organic compounds
9-(1H-Benzo[d]imidazol-2-yl)-2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinoline
aDepartamento de Química, Universidad de Guanajuato, Noria Alta S/N, Col. Noria Alta, CP 36050, Guanajuato, Gto., Mexico
*Correspondence e-mail: muralivenkat@ugto.mx
The title compound, C19H19N3, is a 2-heteroaryl benzimidazole derivative obtained through a straightforward and efficient protocol starting from julolidine-9-carbaldehyde and 1,2-phenylendiamine. The mean planes of the heterocyclic moieties in the molecule, benzimidazole and julolidine, form a dihedral angle of 40.9 (1)°. In the crystal, N—H⋯N hydrogen bonds link the imidazole rings, forming chains along the c-axis direction.
CCDC reference: 1539272
Structure description
Benzimidazole derivatives play an important role as pharmacophores in pharmaceuticals, and have been shown to possess different biological properties, such as antioxidant (Ayhan-Kilcigil et al., 2004) and antifungal (Preston et al., 1974) activity. We present here the of a 2-heteroaryl benzimidazole derivative (Fig. 1). The compound contains two heterocycles, which are skewed with an N1—C1—C8—C9 torsion angle of −34.7 (5)°. The dihedral angle between the mean planes of the benzimidazole and the julolidine moieties is 40.9 (1)°.
In the crystal, a supramolecular structure based on intermolecular N2—H2⋯N1i hydrogen bonds is formed (Table 1), featuring zigzag chains of molecules in the [001] direction (Fig. 2).
Synthesis and crystallization
The title compound was synthesized (Fig. 3) by mixing equimolar amounts of o-phenylenediamine (1 mmol) and 9-julolidine carboxaldehyde (1 mmol) in ethanol. The resulting mixture was refluxed for 3 h. After cooling to room temperature, the solvents were removed under reduced pressure, and the residue purified by silica gel with petroleum ether/ethylacetate (6:4, v:v) as to afford the title compound as a colourless solid (95% yield). The compound was recrystallized from petroleum ether/diethyl ether (1:1, v:v).
1H NMR (500 MHz, CDCl3), δ (p.p.m.): 7.57 (s, 1H), 7.50 (s, 2H), 7.26 (s, 2H), 7.20 (dd, J = 6.0, 3.1 Hz, 2H), 3.24–3.21 (m, 4H), 2.78 (t, J = 6.3 Hz, 4H), 2.00–1.94 (m, 4H). 13C NMR (126 MHz, CDCl3), δ (p.p.m.): 152.8, 144.8, 125.5, 122.4, 121.4, 50.0, 27.8, 21.8.
Refinement
Crystal data, data collection and structure . The methylene C atoms (C11, C12, C13, C16, C17, C18) in the julolidine group were refined with restrained displacement parameters: rigid-bond restraints were applied and atoms closer than 2 Å were restrained to have similar Uij parameters within a standard deviation of 0.04 Å2; finally, these C atoms were restrained to approximate an isotropic behaviour (Sheldrick, 2015).
