Acta Cryst. (2008). E64, o1747 [ doi:10.1107/S1600536808025464 ]
The asymmetric unit of the title compound, C19H22N2, contains one half-molecule. The 1,2,3,4-tetrahydroquinoline units are linked by a methylene bridge, which lies on a twofold rotation axis. The non-aromatic ring adopts a flattened-boat conformation. The dihedral angle between the two symmetry-related benzene rings is 64.03 (7)°.
Heating of 4,4'-methylenedibenzenamine (2 g), bis(4-nitrophenyl)methane (0.5 g), H3AsO4 (1.5 g), concentrated H2SO4 (3 ml), and glycerol (8.6 ml) at 413 K for 5 h, addition of water, removal of resinous matter, making alkalization with NaOH, taking up in ether, dehydration with K2CO3, and recrystallization of the residue from alcohol gives diquinolin-6-ylmethane. The resulting product (1 g) was subsequently heated with Sn (5.5 g) and HCl (22 ml, 32%) in a water bath for 8 h, addition of water, precipitation of the Sn as Sn(OH)2 by NaOH, taking up in ether, and drying with K2CO3, gives the title compound (yield; 0.9 g), which was recrystallized from petroleum ether-ethyl acetate to give colorless prisms.
H1 atom (for bridging CH2) was located in difference syntheses and refined isotropically [C-H = 0.97 (2) Å and Uiso(H) = 0.067 (10) Å2]. The remaining H atoms were positioned geometrically, with N-H = 0.86 Å (for NH) and C-H = 0.93 and 0.97 Å for aromatic and methylene H, respectively, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C).
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./hk2506fig1thm.gif)
| Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme [symmetry code: (a) -x, 1 - y, z]. |
| C19H22N2 | F000 = 1200 |
| Mr = 278.39 | Dx = 1.234 Mg m−3 |
| Orthorhombic, Fdd2 | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: F 2 -2d | Cell parameters from 1297 reflections |
| a = 17.515 (3) Å | θ = 2.9–25.2º |
| b = 29.660 (4) Å | µ = 0.07 mm−1 |
| c = 5.7678 (8) Å | T = 292 (2) K |
| V = 2996.2 (8) Å3 | Prism, colorless |
| Z = 8 | 0.30 × 0.20 × 0.20 mm |
| Enraf–Nonius CAD-4 diffractometer | 814 independent reflections |
| Radiation source: fine-focus sealed tube | 773 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.073 |
| T = 292(2) K | θmax = 26.0º |
| ω/2θ scans | θmin = 2.7º |
| Absorption correction: ψ scan (North et al., 1968) | h = −21→21 |
| Tmin = 0.979, Tmax = 0.986 | k = −36→32 |
| 4545 measured reflections | l = −7→6 |
| 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)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.138 | w = 1/[σ2(Fo2) + (0.0996P)2 + 0.9957P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.08 | (Δ/σ)max < 0.001 |
| 814 reflections | Δρmax = 0.28 e Å−3 |
| 100 parameters | Δρmin = −0.21 e Å−3 |
| 2 restraints | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods |
| C19H22N2 | V = 2996.2 (8) Å3 |
| Mr = 278.39 | Z = 8 |
| Orthorhombic, Fdd2 | Mo Kα |
| a = 17.515 (3) Å | µ = 0.07 mm−1 |
| b = 29.660 (4) Å | T = 292 (2) K |
| c = 5.7678 (8) Å | 0.30 × 0.20 × 0.20 mm |
| Enraf–Nonius CAD-4 diffractometer | 814 independent reflections |
