Acta Cryst. (2011). E67, o832 [ doi:10.1107/S1600536811008130 ]
In the title molecule, C16H14N2O2, the fused cyclohexene and pyran rings adopt an envelope and a flattened boat conformation, respectively. In the crystal, N-H
N and N-HO hydrogen bonds link the molecules into corrugated sheets parallel to the bc plane.
Malononitrile (10 mmol), 1,3-cyclohexanedione (10 mmol),and benzaldehyde(10 mmol)was dissolved in 20 ml e thanol ml in a round-bottom flask. The mixture was warmed, with agitation, to 353 K over a period of 3 h. The resulting solution was cooled. Crystal of (I) suitable for X-ray diffraction analysis were obtained by slow evaporation.
All H atoms were placed in geometrically idealized positions (N—H 0.86 and C—H 0.93–0.98 Å) and treated as riding on their parent atoms, with Uiso(H) = 1.2Ueq(C) (C,N).
Data collection: SMART (Bruker, 2007); cell refinement: SAINT (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: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./cv5040fig1thm.gif)
| Fig. 1. View of (I) showing the atomic numbering and 30% probability displacement ellipsoids. |
| C16H14N2O2 | F(000) = 1120 |
| Mr = 266.29 | Dx = 1.229 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 20.210 (2) Å | Cell parameters from 851 reflections |
| b = 8.8161 (5) Å | θ = 2.5–19.1° |
| c = 16.3862 (13) Å | µ = 0.08 mm−1 |
| β = 99.537 (1)° | T = 298 K |
| V = 2879.2 (4) Å3 | Block, red |
| Z = 8 | 0.32 × 0.21 × 0.15 mm |
| Bruker SMART APEX CCD area-detector diffractometer | 2535 independent reflections |
| Radiation source: fine-focus sealed tube | 1083 reflections with I > 2σ(I) |
| graphite | Rint = 0.063 |
| φ and ω scans | θmax = 25.0°, θmin = 2.0° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −24→17 |
| Tmin = 0.974, Tmax = 0.988 | k = −10→10 |
| 7077 measured reflections | l = −19→19 |
| 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)] = 0.045 | H-atom parameters constrained |
| wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.0454P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 0.81 | (Δ/σ)max = 0.001 |
| 2535 reflections | Δρmax = 0.12 e Å−3 |
| 182 parameters | Δρmin = −0.11 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0017 (2) |
| C16H14N2O2 | V = 2879.2 (4) Å3 |
| Mr = 266.29 | Z = 8 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 20.210 (2) Å | µ = 0.08 mm−1 |
| b = 8.8161 (5) Å | T = 298 K |
| c = 16.3862 (13) Å | 0.32 × 0.21 × 0.15 mm |
| β = 99.537 (1)° |
| Bruker SMART APEX CCD area-detector diffractometer | 2535 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1083 reflections with I > 2σ(I) |
| Tmin = 0.974, Tmax = 0.988 | Rint = 0.063 |
| 7077 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
| wR(F2) = 0.114 | Δρmax = 0.12 e Å−3 |
| S = 0.81 | Δρmin = −0.11 e Å−3 |