details are summarized in Table 2Structural data
CCDC reference: 1539272
https://doi.org/10.1107/S241431461700445X/bh4024sup1.cif
contains datablocks I, global. DOI:Supporting information file. DOI: https://doi.org/10.1107/S241431461700445X/bh4024Isup3.cdx
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461700445X/bh4024Isup4.hkl
Supporting information file. DOI: https://doi.org/10.1107/S241431461700445X/bh4024Isup4.cml
Data collection: CrysAlis PRO (Rigaku OD, 2015); cell
CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: olex2.solve (Bourhis et al., 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C19H19N3 | Dx = 1.262 Mg m−3 |
Mr = 289.37 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pca21 | Cell parameters from 2311 reflections |
a = 14.0540 (11) Å | θ = 4.4–28.4° |
b = 11.2639 (6) Å | µ = 0.08 mm−1 |
c = 9.6184 (5) Å | T = 100 K |
V = 1522.62 (16) Å3 | Block, colourless |
Z = 4 | 0.53 × 0.34 × 0.26 mm |
F(000) = 616 |
Rigaku OD SuperNova, Single source at offset, EosS2 diffractometer | 2727 independent reflections |
Radiation source: SuperNova (Mo) X-ray Source | 2528 reflections with I > 2σ(I) |
Detector resolution: 8.0945 pixels mm-1 | Rint = 0.021 |
ω scans | θmax = 29.4°, θmin = 3.4° |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015) | h = −18→10 |
Tmin = 0.878, Tmax = 1.000 | k = −15→13 |
4617 measured reflections | l = −13→11 |
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) = 0.154 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0917P)2 + 0.6633P] where P = (Fo2 + 2Fc2)/3 |
2727 reflections | (Δ/σ)max < 0.001 |
200 parameters | Δρmax = 0.79 e Å−3 |
67 restraints | Δρmin = −0.34 e Å−3 |
0 constraints |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.1962 (2) | 0.8178 (2) | 0.3418 (3) | 0.0216 (6) | |
N2 | 0.2282 (2) | 0.8416 (2) | 0.5680 (3) | 0.0200 (6) | |
H2 | 0.253182 | 0.828378 | 0.650431 | 0.029 (11)* | |
N3 | 0.4176 (2) | 0.3248 (2) | 0.5017 (3) | 0.0286 (7) | |
C1 | 0.2398 (2) | 0.7740 (2) | 0.4529 (3) | 0.0184 (6) | |
C2 | 0.1513 (2) | 0.9199 (3) | 0.3887 (3) | 0.0215 (7) | |
C3 | 0.1697 (2) | 0.9357 (3) | 0.5316 (3) | 0.0213 (7) | |
C4 | 0.1295 (3) | 1.0267 (3) | 0.6076 (4) | 0.0285 (8) | |
H4 | 0.142022 | 1.035931 | 0.704076 | 0.034* | |
C5 | 0.0695 (3) | 1.1045 (3) | 0.5363 (4) | 0.0345 (9) | |
H5 | 0.040386 | 1.168141 | 0.585225 | 0.041* | |
C6 | 0.0517 (3) | 1.0907 (3) | 0.3954 (5) | 0.0341 (8) | |
H6 | 0.010790 | 1.145665 | 0.350216 | 0.041* | |
C7 | 0.0913 (3) | 0.9995 (3) | 0.3184 (4) | 0.0284 (8) | |
H7 | 0.078437 | 0.991119 | 0.221969 | 0.034* | |
C8 | 0.2907 (2) | 0.6604 (2) | 0.4590 (3) | 0.0189 (6) | |
C9 | 0.2574 (3) | 0.5634 (3) | 0.3814 (4) | 0.0239 (7) | |
H9 | 0.205427 | 0.573953 | 0.319546 | 0.029* | |