| Absorption correction: ψ scan (North et al., 1968) | 773 reflections with I > 2σ(I) |
| Tmin = 0.979, Tmax = 0.986 | Rint = 0.073 |
| 4545 measured reflections |
| R[F2 > 2σ(F2)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.138 | Δρmax = 0.28 e Å−3 |
| S = 1.08 | Δρmin = −0.21 e Å−3 |
| 814 reflections | Absolute structure: ? |
| 100 parameters | Flack parameter: ? |
| 2 restraints | Rogers parameter: ? |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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. |
| x | y | z | Uiso*/Ueq | ||
| N1 | 0.26094 (12) | 0.44383 (8) | 1.0848 (5) | 0.0605 (7) | |
| H11A | 0.2700 | 0.4566 | 1.2159 | 0.073* | |
| C1 | 0.0000 | 0.5000 | 0.5624 (6) | 0.0519 (9) | |
| H1 | 0.0128 (16) | 0.5254 (7) | 0.464 (5) | 0.067 (10)* | |
| C2 | 0.31123 (16) | 0.40914 (9) | 1.0048 (7) | 0.0637 (9) | |
| H2A | 0.3360 | 0.3951 | 1.1368 | 0.076* | |
| H2B | 0.3505 | 0.4224 | 0.9080 | 0.076* | |
| C3 | 0.27005 (17) | 0.37452 (10) | 0.8715 (8) | 0.0662 (9) | |
| H3A | 0.2357 | 0.3584 | 0.9740 | 0.079* | |
| H3B | 0.3064 | 0.3530 | 0.8094 | 0.079* | |
| C4 | 0.22470 (16) | 0.39493 (9) | 0.6743 (6) | 0.0579 (8) | |
| H4A | 0.2595 | 0.4045 | 0.5530 | 0.070* | |
| H4B | 0.1911 | 0.3722 | 0.6097 | 0.070* | |
| C5 | 0.11375 (13) | 0.44942 (7) | 0.6314 (5) | 0.0415 (6) | |
| H5 | 0.1004 | 0.4345 | 0.4954 | 0.050* | |
| C6 | 0.06877 (12) | 0.48523 (8) | 0.7038 (5) | 0.0407 (6) | |
| C7 | 0.09023 (12) | 0.50718 (8) | 0.9058 (5) | 0.0434 (6) | |
| H7 | 0.0615 | 0.5315 | 0.9581 | 0.052* | |
| C8 | 0.15365 (13) | 0.49360 (8) | 1.0313 (5) | 0.0435 (6) | |
| H8 | 0.1667 | 0.5088 | 1.1667 | 0.052* | |
| C9 | 0.19817 (12) | 0.45735 (7) | 0.9568 (5) | 0.0384 (5) | |
| C10 | 0.17797 (12) | 0.43464 (7) | 0.7524 (5) | 0.0390 (6) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0578 (13) | 0.0610 (13) | 0.0628 (17) | 0.0115 (10) | −0.0273 (12) | −0.0153 (13) |
| C1 | 0.0451 (19) | 0.068 (2) | 0.042 (2) | 0.0156 (17) | 0.000 | 0.000 |
| C2 | 0.0537 (15) | 0.0635 (16) | 0.074 (2) | 0.0170 (11) | −0.0201 (16) | 0.0025 (16) |
| C3 | 0.0623 (16) | 0.0582 (15) | 0.078 (2) | 0.0198 (12) | −0.0097 (17) | −0.0042 (16) |
| C4 | 0.0622 (16) | 0.0558 (14) | 0.0558 (18) | 0.0202 (12) | −0.0111 (15) | −0.0126 (14) |
| C5 | 0.0420 (12) | 0.0442 (11) | 0.0384 (13) | 0.0016 (9) | −0.0014 (11) | −0.0069 (10) |
| C6 | 0.0324 (10) | 0.0460 (10) | 0.0437 (13) | 0.0024 (8) | 0.0016 (10) | 0.0000 (11) |
| C7 | 0.0383 (11) | 0.0416 (11) | 0.0504 (15) | 0.0045 (9) | 0.0061 (10) | −0.0052 (11) |
| C8 | 0.0440 (12) | 0.0432 (11) | 0.0433 (14) | −0.0040 (9) | −0.0018 (11) | −0.0113 (11) |
| C9 | 0.0345 (11) | 0.0392 (10) | 0.0416 (13) | −0.0032 (8) | −0.0034 (10) | 0.0013 (10) |
| C10 | 0.0398 (11) | 0.0375 (10) | 0.0398 (12) | 0.0008 (8) | −0.0007 (10) | −0.0036 (11) |
| N1—C2 | 1.431 (3) | C4—H4B | 0.9700 |
| N1—H11A | 0.8600 | C5—C6 | 1.387 (3) |
| C1—C6 | 1.519 (3) | C5—C10 | 1.394 (3) |
| C1—C6i | 1.519 (3) | C5—H5 | 0.9300 |
| C1—H1 | 0.97 (2) | C7—C6 | 1.386 (4) |
| C2—C3 | 1.472 (4) | C7—H7 | 0.9300 |