| 2535 reflections | Absolute structure: ? |
| 182 parameters | Flack parameter: ? |
| 0 restraints | 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 | ||
| O1 | 0.10075 (8) | 0.98207 (19) | 1.01594 (9) | 0.0666 (5) | |
| C1 | 0.07153 (12) | 0.8416 (3) | 1.00139 (16) | 0.0571 (7) | |
| C5 | 0.09662 (11) | 1.0170 (3) | 0.87111 (15) | 0.0550 (7) | |
| C2 | 0.05849 (11) | 0.7806 (3) | 0.92527 (13) | 0.0501 (6) | |
| N1 | 0.05983 (10) | 0.7810 (2) | 1.07271 (11) | 0.0759 (7) | |
| H1A | 0.0419 | 0.6926 | 1.0729 | 0.091* | |
| H1B | 0.0703 | 0.8305 | 1.1182 | 0.091* | |
| C4 | 0.08060 (11) | 0.8555 (3) | 0.85109 (13) | 0.0549 (7) | |
| H4 | 0.0427 | 0.8528 | 0.8053 | 0.066* | |
| O2 | 0.08103 (10) | 1.0779 (2) | 0.73126 (12) | 0.0897 (7) | |
| C10 | 0.09649 (13) | 1.1227 (3) | 0.80287 (19) | 0.0686 (8) | |
| C11 | 0.13891 (14) | 0.7707 (3) | 0.82384 (15) | 0.0569 (7) | |
| C3 | 0.02554 (13) | 0.6406 (4) | 0.91435 (14) | 0.0586 (7) | |
| C6 | 0.10774 (12) | 1.0700 (3) | 0.94811 (17) | 0.0604 (7) | |
| N2 | −0.00226 (12) | 0.5272 (3) | 0.90338 (13) | 0.0839 (8) | |
| C7 | 0.12867 (14) | 1.2263 (3) | 0.97399 (16) | 0.0790 (8) | |
| H7A | 0.1622 | 1.2225 | 1.0237 | 0.095* | |
| H7B | 0.0903 | 1.2825 | 0.9865 | 0.095* | |
| C9 | 0.11266 (18) | 1.2848 (4) | 0.82299 (19) | 0.1061 (11) | |
| H9A | 0.0712 | 1.3400 | 0.8232 | 0.127* | |
| H9B | 0.1346 | 1.3279 | 0.7799 | 0.127* | |
| C16 | 0.13116 (16) | 0.6985 (3) | 0.74839 (18) | 0.0867 (9) | |
| H16 | 0.0904 | 0.7056 | 0.7127 | 0.104* | |
| C8 | 0.15751 (17) | 1.3064 (3) | 0.9057 (2) | 0.1100 (12) | |
| H8A | 0.1621 | 1.4139 | 0.9181 | 0.132* | |
| H8B | 0.2018 | 1.2663 | 0.9029 | 0.132* | |
| C12 | 0.19982 (16) | 0.7600 (3) | 0.87459 (18) | 0.0894 (10) | |
| H12 | 0.2064 | 0.8083 | 0.9258 | 0.107* | |
| C15 | 0.1828 (2) | 0.6155 (4) | 0.7246 (3) | 0.1201 (14) | |
| H15 | 0.1766 | 0.5667 | 0.6736 | 0.144* | |
| C14 | 0.2420 (2) | 0.6057 (5) | 0.7757 (3) | 0.1254 (17) | |
| H14 | 0.2767 | 0.5492 | 0.7600 | 0.150* | |
| C13 | 0.25165 (18) | 0.6783 (5) | 0.8505 (3) | 0.1215 (14) | |
| H13 | 0.2930 | 0.6727 | 0.8850 | 0.146* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0811 (13) | 0.0612 (12) | 0.0571 (11) | −0.0126 (10) | 0.0103 (9) | 0.0013 (10) |
| C1 | 0.0571 (17) | 0.0574 (18) | 0.0580 (17) | −0.0072 (14) | 0.0135 (14) | 0.0012 (15) |
| C5 | 0.0524 (16) | 0.0553 (18) | 0.0593 (17) | 0.0015 (13) | 0.0151 (13) | 0.0061 (15) |
| C2 | 0.0532 (16) | 0.0537 (17) | 0.0443 (15) | −0.0037 (13) | 0.0104 (12) | −0.0004 (13) |
| N1 | 0.1060 (19) | 0.0758 (16) | 0.0488 (13) | −0.0279 (13) | 0.0216 (13) | −0.0051 (12) |
| C4 | 0.0530 (16) | 0.0653 (18) | 0.0462 (15) | −0.0032 (14) | 0.0073 (12) | 0.0070 (13) |
| O2 | 0.1089 (16) | 0.0947 (16) | 0.0703 (13) | 0.0135 (12) | 0.0287 (13) | 0.0276 (12) |