C10 | 0.2991 (3) | 0.4531 (3) | 0.3937 (4) | 0.0253 (7) | |
C11 | 0.2605 (3) | 0.3483 (3) | 0.3122 (5) | 0.0415 (11) | |
H11A | 0.190698 | 0.356295 | 0.301694 | 0.050* | |
H11B | 0.289195 | 0.347109 | 0.218247 | 0.050* | |
C12 | 0.2833 (3) | 0.2335 (3) | 0.3871 (6) | 0.0477 (12) | |
H12A | 0.244727 | 0.228660 | 0.473014 | 0.057* | |
H12B | 0.265494 | 0.165665 | 0.326989 | 0.057* | |
C13 | 0.3849 (3) | 0.2240 (3) | 0.4236 (5) | 0.0405 (10) | |
H13A | 0.395126 | 0.150983 | 0.478932 | 0.049* | |
H13B | 0.422914 | 0.217004 | 0.337263 | 0.049* | |
C14 | 0.3775 (2) | 0.4364 (3) | 0.4838 (3) | 0.0211 (7) | |
C15 | 0.4143 (2) | 0.5353 (3) | 0.5566 (3) | 0.0223 (7) | |
C16 | 0.5092 (3) | 0.3136 (3) | 0.5706 (5) | 0.0398 (9) | |
H16A | 0.560227 | 0.327935 | 0.501689 | 0.048* | |
H16B | 0.516213 | 0.231204 | 0.604927 | 0.048* | |
C17 | 0.5219 (4) | 0.3968 (4) | 0.6891 (6) | 0.0535 (13) | |
H17A | 0.588222 | 0.391328 | 0.723392 | 0.064* | |
H17B | 0.479037 | 0.373227 | 0.765948 | 0.064* | |
C18 | 0.5012 (3) | 0.5218 (3) | 0.6485 (4) | 0.0338 (9) | |
H18A | 0.557154 | 0.554489 | 0.599026 | 0.041* | |
H18B | 0.491807 | 0.569539 | 0.733895 | 0.041* | |
C19 | 0.3690 (2) | 0.6436 (3) | 0.5452 (3) | 0.0208 (6) | |
H19 | 0.392053 | 0.708810 | 0.597922 | 0.025* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0255 (15) | 0.0238 (12) | 0.0156 (12) | −0.0003 (11) | −0.0014 (12) | −0.0011 (10) |
N2 | 0.0275 (15) | 0.0200 (11) | 0.0126 (12) | 0.0018 (10) | 0.0012 (12) | 0.0003 (10) |
N3 | 0.0309 (16) | 0.0221 (13) | 0.0328 (16) | 0.0040 (12) | 0.0029 (14) | −0.0037 (11) |
C1 | 0.0201 (15) | 0.0214 (13) | 0.0138 (13) | −0.0034 (11) | 0.0027 (13) | −0.0010 (11) |
C2 | 0.0269 (17) | 0.0201 (14) | 0.0175 (14) | −0.0017 (12) | 0.0023 (14) | 0.0019 (12) |
C3 | 0.0238 (17) | 0.0211 (13) | 0.0191 (14) | −0.0007 (13) | 0.0039 (14) | 0.0014 (12) |
C4 | 0.036 (2) | 0.0284 (16) | 0.0213 (16) | 0.0023 (15) | 0.0019 (16) | −0.0037 (13) |
C5 | 0.040 (2) | 0.0254 (15) | 0.038 (2) | 0.0084 (15) | 0.0080 (19) | −0.0031 (15) |
C6 | 0.037 (2) | 0.0283 (17) | 0.0370 (19) | 0.0070 (15) | −0.0026 (19) | 0.0035 (15) |
C7 | 0.034 (2) | 0.0272 (15) | 0.0242 (16) | −0.0003 (15) | −0.0042 (16) | 0.0037 (13) |
C8 | 0.0220 (16) | 0.0210 (13) | 0.0137 (12) | −0.0005 (12) | 0.0037 (13) | −0.0005 (11) |
C9 | 0.0244 (17) | 0.0264 (14) | 0.0209 (14) | −0.0006 (13) | −0.0047 (14) | −0.0056 (13) |
C10 | 0.0277 (18) | 0.0234 (15) | 0.0247 (15) | −0.0009 (13) | −0.0044 (16) | −0.0051 (13) |
C11 | 0.046 (3) | 0.0287 (16) | 0.050 (3) | 0.0014 (17) | −0.020 (2) | −0.0132 (17) |
C12 | 0.041 (2) | 0.0299 (18) | 0.072 (3) | −0.0051 (16) | −0.004 (3) | −0.013 (2) |
C13 | 0.056 (3) | 0.0210 (16) | 0.044 (2) | 0.0042 (16) | −0.010 (2) | −0.0074 (15) |
