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access(E)-2,4,6-Trimethyl-N-(pyridin-2-ylmethylidene)aniline
aDepartment of Chemistry, Harbin Institute of Technology, Harbin 150001, People's Republic of China
*Correspondence e-mail: fanruiqing@hit.edu.cn
In the title compound, C15H16N2, has an E conformation about the central N=C bond. The benzene and pyridine rings are almost normal to one another with a dihedral angle of 87.47(8)°. In the crystal, there are no classical hydrogen bonds.
Related literature
For C—N bond forming reactions, see: Alonso-Moreno et al. (2009![[Alonso-Moreno, C., Carrillo-Hermosilla, F., Romero-Fernández, J., Rodríguez, A. M., Otero, A. & Antiñolo, A. (2009). Adv. Synth. Catal. 351, 881-890.]](../../../../../../logos/arrows/e_arr.gif "Alonso-Moreno, C., Carrillo-Hermosilla, F., Romero-Fernández, J., Rodríguez, A. M., Otero, A. & Antiñolo, A. (2009). Adv. Synth. Catal. 351, 881-890.")
); Qiu et al. (2009). For imino C=N bonds in a related structure, see: Nienkemper et al. (2006). For the preparation of related compounds, see: Bianchini et al. (2001); Fan et al. (2009).
![[Scheme 1]](zj2067scheme1.gif)
Experimental
Crystal data
|
Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXP97 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536812015905/zj2067sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536812015905/zj2067Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812015905/zj2067Isup3.cml
The Schiff base was prepared according to the literature methods for analogous compounds (Fan et al., 2009, Bianchini et al., 2002). Pyridine-2-carboxaldehyde (1.69 g, 15.8 mmol) and 2,4,6-trimethyaniline (2.13 g, 15.7 mmol) were dissolved in 20 ml of methanol containing a few drops of formic acid and the resulting mixture was heated at reflux temperature for 4 h. Partial evaporation of solvent under reduced pressure gave yellow soild.Yellow block crystals suitable for X-ray were obtained by recrystallization from n-hexane,and the specific method was that a solution of yellow soild in 15 ml of n-hexane was heated at 338 K and then allowed to cool down to room temperature.Yield:76% (2.68 g).
The C-bound H atoms were positioned geometrically with C—H = 0.93–0.96 Å, and allowed to ride on their parent atoms with Uiso(H) = 1.2 Ueq(C) for CH2 groups, and 1.5 Ueq(C) for CH3 groups.
Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXP97 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./zj2067fig1thm.gif) | Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. |
![[Figure 2]](./zj2067fig2thm.gif) | Fig. 2. Packing of (I) along c axis direction. |
| C15H16N2 | F(000) = 480 |
| Mr = 224.30 | Dx = 1.140 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 12591 reflections |
| a = 8.2490 (16) Å | θ = 3.1–27.5° |
| b = 16.136 (3) Å | µ = 0.07 mm−1 |
| c = 10.150 (2) Å | T = 293 K |
| β = 104.76 (3)° | Block, colorless |
| V = 1306.4 (4) Å3 | 0.36 × 0.34 × 0.29 mm |
| Z = 4 |
| Bruker SMART APEX CCD area-detector diffractometer | 2982 independent reflections |
| Radiation source: fine-focus sealed tube | 1952 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.044 |