| C10 | 0.071 (2) | 0.063 (2) | 0.078 (2) | 0.0115 (15) | 0.0308 (18) | 0.0157 (18) |
| C11 | 0.0616 (18) | 0.0584 (17) | 0.0533 (16) | −0.0055 (14) | 0.0177 (15) | 0.0073 (14) |
| C3 | 0.0683 (18) | 0.066 (2) | 0.0439 (16) | −0.0033 (16) | 0.0159 (14) | 0.0034 (14) |
| C6 | 0.0599 (18) | 0.0542 (18) | 0.0675 (18) | −0.0019 (14) | 0.0115 (14) | 0.0077 (16) |
| N2 | 0.110 (2) | 0.0755 (18) | 0.0680 (16) | −0.0249 (16) | 0.0210 (14) | −0.0018 (14) |
| C7 | 0.084 (2) | 0.062 (2) | 0.093 (2) | −0.0100 (16) | 0.0226 (17) | −0.0057 (17) |
| C9 | 0.150 (3) | 0.072 (2) | 0.110 (3) | 0.007 (2) | 0.061 (2) | 0.019 (2) |
| C16 | 0.100 (3) | 0.088 (2) | 0.076 (2) | −0.0078 (18) | 0.0265 (18) | −0.0177 (18) |
| C8 | 0.137 (3) | 0.064 (2) | 0.141 (3) | −0.031 (2) | 0.058 (3) | −0.008 (2) |
| C12 | 0.066 (2) | 0.116 (3) | 0.088 (2) | 0.015 (2) | 0.018 (2) | 0.0002 (19) |
| C15 | 0.162 (4) | 0.091 (3) | 0.130 (4) | 0.003 (3) | 0.089 (3) | −0.020 (2) |
| C14 | 0.119 (4) | 0.101 (3) | 0.181 (5) | 0.021 (3) | 0.098 (4) | 0.025 (3) |
| C13 | 0.071 (2) | 0.144 (4) | 0.155 (4) | 0.023 (2) | 0.036 (3) | 0.018 (3) |
| O1—C1 | 1.376 (3) | C6—C7 | 1.482 (3) |
| O1—C6 | 1.381 (3) | C7—C8 | 1.520 (3) |
| C1—N1 | 1.341 (3) | C7—H7A | 0.9700 |
| C1—C2 | 1.344 (3) | C7—H7B | 0.9700 |
| C5—C6 | 1.329 (3) | C9—C8 | 1.512 (4) |
| C5—C10 | 1.455 (3) | C9—H9A | 0.9700 |
| C5—C4 | 1.484 (3) | C9—H9B | 0.9700 |
| C2—C3 | 1.400 (3) | C16—C15 | 1.382 (4) |
| C2—C4 | 1.514 (3) | C16—H16 | 0.9300 |
| N1—H1A | 0.8600 | C8—H8A | 0.9700 |
| N1—H1B | 0.8600 | C8—H8B | 0.9700 |
| C4—C11 | 1.524 (3) | C12—C13 | 1.382 (4) |
| C4—H4 | 0.9800 | C12—H12 | 0.9300 |
| O2—C10 | 1.228 (3) | C15—C14 | 1.344 (5) |
| C10—C9 | 1.491 (4) | C15—H15 | 0.9300 |
| C11—C12 | 1.370 (3) | C14—C13 | 1.368 (5) |
| C11—C16 | 1.376 (3) | C14—H14 | 0.9300 |
| C3—N2 | 1.146 (3) | C13—H13 | 0.9300 |
| C1—O1—C6 | 117.64 (19) | C8—C7—H7A | 109.6 |
| N1—C1—C2 | 127.8 (2) | C6—C7—H7B | 109.6 |
| N1—C1—O1 | 109.9 (2) | C8—C7—H7B | 109.6 |
| C2—C1—O1 | 122.3 (2) | H7A—C7—H7B | 108.1 |
| C6—C5—C10 | 118.9 (3) | C10—C9—C8 | 113.3 (3) |
| C6—C5—C4 | 122.9 (2) | C10—C9—H9A | 108.9 |
| C10—C5—C4 | 118.1 (2) | C8—C9—H9A | 108.9 |
| C1—C2—C3 | 119.2 (2) | C10—C9—H9B | 108.9 |
| C1—C2—C4 | 122.1 (2) | C8—C9—H9B | 108.9 |
| C3—C2—C4 | 118.6 (2) | H9A—C9—H9B | 107.7 |
| C1—N1—H1A | 120.0 | C11—C16—C15 | 121.3 (3) |
| C1—N1—H1B | 120.0 | C11—C16—H16 | 119.4 |
| H1A—N1—H1B | 120.0 | C15—C16—H16 | 119.4 |
| C5—C4—C2 | 108.9 (2) | C9—C8—C7 | 110.8 (3) |
| C5—C4—C11 | 112.61 (19) | C9—C8—H8A | 109.5 |
| C2—C4—C11 | 111.50 (19) | C7—C8—H8A | 109.5 |
| C5—C4—H4 | 107.9 | C9—C8—H8B | 109.5 |
| C2—C4—H4 | 107.9 | C7—C8—H8B | 109.5 |
| C11—C4—H4 | 107.9 | H8A—C8—H8B | 108.1 |
| O2—C10—C5 | 119.7 (3) | C11—C12—C13 | 120.6 (3) |
| O2—C10—C9 | 122.1 (3) | C11—C12—H12 | 119.7 |
