Acta Cryst. (2008). E64, o1872 [ doi:10.1107/S1600536808025403 ]
In the title compound, 2-[(4-benzhydrylpiperazin-1-yl)methyl]acrylonitrile, C21H23N3, the substituted piperazine ring adopts a chair conformation and the dihedral angle between the mean planes of the aromatic rings is 71.61 (8)°.
La réaction est effectuée dans un ballon de 250 ml muni d'un barreau aimanté surmonté d'un séparateur à eau et d'un réfrigérant ascendant. Le reflux est réalisé à l'aide d'un bain d'huile. La réaction est terminée lorsqu'il ne se forme plus d'eau (environ 2 heures). A une solution d'acide cyanoacétique (0,3 mol) dans 300 ml de benzène, sont ajoutés 0,72 mol de paraformaldéhyde et 0,3 mol de 1-(diphénylméthyl)pipérazine. Le mélange est chauffé à reflux pendant 4 heures. Après refroidissement, le solvant est évaporé sous sec et le résidu est repris par 80 ml de chloroforme, lavé à l'eau (2 × 20 ml) et séché sur du sulfate de magnésium. Le solvant est évaporé sous sec et le produit obtenu est purifié par chromatographie sur colonne en utilisant l'éther diéthylique comme éluant.
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./hb2772fig1thm.gif)
| Fig. 1. Représentation de la molécule C21H23N3. Les ellipsoïdes d'agitation thermique ont 50% de probabilité de présence. |
| C21H23N3 | F(000) = 680 |
| Mr = 317.42 | Dx = 1.154 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
| a = 17.443 (5) Å | θ = 11.6–15.0° |
| b = 6.183 (3) Å | µ = 0.07 mm−1 |
| c = 17.717 (5) Å | T = 298 K |
| β = 107.00 (3)° | Slab, colourless |
| V = 1827.4 (12) Å3 | 0.72 × 0.58 × 0.22 mm |
| Z = 4 |
| Enraf–Nonius CAD-4 diffractometer | 1625 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.052 |
| graphite | θmax = 26.0°, θmin = 2.4° |
| Non–profiled ω/2θ scans | h = −21→1 |
| Absorption correction: ψ scan (North et al., 1968) | k = 0→7 |
| Tmin = 0.904, Tmax = 0.985 | l = −21→21 |
| 3708 measured reflections | 2 standard reflections every 120 min |
| 3587 independent reflections | intensity decay: 7% |
| 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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.156 | All H-atom parameters refined |
| S = 0.98 | w = 1/[σ2(Fo2) + (0.0682P)2] where P = (Fo2 + 2Fc2)/3 |
| 3587 reflections | (Δ/σ)max < 0.001 |
| 309 parameters | Δρmax = 0.17 e Å−3 |
| 0 restraints | Δρmin = −0.20 e Å−3 |
| C21H23N3 | V = 1827.4 (12) Å3 |
| Mr = 317.42 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 17.443 (5) Å | µ = 0.07 mm−1 |
| b = 6.183 (3) Å | T = 298 K |
| c = 17.717 (5) Å | 0.72 × 0.58 × 0.22 mm |
| β = 107.00 (3)° |
| Enraf–Nonius CAD-4 diffractometer | 1625 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.052 |
| Tmin = 0.904, Tmax = 0.985 | θmax = 26.0° |
| 3708 measured reflections | 2 standard reflections every 120 min |
| 3587 independent reflections | intensity decay: 7% |
| R[F2 > 2σ(F2)] = 0.054 | All H-atom parameters refined |
| wR(F2) = 0.156 | Δρmax = 0.17 e Å−3 |