| phi and ω scans | θmax = 27.5°, θmin = 3.1° |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −10→10 |
| Tmin = 0.976, Tmax = 0.981 | k = −20→20 |
| 12591 measured reflections | l = −13→13 |
| 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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.200 | H-atom parameters constrained |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.1315P)2] where P = (Fo2 + 2Fc2)/3 |
| 2982 reflections | (Δ/σ)max = 0.017 |
| 154 parameters | Δρmax = 0.22 e Å−3 |
| 0 restraints | Δρmin = −0.22 e Å−3 |
| C15H16N2 | V = 1306.4 (4) Å3 |
| Mr = 224.30 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 8.2490 (16) Å | µ = 0.07 mm−1 |
| b = 16.136 (3) Å | T = 293 K |
| c = 10.150 (2) Å | 0.36 × 0.34 × 0.29 mm |
| β = 104.76 (3)° |
| Bruker SMART APEX CCD area-detector diffractometer | 2982 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1952 reflections with I > 2σ(I) |
| Tmin = 0.976, Tmax = 0.981 | Rint = 0.044 |
| 12591 measured reflections |
| R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
| wR(F2) = 0.200 | H-atom parameters constrained |
| S = 1.03 | Δρmax = 0.22 e Å−3 |
| 2982 reflections | Δρmin = −0.22 e Å−3 |
| 154 parameters |
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 | ||
| N1 | −0.08242 (19) | −0.04738 (10) | 0.77519 (15) | 0.0748 (5) | |
| N2 | 0.20612 (16) | 0.11712 (9) | 0.82639 (12) | 0.0612 (4) | |
| C1 | −0.02245 (18) | 0.02378 (10) | 0.74182 (15) | 0.0559 (4) | |
| C2 | −0.0893 (2) | 0.06280 (13) | 0.61937 (16) | 0.0714 (5) | |
| H2A | −0.0460 | 0.1131 | 0.5993 | 0.086* | |
| C3 | −0.2097 (2) | −0.08143 (14) | 0.6828 (2) | 0.0830 (6) | |
| H3A | −0.2515 | −0.1318 | 0.7042 | 0.100* | |
| C4 | −0.2827 (2) | −0.04703 (15) | 0.55889 (18) | 0.0816 (6) | |
| H4A | −0.3718 | −0.0731 | 0.4983 | 0.098* | |
| C5 | −0.2218 (3) | 0.02585 (16) | 0.52670 (19) | 0.0854 (6) | |
| H5A | −0.2686 | 0.0509 | 0.4431 | 0.102* | |
| C6 | 0.12079 (18) | 0.05750 (10) | 0.84678 (15) | 0.0572 (4) | |
| H6A | 0.1483 | 0.0328 | 0.9324 | 0.069* | |
| C7 | 0.34417 (17) | 0.14354 (9) | 0.93500 (15) | 0.0529 (4) | |
| C8 | 0.50580 (18) | 0.11695 (10) | 0.93612 (15) | 0.0561 (4) | |
| C9 | 0.63854 (18) | 0.14503 (10) | 1.04089 (16) | 0.0598 (4) | |
| H9A | 0.7465 | 0.1274 | 1.0430 | 0.072* | |
| C10 | 0.61645 (18) | 0.19772 (10) | 1.14131 (17) | 0.0600 (4) | |
| C11 | 0.45476 (19) | 0.22368 (11) | 1.13626 (16) | 0.0611 (4) | |
| H11A | 0.4379 | 0.2595 | 1.2033 | 0.073* | |
| C12 | 0.31661 (18) | 0.19793 (10) | 1.03427 (15) | 0.0556 (4) | |
| C13 | 0.5355 (2) | 0.05931 (13) | 0.82917 (18) | 0.0760 (5) | |
| H13A | 0.6532 | 0.0479 | 0.8462 | 0.114* | |
| H13B | 0.4964 | 0.0846 | 0.7411 | 0.114* | |
| H13C | 0.4758 | 0.0085 | 0.8316 | 0.114* | |
| C14 | 0.7641 (2) | 0.22552 (14) | 1.2553 (2) | 0.0844 (6) | |
| H14A | 0.8654 | 0.2017 | 1.2422 | 0.127* | |
| H14B | 0.7479 | 0.2076 | 1.3413 | 0.127* | |
| H14C | 0.7723 | 0.2849 | 1.2546 | 0.127* | |
| C15 | 0.1431 (2) | 0.22807 (13) | 1.0332 (2) | 0.0755 (6) | |
| H15A | 0.1494 | 0.2642 | 1.1094 | 0.113* | |
| H15B | 0.0730 | 0.1815 | 1.0393 | 0.113* | |
| H15C | 0.0965 | 0.2577 | 0.9501 | 0.113* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0668 (9) | 0.0740 (10) | 0.0716 (9) | −0.0142 (7) | −0.0044 (7) | 0.0011 (7) |