| C2—H2A | 0.9700 | C8—C7 | 1.386 (3) |
| C2—H2B | 0.9700 | C8—H8 | 0.9300 |
| C3—H3A | 0.9700 | C9—N1 | 1.384 (3) |
| C3—H3B | 0.9700 | C9—C8 | 1.396 (3) |
| C4—C3 | 1.514 (4) | C9—C10 | 1.403 (4) |
| C4—H4A | 0.9700 | C10—C4 | 1.503 (3) |
| C9—N1—C2 | 121.7 (3) | C10—C4—H4B | 109.2 |
| C9—N1—H11A | 119.2 | C3—C4—H4B | 109.2 |
| C2—N1—H11A | 119.2 | H4A—C4—H4B | 107.9 |
| C6—C1—C6i | 115.1 (3) | C6—C5—C10 | 123.3 (2) |
| C6—C1—H1 | 110.8 (18) | C6—C5—H5 | 118.4 |
| C6i—C1—H1 | 105.9 (19) | C10—C5—H5 | 118.4 |
| N1—C2—C3 | 111.6 (2) | C7—C6—C5 | 117.3 (2) |
| N1—C2—H2A | 109.3 | C7—C6—C1 | 122.0 (2) |
| C3—C2—H2A | 109.3 | C5—C6—C1 | 120.6 (2) |
| N1—C2—H2B | 109.3 | C8—C7—C6 | 121.3 (2) |
| C3—C2—H2B | 109.3 | C8—C7—H7 | 119.3 |
| H2A—C2—H2B | 108.0 | C6—C7—H7 | 119.3 |
| C2—C3—C4 | 111.8 (2) | C7—C8—C9 | 120.7 (2) |
| C2—C3—H3A | 109.3 | C7—C8—H8 | 119.6 |
| C4—C3—H3A | 109.3 | C9—C8—H8 | 119.6 |
| C2—C3—H3B | 109.3 | N1—C9—C8 | 120.2 (2) |
| C4—C3—H3B | 109.3 | N1—C9—C10 | 120.6 (2) |
| H3A—C3—H3B | 107.9 | C8—C9—C10 | 119.2 (2) |
| C10—C4—C3 | 112.0 (2) | C5—C10—C9 | 118.2 (2) |
| C10—C4—H4A | 109.2 | C5—C10—C4 | 122.4 (2) |
| C3—C4—H4A | 109.2 | C9—C10—C4 | 119.4 (2) |
| C9—N1—C2—C3 | −33.5 (4) | C9—C8—C7—C6 | 0.3 (4) |
| C6i—C1—C6—C7 | −39.05 (19) | C8—C9—N1—C2 | −175.1 (2) |
| C6i—C1—C6—C5 | 142.3 (3) | C10—C9—N1—C2 | 5.6 (4) |
| N1—C2—C3—C4 | 54.2 (4) | N1—C9—C8—C7 | −179.4 (2) |
| C10—C4—C3—C2 | −48.1 (4) | C10—C9—C8—C7 | 0.0 (4) |
| C10—C5—C6—C7 | 0.6 (4) | N1—C9—C10—C5 | 179.4 (2) |
| C10—C5—C6—C1 | 179.3 (2) | C8—C9—C10—C5 | 0.0 (3) |
| C6—C5—C10—C9 | −0.3 (4) | N1—C9—C10—C4 | 0.7 (4) |
| C6—C5—C10—C4 | 178.3 (2) | C8—C9—C10—C4 | −178.6 (2) |
| C8—C7—C6—C5 | −0.6 (4) | C5—C10—C4—C3 | −157.7 (2) |
| C8—C7—C6—C1 | −179.2 (2) | C9—C10—C4—C3 | 20.9 (4) |
| Symmetry codes: (i) −x, −y+1, z. |
The work was financed by the Natural Science Foundation of Jiangsu Province (grant No. BK2007081).
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Xiao, Z.-P., Shi, D.-H., Li, H.-Q., Zhang, L.-N., Xu, C. & Zhu, H.-L. (2007b). Bioorg. Med. Chem. 15, 3703–3710.
Xiao, Z.-P., Xue, J.-Y., Tan, S.-H., Li, H.-Q. & Zhu, H.-L. (2007a). Bioorg. Med. Chem. 15, 4212–4219.
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Nitrogen heterocyclic compounds show diverse biological activities such as antiproliferative (Xiao et al., 2008a,b), antibacterial (Xiao et al., 2007a; Xue et al., 2007; Xiao et al., 2008c), and urease inhibitory (Xiao et al., 2007b) activities. The title compound is a heterocyclic compound, which may be used for screening the biological activities. We report herein its crystal structure.
The asymmetric unit of the title compound (Fig. 1) contains one-half molecule. 1,2,3,4-Tetrahydroquinoline moieties are joined by a methylene bridge. Ring A (N1/C2-C4/C9/C10) adopts flattened-boat [φ = 126.28 (2)°, θ = 26.77 (3)°] conformation, having total puckering amplitude, QT, of 0.448 (3) Å (Cremer & Pople, 1975). The dihedral angle between the two symmetry related phenyl rings is 64.03 (7)°.