C14 | 0.0245 (17) | 0.0221 (13) | 0.0167 (15) | 0.0002 (12) | 0.0044 (14) | −0.0009 (11) |
C15 | 0.0236 (16) | 0.0273 (14) | 0.0160 (14) | 0.0017 (12) | 0.0000 (14) | −0.0006 (12) |
C16 | 0.046 (2) | 0.0370 (18) | 0.0358 (19) | 0.0163 (18) | −0.012 (2) | −0.0017 (17) |
C17 | 0.054 (3) | 0.049 (2) | 0.057 (3) | 0.012 (2) | −0.023 (3) | −0.002 (2) |
C18 | 0.034 (2) | 0.0352 (18) | 0.0320 (19) | 0.0059 (17) | −0.0124 (18) | −0.0063 (15) |
C19 | 0.0250 (16) | 0.0235 (13) | 0.0139 (14) | −0.0047 (12) | 0.0004 (14) | −0.0026 (11) |
N1—C1 | 1.327 (4) | C10—C14 | 1.415 (5) |
N1—C2 | 1.387 (4) | C10—C11 | 1.517 (5) |
N2—C1 | 1.354 (4) | C11—C12 | 1.514 (6) |
N2—C3 | 1.386 (4) | C11—H11A | 0.9900 |
N2—H2 | 0.8800 | C11—H11B | 0.9900 |
N3—C14 | 1.388 (4) | C12—C13 | 1.475 (6) |
N3—C13 | 1.438 (5) | C12—H12A | 0.9900 |
N3—C16 | 1.452 (5) | C12—H12B | 0.9900 |
C1—C8 | 1.467 (4) | C13—H13A | 0.9900 |
C2—C7 | 1.405 (5) | C13—H13B | 0.9900 |
C2—C3 | 1.410 (5) | C14—C15 | 1.413 (4) |
C3—C4 | 1.380 (5) | C15—C19 | 1.380 (4) |
C4—C5 | 1.396 (5) | C15—C18 | 1.516 (5) |
C4—H4 | 0.9500 | C16—C17 | 1.487 (6) |
C5—C6 | 1.387 (6) | C16—H16A | 0.9900 |
C5—H5 | 0.9500 | C16—H16B | 0.9900 |
C6—C7 | 1.383 (5) | C17—C18 | 1.490 (6) |
C6—H6 | 0.9500 | C17—H17A | 0.9900 |
C7—H7 | 0.9500 | C17—H17B | 0.9900 |
C8—C19 | 1.390 (5) | C18—H18A | 0.9900 |
C8—C9 | 1.403 (4) | C18—H18B | 0.9900 |
C9—C10 | 1.379 (4) | C19—H19 | 0.9500 |
C9—H9 | 0.9500 | ||
C1—N1—C2 | 104.9 (3) | C10—C11—H11B | 109.7 |
C1—N2—C3 | 107.2 (3) | H11A—C11—H11B | 108.2 |
C1—N2—H2 | 126.4 | C13—C12—C11 | 112.4 (4) |
C3—N2—H2 | 126.4 | C13—C12—H12A | 109.1 |
C14—N3—C13 | 121.4 (3) | C11—C12—H12A | 109.1 |
C14—N3—C16 | 119.7 (3) | C13—C12—H12B | 109.1 |
C13—N3—C16 | 116.9 (3) | C11—C12—H12B | 109.1 |
N1—C1—N2 | 113.2 (3) | H12A—C12—H12B | 107.9 |
N1—C1—C8 | 125.6 (3) | N3—C13—C12 | 112.1 (3) |
N2—C1—C8 | 121.1 (3) | N3—C13—H13A | 109.2 |
N1—C2—C7 | 130.3 (3) | C12—C13—H13A | 109.2 |
N1—C2—C3 | 109.8 (3) | N3—C13—H13B | 109.2 |
C7—C2—C3 | 119.9 (3) | C12—C13—H13B | 109.2 |
C4—C3—N2 | 132.6 (3) | H13A—C13—H13B | 107.9 |
C4—C3—C2 | 122.4 (3) | N3—C14—C15 | 120.2 (3) |
N2—C3—C2 | 105.0 (3) | N3—C14—C10 | 120.8 (3) |
C3—C4—C5 | 117.0 (3) | C15—C14—C10 | 118.9 (3) |
C3—C4—H4 | 121.5 | C19—C15—C14 | 119.2 (3) |
C5—C4—H4 | 121.5 | C19—C15—C18 | 120.5 (3) |
C6—C5—C4 | 121.2 (3) | C14—C15—C18 | 120.3 (3) |
C6—C5—H5 | 119.4 | N3—C16—C17 | 113.7 (3) |
C4—C5—H5 | 119.4 | N3—C16—H16A | 108.8 |
C7—C6—C5 | 122.3 (4) | C17—C16—H16A | 108.8 |
C7—C6—H6 | 118.9 | N3—C16—H16B | 108.8 |
C5—C6—H6 | 118.9 | C17—C16—H16B | 108.8 |
C6—C7—C2 | 117.3 (3) | H16A—C16—H16B | 107.7 |
C6—C7—H7 | 121.3 | C16—C17—C18 | 111.8 (4) |