| S = 0.98 | Δρmin = −0.20 e Å−3 |
| 3587 reflections | Absolute structure: ? |
| 309 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 | ||
| N1 | −0.13498 (16) | 0.4548 (5) | 0.10237 (17) | 0.0949 (9) | |
| N2 | 0.08178 (11) | 0.5724 (3) | 0.18358 (11) | 0.0514 (5) | |
| N3 | 0.22797 (11) | 0.3529 (3) | 0.17780 (11) | 0.0484 (5) | |
| C1 | −0.09372 (17) | 0.6013 (5) | 0.11096 (15) | 0.0625 (7) | |
| C2 | −0.04111 (15) | 0.7881 (4) | 0.12169 (16) | 0.0564 (7) | |
| C3 | −0.0645 (2) | 0.9613 (6) | 0.0767 (2) | 0.0792 (9) | |
| C4 | 0.03676 (16) | 0.7713 (5) | 0.18724 (18) | 0.0616 (7) | |
| C5 | 0.15513 (15) | 0.5667 (5) | 0.25155 (16) | 0.0558 (7) | |
| C6 | 0.20291 (16) | 0.3636 (5) | 0.24995 (15) | 0.0535 (7) | |
| C7 | 0.10589 (17) | 0.5601 (5) | 0.11123 (16) | 0.0560 (7) | |
| C8 | 0.15533 (15) | 0.3575 (5) | 0.11019 (15) | 0.0545 (7) | |
| C9 | 0.27587 (14) | 0.1535 (4) | 0.17883 (14) | 0.0492 (6) | |
| C10 | 0.35248 (13) | 0.1564 (4) | 0.24803 (14) | 0.0504 (6) | |
| C11 | 0.40273 (16) | 0.3359 (5) | 0.26327 (17) | 0.0642 (8) | |
| C12 | 0.47357 (17) | 0.3339 (7) | 0.3254 (2) | 0.0781 (10) | |
| C13 | 0.4938 (2) | 0.1530 (7) | 0.3721 (2) | 0.0842 (11) | |
| C14 | 0.4453 (2) | −0.0264 (7) | 0.3578 (2) | 0.0816 (10) | |
| C15 | 0.37478 (18) | −0.0246 (6) | 0.29607 (17) | 0.0660 (8) | |
| C16 | 0.29580 (13) | 0.1168 (4) | 0.10145 (14) | 0.0495 (6) | |
| C17 | 0.32827 (19) | 0.2798 (5) | 0.06644 (17) | 0.0685 (8) | |
| C18 | 0.3497 (2) | 0.2389 (6) | −0.00144 (19) | 0.0807 (10) | |
| C19 | 0.33888 (18) | 0.0384 (6) | −0.03670 (18) | 0.0738 (9) | |
| C20 | 0.30501 (19) | −0.1234 (6) | −0.00327 (19) | 0.0746 (9) | |
| C21 | 0.28447 (16) | −0.0861 (5) | 0.06555 (18) | 0.0623 (7) | |
| H13 | −0.0285 (19) | 1.088 (5) | 0.0898 (18) | 0.098 (11)* | |
| H23 | −0.1189 (16) | 0.972 (4) | 0.0391 (16) | 0.068 (8)* | |
| H14 | 0.0235 (14) | 0.767 (4) | 0.2404 (16) | 0.074 (8)* | |
| H24 | 0.0693 (16) | 0.909 (4) | 0.1835 (15) | 0.075 (8)* | |
| H15 | 0.1394 (13) | 0.573 (4) | 0.2995 (14) | 0.058 (7)* | |
| H25 | 0.1883 (16) | 0.704 (4) | 0.2488 (15) | 0.078 (8)* | |
| H16 | 0.1723 (15) | 0.231 (4) | 0.2543 (14) | 0.068 (8)* | |
| H26 | 0.2498 (14) | 0.361 (3) | 0.2972 (13) | 0.053 (6)* | |
| H17 | 0.0579 (14) | 0.552 (4) | 0.0641 (15) | 0.057 (7)* | |
| H27 | 0.1379 (14) | 0.692 (4) | 0.1039 (13) | 0.060 (7)* | |
| H18 | 0.1224 (15) | 0.228 (4) | 0.1109 (14) | 0.068 (8)* | |
| H28 | 0.1719 (13) | 0.360 (4) | 0.0624 (14) | 0.055 (7)* | |
| H19 | 0.2430 (12) | 0.032 (3) | 0.1842 (11) | 0.039 (6)* | |
| H111 | 0.3885 (13) | 0.460 (4) | 0.2327 (14) | 0.056 (8)* | |
| H112 | 0.5043 (17) | 0.462 (5) | 0.3322 (17) | 0.088 (10)* | |
| H113 | 0.5413 (19) | 0.155 (5) | 0.4162 (18) | 0.093 (10)* | |
| H114 | 0.4583 (19) | −0.147 (5) | 0.3893 (18) | 0.096 (11)* | |
| H115 | 0.3425 (16) | −0.147 (5) | 0.2845 (15) | 0.078 (10)* | |
| H117 | 0.3375 (17) | 0.426 (5) | 0.0924 (18) | 0.094 (10)* | |
