 | 0.1636 (2) | 0.2094 (2) | 0.7610 (2) | 0.0526 (7) | |
| H5A | 0.1790 | 0.1605 | 0.8220 | 0.063* | |
| C6 | 0.1773 (2) | 0.3265 (2) | 0.77534 (19) | 0.0484 (6) | |
| C7 | 0.2135 (3) | 0.3729 (2) | 0.8858 (2) | 0.0564 (7) | |
| C8 | 0.1546 (2) | 0.3991 (2) | 0.6841 (2) | 0.0544 (7) | |
| H8A | 0.1640 | 0.4777 | 0.6942 | 0.065* | |
| C9 | 0.1181 (2) | 0.3551 (2) | 0.5786 (2) | 0.0525 (7) | |
| H9A | 0.1034 | 0.4043 | 0.5179 | 0.063* | |
| N1 | 0.0325 (2) | 0.2397 (2) | 0.35441 (17) | 0.0643 (7) | |
| N2 | 0.2416 (3) | 0.4101 (2) | 0.9729 (2) | 0.0772 (8) | |
| O1 | 0.0000 | 0.0683 (2) | 0.2500 | 0.0655 (8) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0458 (18) | 0.055 (2) | 0.0363 (17) | 0.000 | 0.0039 (13) | 0.000 |
| C2 | 0.0485 (13) | 0.0509 (14) | 0.0428 (12) | −0.0062 (10) | 0.0065 (10) | −0.0032 (9) |
| C3 | 0.0412 (12) | 0.0466 (13) | 0.0384 (12) | −0.0019 (9) | 0.0081 (9) | 0.0009 (9) |
| C4 | 0.0628 (15) | 0.0472 (14) | 0.0412 (13) | −0.0034 (11) | 0.0085 (10) | −0.0011 (10) |
| C5 | 0.0608 (16) | 0.0575 (16) | 0.0394 (12) | 0.0015 (12) | 0.0087 (11) | 0.0065 (11) |
| C6 | 0.0449 (13) | 0.0595 (15) | 0.0404 (13) | 0.0016 (11) | 0.0058 (10) | −0.0095 (11) |
| C7 | 0.0638 (16) | 0.0577 (16) | 0.0468 (15) | 0.0041 (12) | 0.0073 (12) | −0.0036 (12) |
| C8 | 0.0626 (16) | 0.0484 (14) | 0.0509 (14) | −0.0036 (11) | 0.0063 (11) | −0.0025 (11) |
| C9 | 0.0604 (15) | 0.0522 (14) | 0.0435 (13) | −0.0021 (12) | 0.0049 (11) | 0.0055 (11) |
| N1 | 0.0696 (15) | 0.0745 (17) | 0.0472 (12) | 0.0003 (12) | 0.0055 (10) | 0.0023 (10) |
| N2 | 0.106 (2) | 0.0707 (17) | 0.0511 (14) | 0.0061 (14) | 0.0034 (13) | −0.0151 (12) |
| O1 | 0.098 (2) | 0.0506 (16) | 0.0442 (14) | 0.000 | 0.0009 (13) | 0.000 |
| C1—O1 | 1.221 (4) | C4—H4A | 0.9300 |
| C1—N1 | 1.484 (3) | C5—C6 | 1.384 (4) |
| C1—N1i | 1.484 (3) | C5—H5A | 0.9300 |
| C2—N1 | 1.334 (3) | C6—C8 | 1.387 (4) |
| C2—C3 | 1.455 (3) | C6—C7 | 1.442 (3) |
| C2—H2A | 0.9300 | C7—N2 | 1.138 (3) |
| C3—C4 | 1.384 (3) | C8—C9 | 1.377 (3) |
| C3—C9 | 1.405 (3) | C8—H8A | 0.9300 |
| C4—C5 | 1.390 (3) | C9—H9A | 0.9300 |
| O1—C1—N1 | 121.83 (16) | C6—C5—H5A | 120.5 |
| O1—C1—N1i | 121.83 (16) | C4—C5—H5A | 120.5 |
| N1—C1—N1i | 116.3 (3) | C5—C6—C8 | 120.2 (2) |
| N1—C2—C3 | 128.4 (2) | C5—C6—C7 | 119.7 (2) |
| N1—C2—H2A | 115.8 | C8—C6—C7 | 120.1 (2) |
| C3—C2—H2A | 115.8 | N2—C7—C6 | 179.5 (3) |
| C4—C3—C9 | 118.0 (2) | C9—C8—C6 | 120.2 (2) |
| C4—C3—C2 | 119.5 (2) | C9—C8—H8A | 119.9 |
| C9—C3—C2 | 122.5 (2) | C6—C8—H8A | 119.9 |
| C3—C4—C5 | 121.8 (2) | C8—C9—C3 | 120.7 (2) |
| C3—C4—H4A | 119.1 | C8—C9—H9A | 119.7 |
| C5—C4—H4A | 119.1 | C3—C9—H9A | 119.7 |
| C6—C5—C4 | 119.1 (2) | C2—N1—C1 | 120.3 (3) |
| Symmetry codes: (i) −x, y, −z+1/2. |
The authors thank the Jiangsu Planned Projects for Postdoctoral Research Funds (grant No. 0802003B) and Professor Dr Rengen Xiong.
Íkizler, A. A. & Sancak, K. (1992). Monatsh. Chem. 123, 257–263.
Martínez-García, A., Ortiz, M., Martínez, R., Ortiz, P. & Reguera, E. (2004). Ind. Crops Prod. 19, 99–106.
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Nitriles are parent compounds for the preparation of various functional organic materials having imidazole, triazole, or thidiazole functionalities (Íkizler & Sancak, 1992). The Schiff-base compounds derived from the condensation of urea with alkynes are very few (Martínez-García et al., 2004) because of the low reactivity of the NH2 group of urea. Here we report the crystal structure of the title compound, which was obtained by the reaction of urea with 4-cyanobenzaldehyde in acetic acid with ammonium chloride as a catalyzer.
The molecule of the title compound (Fig. 1) possesses a crystallographically imposed C2 symmetry, with atoms C1 and O1 located on a two-fold axis. The urea group and the aromatic rings are nearly coplanar, forming a dihedral angle of 4.15 (7)°. In the crystal packing, molecules are linked along the a axis by aromatic π–π stacking interactions, with centroid-to-centroid separations of 3.833 (4) Å, perpendicular interplanar distances of 3.474 (4) Å and centroid–centroid offsets of 1.620 (3) Å.