| C5—C10—C9 | 118.1 (3) | C13—C12—H12 | 119.7 |
| C12—C11—C16 | 118.1 (3) | C14—C15—C16 | 119.7 (4) |
| C12—C11—C4 | 121.1 (2) | C14—C15—H15 | 120.2 |
| C16—C11—C4 | 120.8 (3) | C16—C15—H15 | 120.2 |
| N2—C3—C2 | 178.2 (3) | C15—C14—C13 | 120.4 (4) |
| C5—C6—O1 | 122.9 (2) | C15—C14—H14 | 119.8 |
| C5—C6—C7 | 126.4 (2) | C13—C14—H14 | 119.8 |
| O1—C6—C7 | 110.7 (2) | C14—C13—C12 | 119.9 (4) |
| C6—C7—C8 | 110.3 (2) | C14—C13—H13 | 120.0 |
| C6—C7—H7A | 109.6 | C12—C13—H13 | 120.0 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···N2i | 0.86 | 2.16 | 3.007 (3) | 170 |
| N1—H1B···O2ii | 0.86 | 2.00 | 2.848 (2) | 169 |
| Symmetry codes: (i) −x, −y+1, −z+2; (ii) x, −y+2, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···N2i | 0.86 | 2.16 | 3.007 (3) | 170 |
| N1—H1B···O2ii | 0.86 | 2.00 | 2.848 (2) | 169 |
| Symmetry codes: (i) −x, −y+1, −z+2; (ii) x, −y+2, z+1/2. |
The authors acknowledge financial support from the Shenyang University of Technology.
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Lokaj, J., Kettmann, V., Pavelčík, F., Ilavský, D. & Marchalín, Š. (1990). Acta Cryst. C46, 788–791.
Marco, J. L., Martin, G., Martin, N., Martinez-Grau, A., Seoane, C., Albert, A. & Cano, F. H. (1993). Tetrahedron, 49, 7133–7144.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Tu, S.-J., Deng, X., Fang, Y.-Y., Guo, Y.-M., Du, M. & Liu, X.-H. (2001). Acta Cryst. E57, o358–o359.
Much interest has recently been paid to the design of polyfunctionalized substituted pyran derivatives, owing to their wide range of biological activities (Lokaj et al., 1990; Marco et al., 1993). We obtained the title compound, (I), and report here its crystal structure.
In (I) (Fig. 1), the bond lengths and angles of the main molecule are normal and correspond to those observed in 2-amino-7,7-dimethyl- 5-oxo-4-phenyl-5,6,7,8-tetra- hydro-4H-chromene-3-carbonitrile (Tu et al., 2001). The fused cyclohexene and pyran rings adopt an envelope and a flattened bath conformations, respecteviley. The dihedral angle between the O1/C1/C2/C5/C6 and C2/C4/C5 planes is 16.67 (14) °. The O1/ C1/C2/C5/C6 plane forms an angle of 89.01 (8)° with the phenyl plane. In the crystal, the nitrile group is typical [N≡C = 1.146 (3) Å] and the carbonyl group also is reasonable [C═O =1.228 (3) Å]. The C5/C6/C7/C8/C9/C10 plane also adopt an chair configuration in the compound, and the the dihedral angle between the C5/C6/C7/C9/C10 plane and the C7/C8/C9 plane is 46.14 (3)°.
In the crystal structure, there exist typical intermolecular N—H···O and N—H···N hydrogen bonds (Table 1). The amino N1 atom of one molecule links through H1B to the nitrile N2 atom of another molecule, creating a dimer. The amino N1 atom of one molecule also links through H1A to the keto O2 atom of another molecule to form the two-dimensional framework.