| H118 | 0.3684 (18) | 0.350 (5) | −0.0223 (17) | 0.086 (10)* | |
| H119 | 0.3571 (17) | 0.006 (5) | −0.0838 (19) | 0.100 (10)* | |
| H120 | 0.2960 (16) | −0.263 (5) | −0.0260 (17) | 0.084 (9)* | |
| H121 | 0.2654 (16) | −0.199 (4) | 0.0925 (15) | 0.072 (9)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0769 (18) | 0.088 (2) | 0.102 (2) | −0.0164 (16) | −0.0001 (16) | 0.0096 (17) |
| N2 | 0.0447 (11) | 0.0591 (14) | 0.0510 (11) | −0.0024 (10) | 0.0149 (9) | −0.0069 (10) |
| N3 | 0.0423 (11) | 0.0535 (13) | 0.0495 (11) | −0.0019 (10) | 0.0135 (9) | −0.0029 (10) |
| C1 | 0.0554 (16) | 0.067 (2) | 0.0588 (16) | 0.0055 (16) | 0.0067 (14) | 0.0023 (14) |
| C2 | 0.0517 (15) | 0.0572 (17) | 0.0614 (15) | 0.0058 (14) | 0.0182 (13) | −0.0068 (14) |
| C3 | 0.077 (2) | 0.067 (2) | 0.089 (2) | 0.0144 (19) | 0.016 (2) | 0.0031 (19) |
| C4 | 0.0583 (17) | 0.0565 (18) | 0.0700 (18) | 0.0005 (15) | 0.0187 (14) | −0.0111 (15) |
| C5 | 0.0483 (14) | 0.0703 (19) | 0.0507 (15) | −0.0033 (14) | 0.0173 (13) | −0.0077 (14) |
| C6 | 0.0451 (14) | 0.0679 (18) | 0.0462 (14) | −0.0038 (14) | 0.0116 (12) | 0.0029 (13) |
| C7 | 0.0476 (14) | 0.0635 (19) | 0.0549 (16) | 0.0044 (14) | 0.0116 (13) | 0.0034 (14) |
| C8 | 0.0485 (15) | 0.0639 (19) | 0.0496 (15) | −0.0018 (15) | 0.0118 (12) | −0.0023 (13) |
| C9 | 0.0439 (13) | 0.0488 (16) | 0.0553 (15) | −0.0116 (13) | 0.0151 (11) | 0.0002 (12) |
| C10 | 0.0430 (13) | 0.0553 (16) | 0.0538 (14) | −0.0007 (13) | 0.0156 (11) | −0.0040 (13) |
| C11 | 0.0516 (16) | 0.066 (2) | 0.0726 (19) | −0.0047 (15) | 0.0145 (15) | −0.0038 (16) |
| C12 | 0.0488 (18) | 0.094 (3) | 0.089 (2) | −0.0114 (19) | 0.0162 (17) | −0.029 (2) |
| C13 | 0.0546 (19) | 0.115 (3) | 0.073 (2) | 0.021 (2) | 0.0031 (17) | −0.019 (2) |
| C14 | 0.074 (2) | 0.092 (3) | 0.071 (2) | 0.023 (2) | 0.0090 (18) | 0.007 (2) |
| C15 | 0.0605 (18) | 0.068 (2) | 0.0673 (19) | 0.0052 (17) | 0.0149 (15) | 0.0057 (16) |
| C16 | 0.0382 (13) | 0.0520 (16) | 0.0557 (14) | −0.0013 (11) | 0.0097 (11) | −0.0020 (12) |
| C17 | 0.086 (2) | 0.0594 (19) | 0.0687 (18) | −0.0062 (16) | 0.0367 (16) | −0.0035 (15) |
| C18 | 0.098 (2) | 0.079 (2) | 0.078 (2) | 0.002 (2) | 0.0455 (19) | 0.008 (2) |
| C19 | 0.0669 (19) | 0.098 (3) | 0.0570 (18) | 0.0194 (18) | 0.0184 (15) | −0.0029 (18) |
| C20 | 0.0671 (19) | 0.075 (2) | 0.077 (2) | 0.0013 (18) | 0.0152 (16) | −0.0247 (19) |
| C21 | 0.0546 (16) | 0.0583 (19) | 0.0751 (19) | −0.0043 (14) | 0.0208 (14) | −0.0071 (16) |
| N1—C1 | 1.139 (3) | C9—C10 | 1.527 (3) |
| N2—C7 | 1.463 (3) | C9—H19 | 0.97 (2) |
| N2—C4 | 1.471 (3) | C10—C11 | 1.391 (4) |
| N2—C5 | 1.479 (3) | C10—C15 | 1.391 (4) |
| N3—C8 | 1.467 (3) | C11—C12 | 1.394 (4) |
| N3—C6 | 1.469 (3) | C11—H111 | 0.93 (2) |
| N3—C9 | 1.486 (3) | C12—C13 | 1.374 (5) |
| C1—C2 | 1.453 (4) | C12—H112 | 0.95 (3) |
| C2—C3 | 1.326 (4) | C13—C14 | 1.373 (5) |
| C2—C4 | 1.511 (4) | C13—H113 | 0.96 (3) |
| C3—H13 | 0.99 (3) | C14—C15 | 1.387 (4) |