| N2 | 0.0550 (7) | 0.0706 (9) | 0.0494 (7) | −0.0078 (6) | −0.0024 (6) | 0.0029 (6) |
| C1 | 0.0461 (7) | 0.0634 (9) | 0.0540 (8) | 0.0000 (6) | 0.0050 (6) | −0.0066 (7) |
| C2 | 0.0625 (9) | 0.0853 (13) | 0.0584 (9) | −0.0121 (8) | 0.0006 (8) | 0.0021 (8) |
| C3 | 0.0724 (11) | 0.0809 (13) | 0.0839 (13) | −0.0218 (9) | −0.0016 (10) | −0.0076 (10) |
| C4 | 0.0599 (10) | 0.1080 (16) | 0.0677 (11) | −0.0180 (10) | −0.0007 (9) | −0.0236 (11) |
| C5 | 0.0723 (12) | 0.1173 (17) | 0.0541 (9) | −0.0139 (11) | −0.0067 (8) | 0.0006 (10) |
| C6 | 0.0515 (8) | 0.0627 (9) | 0.0499 (7) | −0.0020 (7) | −0.0008 (6) | 0.0013 (7) |
| C7 | 0.0489 (7) | 0.0565 (9) | 0.0470 (7) | −0.0056 (6) | 0.0006 (6) | 0.0057 (6) |
| C8 | 0.0537 (8) | 0.0609 (9) | 0.0506 (8) | −0.0007 (7) | 0.0077 (6) | 0.0032 (6) |
| C9 | 0.0429 (7) | 0.0695 (10) | 0.0631 (9) | −0.0015 (6) | 0.0062 (7) | 0.0033 (7) |
| C10 | 0.0473 (8) | 0.0654 (10) | 0.0600 (9) | −0.0091 (7) | 0.0001 (7) | −0.0011 (7) |
| C11 | 0.0556 (8) | 0.0634 (10) | 0.0593 (8) | −0.0052 (7) | 0.0055 (7) | −0.0090 (7) |
| C12 | 0.0463 (7) | 0.0590 (9) | 0.0564 (8) | −0.0009 (6) | 0.0038 (6) | 0.0015 (7) |
| C13 | 0.0742 (11) | 0.0847 (13) | 0.0654 (10) | 0.0051 (9) | 0.0113 (9) | −0.0099 (9) |
| C14 | 0.0577 (10) | 0.0992 (15) | 0.0829 (12) | −0.0133 (9) | −0.0066 (9) | −0.0186 (11) |
| C15 | 0.0522 (9) | 0.0831 (12) | 0.0836 (12) | 0.0113 (8) | 0.0035 (8) | −0.0091 (10) |
| N1—C1 | 1.328 (2) | C8—C13 | 1.496 (2) |
| N1—C3 | 1.335 (2) | C9—C10 | 1.375 (2) |
| N2—C6 | 1.240 (2) | C9—H9A | 0.9300 |
| N2—C7 | 1.4333 (18) | C10—C11 | 1.386 (2) |
| C1—C2 | 1.377 (2) | C10—C14 | 1.518 (2) |
| C1—C6 | 1.478 (2) | C11—C12 | 1.393 (2) |
| C2—C5 | 1.383 (2) | C11—H11A | 0.9300 |
| C2—H2A | 0.9300 | C12—C15 | 1.509 (2) |
| C3—C4 | 1.366 (3) | C13—H13A | 0.9600 |
| C3—H3A | 0.9300 | C13—H13B | 0.9600 |
| C4—C5 | 1.351 (3) | C13—H13C | 0.9600 |
| C4—H4A | 0.9300 | C14—H14A | 0.9600 |
| C5—H5A | 0.9300 | C14—H14B | 0.9600 |
| C6—H6A | 0.9300 | C14—H14C | 0.9600 |
| C7—C12 | 1.398 (2) | C15—H15A | 0.9600 |
| C7—C8 | 1.398 (2) | C15—H15B | 0.9600 |
| C8—C9 | 1.394 (2) | C15—H15C | 0.9600 |
| C1—N1—C3 | 117.01 (15) | C8—C9—H9A | 118.7 |
| C6—N2—C7 | 118.42 (13) | C9—C10—C11 | 117.87 (14) |
| N1—C1—C2 | 122.42 (15) | C9—C10—C14 | 121.05 (15) |
| N1—C1—C6 | 114.57 (13) | C11—C10—C14 | 121.08 (17) |
| C2—C1—C6 | 123.01 (16) | C10—C11—C12 | 122.30 (16) |
| C1—C2—C5 | 118.83 (19) | C10—C11—H11A | 118.8 |
| C1—C2—H2A | 120.6 | C12—C11—H11A | 118.8 |
| C5—C2—H2A | 120.6 | C11—C12—C7 | 118.05 (14) |
| N1—C3—C4 | 124.2 (2) | C11—C12—C15 | 120.26 (16) |
| N1—C3—H3A | 117.9 | C7—C12—C15 | 121.68 (14) |
| C4—C3—H3A | 117.9 | C8—C13—H13A | 109.5 |
| C5—C4—C3 | 118.21 (16) | C8—C13—H13B | 109.5 |
| C5—C4—H4A | 120.9 | H13A—C13—H13B | 109.5 |
| C3—C4—H4A | 120.9 | C8—C13—H13C | 109.5 |
| C4—C5—C2 | 119.27 (17) | H13A—C13—H13C | 109.5 |
| C4—C5—H5A | 120.4 | H13B—C13—H13C | 109.5 |
| C2—C5—H5A | 120.4 | C10—C14—H14A | 109.5 |
| N2—C6—C1 | 123.27 (14) | C10—C14—H14B | 109.5 |
| N2—C6—H6A | 118.4 | H14A—C14—H14B | 109.5 |
| C1—C6—H6A | 118.4 | C10—C14—H14C | 109.5 |
| C12—C7—C8 | 121.12 (13) | H14A—C14—H14C | 109.5 |