C2—C7—H7 | 121.3 | C16—C17—H17A | 109.3 |
C19—C8—C9 | 118.3 (3) | C18—C17—H17A | 109.3 |
C19—C8—C1 | 121.9 (3) | C16—C17—H17B | 109.3 |
C9—C8—C1 | 119.7 (3) | C18—C17—H17B | 109.3 |
C10—C9—C8 | 121.0 (3) | H17A—C17—H17B | 107.9 |
C10—C9—H9 | 119.5 | C17—C18—C15 | 113.9 (3) |
C8—C9—H9 | 119.5 | C17—C18—H18A | 108.8 |
C9—C10—C14 | 120.2 (3) | C15—C18—H18A | 108.8 |
C9—C10—C11 | 120.3 (3) | C17—C18—H18B | 108.8 |
C14—C10—C11 | 119.5 (3) | C15—C18—H18B | 108.8 |
C12—C11—C10 | 110.0 (3) | H18A—C18—H18B | 107.7 |
C12—C11—H11A | 109.7 | C15—C19—C8 | 122.2 (3) |
C10—C11—H11A | 109.7 | C15—C19—H19 | 118.9 |
C12—C11—H11B | 109.7 | C8—C19—H19 | 118.9 |
C2—N1—C1—N2 | −1.3 (4) | C14—C10—C11—C12 | 25.5 (6) |
C2—N1—C1—C8 | 174.5 (3) | C10—C11—C12—C13 | −51.3 (5) |
C3—N2—C1—N1 | 2.1 (4) | C14—N3—C13—C12 | −30.0 (5) |
C3—N2—C1—C8 | −174.0 (3) | C16—N3—C13—C12 | 166.2 (4) |
C1—N1—C2—C7 | −176.8 (4) | C11—C12—C13—N3 | 54.2 (6) |
C1—N1—C2—C3 | 0.1 (4) | C13—N3—C14—C15 | −176.7 (3) |
C1—N2—C3—C4 | 175.1 (4) | C16—N3—C14—C15 | −13.4 (5) |
C1—N2—C3—C2 | −1.9 (3) | C13—N3—C14—C10 | 3.8 (5) |
N1—C2—C3—C4 | −176.3 (3) | C16—N3—C14—C10 | 167.1 (3) |
C7—C2—C3—C4 | 1.0 (5) | C9—C10—C14—N3 | 177.2 (3) |
N1—C2—C3—N2 | 1.1 (4) | C11—C10—C14—N3 | −2.0 (5) |
C7—C2—C3—N2 | 178.4 (3) | C9—C10—C14—C15 | −2.3 (5) |
N2—C3—C4—C5 | −177.1 (4) | C11—C10—C14—C15 | 178.5 (4) |
C2—C3—C4—C5 | −0.6 (5) | N3—C14—C15—C19 | −175.2 (3) |
C3—C4—C5—C6 | −0.1 (6) | C10—C14—C15—C19 | 4.3 (5) |
C4—C5—C6—C7 | 0.4 (7) | N3—C14—C15—C18 | 3.4 (5) |
C5—C6—C7—C2 | 0.0 (6) | C10—C14—C15—C18 | −177.0 (3) |
N1—C2—C7—C6 | 175.9 (4) | C14—N3—C16—C17 | 38.2 (5) |
C3—C2—C7—C6 | −0.7 (5) | C13—N3—C16—C17 | −157.8 (4) |
N1—C1—C8—C19 | 148.5 (3) | N3—C16—C17—C18 | −51.9 (6) |
N2—C1—C8—C19 | −36.0 (5) | C16—C17—C18—C15 | 41.9 (6) |
N1—C1—C8—C9 | −34.7 (5) | C19—C15—C18—C17 | 160.0 (4) |
N2—C1—C8—C9 | 140.9 (3) | C14—C15—C18—C17 | −18.6 (5) |
C19—C8—C9—C10 | 2.2 (5) | C14—C15—C19—C8 | −3.1 (5) |
C1—C8—C9—C10 | −174.7 (3) | C18—C15—C19—C8 | 178.2 (3) |
C8—C9—C10—C14 | −1.0 (6) | C9—C8—C19—C15 | −0.1 (5) |
C8—C9—C10—C11 | 178.2 (4) | C1—C8—C19—C15 | 176.8 (3) |
C9—C10—C11—C12 | −153.7 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N1i | 0.88 | 1.98 | 2.852 (4) | 173 |
Symmetry code: (i) −x+1/2, y, z+1/2. |
Acknowledgements
The authors are grateful to the Universidad de Guanajuato for access to the single-crystal analysis facility.
Funding information
Funding for this research was provided by: Consejo Nacional de Ciencia y Tecnologíahttps://doi.org/10.13039/501100003141 (award No. 123732); Universidad de Guanajuatohttps://doi.org/10.13039/501100006054 (award No. DAIP-1105/2016).
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