| C3—H23 | 0.99 (3) | C14—H114 | 0.92 (3) |
| C4—H14 | 1.03 (3) | C15—H115 | 0.93 (3) |
| C4—H24 | 1.03 (3) | C16—C17 | 1.388 (4) |
| C5—C6 | 1.512 (4) | C16—C21 | 1.394 (3) |
| C5—H15 | 0.97 (2) | C17—C18 | 1.383 (4) |
| C5—H25 | 1.03 (3) | C17—H117 | 1.00 (3) |
| C6—H16 | 0.99 (3) | C18—C19 | 1.376 (4) |
| C6—H26 | 0.99 (2) | C18—H118 | 0.89 (3) |
| C7—C8 | 1.524 (4) | C19—C20 | 1.380 (4) |
| C7—H17 | 1.00 (2) | C19—H119 | 1.00 (3) |
| C7—H27 | 1.02 (2) | C20—C21 | 1.387 (4) |
| C8—H18 | 0.99 (3) | C20—H120 | 0.94 (3) |
| C8—H28 | 0.97 (2) | C21—H121 | 0.96 (3) |
| C9—C16 | 1.527 (3) | ||
| C7—N2—C4 | 112.1 (2) | N3—C9—C16 | 112.77 (19) |
| C7—N2—C5 | 108.08 (19) | N3—C9—C10 | 110.9 (2) |
| C4—N2—C5 | 109.3 (2) | C16—C9—C10 | 110.31 (19) |
| C8—N3—C6 | 107.69 (19) | N3—C9—H19 | 107.4 (12) |
| C8—N3—C9 | 111.96 (19) | C16—C9—H19 | 105.7 (12) |
| C6—N3—C9 | 109.63 (19) | C10—C9—H19 | 109.6 (12) |
| N1—C1—C2 | 179.8 (3) | C11—C10—C15 | 118.4 (3) |
| C3—C2—C1 | 119.4 (3) | C11—C10—C9 | 121.3 (2) |
| C3—C2—C4 | 124.6 (3) | C15—C10—C9 | 120.3 (2) |
| C1—C2—C4 | 115.9 (3) | C10—C11—C12 | 120.6 (3) |
| C2—C3—H13 | 115.8 (18) | C10—C11—H111 | 119.9 (15) |
| C2—C3—H23 | 121.7 (16) | C12—C11—H111 | 119.5 (15) |
| H13—C3—H23 | 122 (2) | C13—C12—C11 | 119.6 (3) |
| N2—C4—C2 | 113.3 (2) | C13—C12—H112 | 124.8 (19) |
| N2—C4—H14 | 106.4 (14) | C11—C12—H112 | 115.6 (19) |
| C2—C4—H14 | 108.2 (14) | C14—C13—C12 | 120.8 (3) |
| N2—C4—H24 | 111.9 (14) | C14—C13—H113 | 119.8 (18) |
| C2—C4—H24 | 106.4 (15) | C12—C13—H113 | 119.4 (18) |
| H14—C4—H24 | 111 (2) | C13—C14—C15 | 119.6 (4) |
| N2—C5—C6 | 110.8 (2) | C13—C14—H114 | 121 (2) |
| N2—C5—H15 | 108.4 (13) | C15—C14—H114 | 119 (2) |
| C6—C5—H15 | 110.5 (14) | C14—C15—C10 | 121.0 (4) |
| N2—C5—H25 | 107.7 (15) | C14—C15—H115 | 120.4 (17) |
| C6—C5—H25 | 111.1 (14) | C10—C15—H115 | 118.5 (17) |
| H15—C5—H25 | 108.3 (19) | C17—C16—C21 | 118.1 (3) |
| N3—C6—C5 | 111.1 (2) | C17—C16—C9 | 121.5 (2) |
| N3—C6—H16 | 109.6 (14) | C21—C16—C9 | 120.3 (2) |
| C5—C6—H16 | 111.8 (14) | C18—C17—C16 | 120.4 (3) |
| N3—C6—H26 | 110.7 (12) | C18—C17—H117 | 120.9 (17) |
| C5—C6—H26 | 109.0 (13) | C16—C17—H117 | 118.7 (17) |
| H16—C6—H26 | 105 (2) | C19—C18—C17 | 121.5 (3) |
| N2—C7—C8 | 111.2 (2) | C19—C18—H118 | 121.9 (19) |
| N2—C7—H17 | 110.6 (13) | C17—C18—H118 | 116.5 (19) |
| C8—C7—H17 | 106.9 (13) | C18—C19—C20 | 118.5 (3) |
| N2—C7—H27 | 112.3 (13) | C18—C19—H119 | 121.8 (18) |
| C8—C7—H27 | 108.8 (13) | C20—C19—H119 | 119.6 (18) |
| H17—C7—H27 | 106.8 (19) | C19—C20—C21 | 120.6 (3) |
| N3—C8—C7 | 111.3 (2) | C19—C20—H120 | 121.2 (17) |
| N3—C8—H18 | 109.9 (15) | C21—C20—H120 | 118.2 (17) |
| C7—C8—H18 | 109.5 (14) | C20—C21—C16 | 120.8 (3) |
| N3—C8—H28 | 107.8 (13) | C20—C21—H121 | 122.3 (16) |
| C7—C8—H28 | 108.2 (13) | C16—C21—H121 | 116.7 (16) |
| H18—C8—H28 | 110.2 (19) |
Brandenburg, K. (1998). DIAMOND. Université de Bonn, Allemagne.
