organic compounds
2-Methyl-4-(pyridin-2-yl)-3H-1,5-benzodiazepine
aLaboratoire de Chimie Organique Heterocyclique URAC 21, Av. Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco, bLaboratory of Medicinal Chemistry, Faculty of Medicine and Pharmacy, Mohammed V University Rabat, Morocco, cNational Center of Energy Sciences and Nuclear Techniques, Rabat, Morocco, dLaboratoire de Chimie Bio Organique Appliquee, Faculté des Sciences, Université Ibn Zohr, Agadir, Morocco, and eDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
*Correspondence e-mail: lelghayati@yahoo.com
In the title compound, C15H13N3, the seven-membered ring adopts a boat conformation. In the crystal, inversion-related C—H⋯N hydrogen bonds form dimers, which pack in an alternating fashion.
Keywords: crystal structure; hydrogen bond; benzodiazepine.
CCDC reference: 1853275
Structure description
The renewed interest in bicyclic heterocycles derived from 1,5-benzodiazepine is based mainly on their biological properties and therapeutic functions (Wang et al., 2015). As a continuation of our research into 1,5-benzodiazepine derivatives (Tjiou et al., 2005), we prepared the title compound and characterized it by X-ray diffraction.
In the title compound (Fig. 1), the seven-membered ring adopts a boat conformation with Cremer–Pople puckering parameters Q(2) = 0.8492 (11) Å, Q(3) = 0.2494 (12) Å, φ(2) = 205.89 (8)° and φ(3) = 307.6 (3)°. The total puckering amplitude is 0.8850 (12) Å. The C1–C6 phenyl ring makes a dihedral angle of 30.05 (6)° with the N3/C11–C15 pyridine ring. In the crystal, inversion-related C15—H15⋯N3 hydrogen bonds form weak dimers, which pack in an alternating fashion (Table 1 and Fig. 2).
Synthesis and crystallization
A mixture of o-phenylenediamine (3 mmol) and 1-(pyridin-2-yl)butane-1,3-dione (3 mmol) in 30 ml of xylene was heated under reflux for 3 h. The reaction mixture was cooled at room temperature, the precipitated solid was collected by filtration and recrystallized from dry ethanol to give yellow crystals, m.p. 99–100°C.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1853275
https://doi.org/10.1107/S2414314618009537/vm4036sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618009537/vm4036Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314618009537/vm4036Isup3.cml
Data collection: APEX3 (Bruker, 2016); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C15H13N3 | F(000) = 496 |
Mr = 235.28 | Dx = 1.322 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 5.9642 (6) Å | Cell parameters from 3540 reflections |
b = 17.7004 (17) Å | θ = 2.3–28.7° |
c = 11.3963 (11) Å | µ = 0.08 mm−1 |
β = 100.695 (1)° | T = 100 K |
V = 1182.2 (2) Å3 | Plate, colorless |
Z = 4 | 0.27 × 0.20 × 0.07 mm |
Bruker SMART APEX CCD diffractometer | 3013 independent reflections |
Radiation source: fine-focus sealed tube | 2144 reflections with I > 2σ(I) |
Detector resolution: 8.3333 pixels mm-1 | Rint = 0.035 |
ω scans | θmax = 29.2°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −8→8 |
Tmin = 0.84, Tmax = 0.99 | k = −23→23 |