| C12—C7—N2 | 119.87 (13) | H14B—C14—H14C | 109.5 |
| C8—C7—N2 | 118.96 (14) | C12—C15—H15A | 109.5 |
| C9—C8—C7 | 117.96 (15) | C12—C15—H15B | 109.5 |
| C9—C8—C13 | 120.92 (14) | H15A—C15—H15B | 109.5 |
| C7—C8—C13 | 121.12 (14) | C12—C15—H15C | 109.5 |
| C10—C9—C8 | 122.69 (14) | H15A—C15—H15C | 109.5 |
| C10—C9—H9A | 118.7 | H15B—C15—H15C | 109.5 |
Experimental details
| Crystal data | |
| Chemical formula | C15H16N2 |
| Mr | 224.30 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 293 |
| a, b, c (Å) | 8.2490 (16), 16.136 (3), 10.150 (2) |
| β (°) | 104.76 (3) |
| V (Å3) | 1306.4 (4) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.07 |
| Crystal size (mm) | 0.36 × 0.34 × 0.29 |
| Data collection | |
| Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
| Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
| Tmin, Tmax | 0.976, 0.981 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 12591, 2982, 1952 |
| Rint | 0.044 |
| (sin θ/λ)max (Å−1) | 0.649 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.200, 1.03 |
| No. of reflections | 2982 |
| No. of parameters | 154 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.22, −0.22 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXP97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This work was supported by the National Natural Science Foundation of China (grant Nos. 20971031, 21071035 and 21171044), the China Postdoctoral Science Foundation Funded Project (No. 65204) and the Key Natural Science Foundation of the Heilongjiang Province, China (No. ZD201009).
References
Alonso-Moreno, C., Carrillo-Hermosilla, F., Romero-Fernández, J., Rodríguez, A. M., Otero, A. & Antiñolo, A. (2009). Adv. Synth. Catal. 351, 881–890. CAS Google Scholar
Bianchini, C., Lee, H. M., Mantovani, G., Meli, A. & Oberhauser, W. (2001). New J. Chem. 26, 387–397. Web of Science CSD CrossRef Google Scholar
Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fan, R. Q., Yang, Y. L., Yin, Y. B., Hasi, W. L. J. & Mu, Y. (2009). Inorg. Chem. 48, 6034–6043. Web of Science CSD CrossRef PubMed CAS Google Scholar
Nienkemper, K., Kotov, V. V., Kehr, G., Erker, G. & Fröhlich, R. (2006). Eur. J. Inorg. Chem. pp. 366–379. Web of Science CSD CrossRef Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
C—N bond forming reactions are of considerable interest in both synthetic organic due to the importance of amines and their derivatives in almost all areas of chemistry (Alonso-Moreno et al., 2009, Qiu et al., 2009). It is still challenging to design and rationally synthesize ligand with unique structures and functions. For this regard, we reported the crystal structure of compound (I). The molecular structure of (I) is shown in Fig. 1 and selected bond distances are given in Table 1. The imino C==N bonds have typical double-bond characteristic with bond lengths of 1.240 (2), which are similar to that in (2,6-diisopropylphenyl)[1-(pyridin-2-yl)ethylidene]amine, 1.280 (2) Å (Nienkemper et al., 2006). The compound (I) possesses a structure with approximate P21/c symmetry. The dihedral angles between 2,4,6- trimethyl-substituted phenyl rings and the pyridine ring are 87.5° respectively.