Duisenberg, A. J. M. (1992). J. Appl. Cryst. 25, 92–96. [Reference not cited - may it be removed?]
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, les Pays-Bas.
Harms, K. & Wocadlo, S. (1995). XCAD4. Université de Marburg, Allemagne.
Mikami, K., Terada, M., Motoyama, Y. & Nakai, T. (1991). Tetrahedron Asymmetry, 2, 643–646.
Mrabet, H. & Zantour, H. (2004). J. Soc. Alger. Chim. 14, 197–204.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
Ould M'hamed, M., Mrabet, H. & Efrit, M. L. (2007). C. R. Chim. 10, 1147–1156.
Ould M'hamed, M., Mrabet, H. & Efrit, M. L. (2008). J. Soc. Chim. Tunis. 10. Sous presse. [Any update?]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Toumi, M., Ben Amor, F., Raouafi, N., Bordeau, M., Driss, A. & Boujlel, K. (2007). Acta Cryst. E63, o2735.
Des travaux récents réalisés dans notre laboratoire ont montré que les dérivés acryliques sont d'excellents agents bi-électrophiles-1,3. Ils constituent des précurseurs d'une large gamme d'hétérocycles (Mrabet & Zantour, 2004; Ould M'hamed et al., 2007). Ces synthons sont également de bons diénophiles dans la réaction de Diels–Alder (Ould M'hamed et al., 2008), ce qui permet d'obtenir des composés bicycliques très recherchés en tant qu'analogues de substances naturelles (Mikami et al., 1991).
La molécule C21H23N3 est caractérisée par la présence d'un groupement pipérazinyle ayant chaque atome d'azote substitué. L'atome d'azote N3 est lié au carbone C9 qui est lui-même lié à deux noyaux phényles. L'autre atome d'azote N2 est lié au carbone C4 qui porte le groupement 1-cyanovinyle (C1, C2, C3, N1).
Le noyau phényle formé par les atomes C10, C11, C12, C13, C14 et C15 (phényle 1) est sur un plan moyen d'équation: 12,26 (1) x - 2,226 (7) y - 14,04 (1) z = 0,493 (8).
La déviation moyenne de ses atomes est de 0,002 Å. Les atomes de carbone C16, C17, C18, C19, C20 et C21 du deuxième phényle (phényle 2) définissent un plan moyen d'équation 13,76 (1) x - 1,692 (8) y + 5,23 (2) z = 4,399 (4). Ils dévient en moyenne de ce plan de 0,007 Å. L'atome de carbone C9 qui porte les deux phényles dévie de leurs plans de 0,037 (4) Å et 0,073 (4) Å respectivement. Les deux phényles forment entre eux un angle de 71,61 (8)°. Les atomes N1, C1, C2 et C3 du groupement 1-cyanovinyle forment eux aussi un plan d'équation: -11,20 (4) x + 2,303 (9) y + 14,68 (4) z = 4,062 (6). Leur déviation moyenne est de 0,0006 Å. Ce groupement fait un angle de 4,8(3)° avec le premier phényle et un angle de 76,1(2)° avec le deuxième phényle. La valeur de la distance N1—C1 [1,139 (3) Å] et les valeurs moyennes des distances N—C [1,469 (3) Å] et C—C [1,518 (4) Å] du groupement pipérazinyle sont en accord avec celles rencontrées dans des composés ayant ces types de liaisons (Toumi et al., 2007).