11157 measured reflections | l = −15→15 |
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)] = 0.043 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.108 | All H-atom parameters refined |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0657P)2] where P = (Fo2 + 2Fc2)/3 |
3013 reflections | (Δ/σ)max < 0.001 |
215 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
Experimental. The diffraction data were collected in three sets of 363 frames (0.5° width in ω) at φ = 0, 120 and 240°. A scan time of 30 sec/frame was used. |
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 | 0.34913 (16) | 0.27417 (5) | 0.30084 (8) | 0.0224 (2) | |
N2 | 0.27587 (16) | 0.42244 (5) | 0.16780 (8) | 0.0204 (2) | |
N3 | 0.76518 (16) | 0.49702 (5) | 0.35890 (8) | 0.0228 (2) | |
C1 | 0.11011 (19) | 0.36589 (6) | 0.16439 (10) | 0.0207 (3) | |
C2 | −0.0941 (2) | 0.37687 (7) | 0.08182 (11) | 0.0244 (3) | |
H2 | −0.111 (2) | 0.4250 (7) | 0.0379 (11) | 0.025 (3)* | |
C3 | −0.2649 (2) | 0.32385 (8) | 0.06639 (11) | 0.0281 (3) | |
H3 | −0.409 (2) | 0.3340 (8) | 0.0098 (12) | 0.037 (4)* | |
C4 | −0.2331 (2) | 0.25575 (7) | 0.12854 (11) | 0.0282 (3) | |
H4 | −0.353 (2) | 0.2159 (8) | 0.1160 (11) | 0.033 (4)* | |
C5 | −0.0300 (2) | 0.24196 (7) | 0.20519 (11) | 0.0252 (3) | |
H5 | 0.001 (2) | 0.1925 (8) | 0.2492 (11) | 0.029 (3)* | |
C6 | 0.1437 (2) | 0.29660 (6) | 0.22717 (10) | 0.0215 (3) | |
C7 | 0.4687 (2) | 0.32169 (7) | 0.37092 (10) | 0.0217 (3) | |
C8 | 0.3899 (2) | 0.40186 (7) | 0.38289 (10) | 0.0217 (3) | |
H8A | 0.224 (2) | 0.4008 (7) | 0.3882 (10) | 0.023 (3)* | |
H8B | 0.483 (2) | 0.4274 (7) | 0.4525 (11) | 0.024 (3)* | |
C9 | 0.41139 (19) | 0.43848 (6) | 0.26626 (10) | 0.0196 (3) | |
C10 | 0.6968 (2) | 0.29969 (8) | 0.43983 (12) | 0.0267 (3) | |
H10A | 0.815 (2) | 0.3338 (8) | 0.4217 (12) | 0.039 (4)* | |
H10B | 0.702 (2) | 0.3068 (8) | 0.5264 (13) | 0.036 (4)* | |
H10C | 0.736 (2) | 0.2461 (9) | 0.4232 (12) | 0.036 (4)* | |
C11 | 0.59968 (19) | 0.49276 (6) | 0.26147 (10) | 0.0193 (2) | |
C12 | 0.6041 (2) | 0.53489 (6) | 0.15832 (10) | 0.0224 (3) | |
H12 | 0.477 (2) | 0.5293 (7) | 0.0896 (11) | 0.023 (3)* | |
C13 | 0.7871 (2) | 0.58193 (7) | 0.15521 (11) | 0.0239 (3) | |
H13 | 0.792 (2) | 0.6104 (7) | 0.0838 (12) | 0.028 (3)* | |
C14 | 0.9602 (2) | 0.58643 (7) | 0.25468 (11) | 0.0245 (3) | |
H14 | 1.090 (2) | 0.6186 (7) | 0.2554 (11) | 0.026 (3)* | |
C15 | 0.9410 (2) | 0.54339 (7) | 0.35369 (11) | 0.0255 (3) | |
H15 | 1.062 (2) | 0.5457 (7) | 0.4260 (12) | 0.030 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0229 (5) | 0.0219 (5) | 0.0233 (5) | −0.0002 (4) | 0.0060 (4) | 0.0016 (4) |
N2 | 0.0201 (5) | 0.0188 (5) | 0.0219 (5) | 0.0006 (4) | 0.0023 (4) | −0.0003 (4) |
N3 | 0.0242 (5) | 0.0210 (5) | 0.0220 (5) | −0.0009 (4) | 0.0007 (4) | −0.0015 (4) |
C1 | 0.0213 (6) | 0.0219 (6) | 0.0198 (6) | −0.0004 (5) | 0.0061 (5) | −0.0028 (4) |
C2 | 0.0224 (6) | 0.0255 (6) | 0.0246 (6) | 0.0011 (5) | 0.0024 (5) | −0.0021 (5) |
C3 | 0.0199 (6) | 0.0343 (7) | 0.0294 (7) | −0.0007 (5) | 0.0023 (5) | −0.0037 (5) |
C4 | 0.0237 (6) | 0.0312 (7) | 0.0304 (7) | −0.0079 (6) | 0.0069 (5) | −0.0058 (5) |
C5 | 0.0279 (7) | 0.0239 (6) | 0.0254 (6) | −0.0030 (5) | 0.0091 (5) | −0.0012 (5) |
C6 | 0.0224 (6) | 0.0229 (6) | 0.0206 (6) | 0.0007 (5) | 0.0074 (5) | −0.0028 (4) |
C7 | 0.0252 (6) | 0.0218 (6) | 0.0195 (6) | −0.0004 (5) | 0.0074 (5) | 0.0046 (4) |
C8 | 0.0226 (6) | 0.0231 (6) | 0.0194 (6) | −0.0010 (5) | 0.0040 (5) | −0.0008 (5) |
C9 | 0.0207 (6) | 0.0174 (5) | 0.0204 (6) | 0.0040 (5) | 0.0030 (5) | −0.0004 (4) |
C10 | 0.0260 (7) | 0.0269 (7) | 0.0261 (7) | 0.0017 (5) | 0.0019 (5) | 0.0036 (5) |
C11 | 0.0213 (6) | 0.0162 (5) | 0.0200 (6) | 0.0028 (4) | 0.0028 (4) | −0.0022 (4) |
C12 | 0.0249 (6) | 0.0195 (6) | 0.0215 (6) | 0.0023 (5) | 0.0010 (5) | −0.0011 (5) |
C13 | 0.0288 (7) | 0.0197 (6) | 0.0238 (6) | 0.0021 (5) | 0.0065 (5) | 0.0022 (5) |
C14 | 0.0234 (6) | 0.0196 (6) | 0.0307 (7) | −0.0021 (5) | 0.0055 (5) | −0.0017 (5) |
C15 | 0.0240 (6) | 0.0240 (6) | 0.0265 (6) | −0.0007 (5) | −0.0006 (5) | −0.0026 (5) |
N1—C7 | 1.2816 (14) | C7—C8 | 1.5089 (17) |
N1—C6 | 1.4080 (15) | C8—C9 | 1.5055 (16) |
N2—C9 | 1.2871 (14) | C8—H8A | 1.001 (13) |
N2—C1 | 1.4023 (14) | C8—H8B | 0.990 (12) |
N3—C15 | 1.3418 (15) | C9—C11 | 1.4865 (16) |
N3—C11 | 1.3439 (14) | C10—H10A | 0.981 (15) |
C1—C2 | 1.4076 (16) | C10—H10B | 0.989 (14) |
C1—C6 | 1.4152 (16) | C10—H10C | 1.003 (15) |
C2—C3 | 1.3724 (17) | C11—C12 | 1.3965 (16) |
C2—H2 | 0.984 (13) | C12—C13 | 1.3784 (17) |
C3—C4 | 1.3931 (19) | C12—H12 | 0.987 (12) |
C3—H3 | 0.990 (14) | C13—C14 | 1.3865 (17) |
C4—C5 | 1.3775 (17) | C13—H13 | 0.963 (13) |
C4—H4 | 0.997 (13) | C14—C15 | 1.3835 (17) |
C5—C6 | 1.4050 (16) | C14—H14 | 0.961 (14) |
C5—H5 | 1.008 (13) | C15—H15 | 0.989 (13) |
C7—C10 | 1.4909 (17) | ||
C7—N1—C6 | 120.57 (10) | C9—C8—H8B | 112.6 (7) |
C9—N2—C1 | 120.46 (10) | C7—C8—H8B | 111.4 (7) |
C15—N3—C11 | 117.27 (10) | H8A—C8—H8B | 111.9 (10) |
N2—C1—C2 | 115.98 (10) | N2—C9—C11 | 117.84 (10) |
N2—C1—C6 | 124.87 (10) | N2—C9—C8 | 122.15 (10) |
C2—C1—C6 | 118.76 (10) | C11—C9—C8 | 119.97 (10) |
C3—C2—C1 | 121.40 (12) | C7—C10—H10A | 110.5 (8) |
C3—C2—H2 | 121.7 (7) | C7—C10—H10B | 110.5 (8) |
C1—C2—H2 | 116.9 (7) | H10A—C10—H10B | 104.0 (11) |
C2—C3—C4 | 119.91 (12) | C7—C10—H10C | 111.7 (8) |
C2—C3—H3 | 119.5 (8) | H10A—C10—H10C | 110.0 (12) |
C4—C3—H3 | 120.6 (8) | H10B—C10—H10C | 110.0 (11) |
C5—C4—C3 | 119.78 (12) | N3—C11—C12 | 122.66 (10) |
C5—C4—H4 | 119.4 (7) | N3—C11—C9 | 116.74 (10) |
C3—C4—H4 | 120.8 (7) | C12—C11—C9 | 120.56 (10) |
C4—C5—C6 | 121.56 (12) | C13—C12—C11 | 118.88 (11) |
C4—C5—H5 | 121.9 (8) | C13—C12—H12 | 122.3 (7) |
C6—C5—H5 | 116.5 (8) | C11—C12—H12 | 118.9 (7) |
C5—C6—N1 | 116.31 (10) | C12—C13—C14 | 119.11 (11) |
C5—C6—C1 | 118.43 (11) | C12—C13—H13 | 119.1 (8) |
N1—C6—C1 | 124.86 (10) | C14—C13—H13 | 121.8 (8) |
N1—C7—C10 | 120.31 (11) | C15—C14—C13 | 118.27 (11) |
N1—C7—C8 | 121.79 (10) | C15—C14—H14 | 120.5 (7) |
C10—C7—C8 | 117.86 (11) | C13—C14—H14 | 121.2 (7) |
C9—C8—C7 | 104.25 (9) | N3—C15—C14 | 123.80 (11) |
C9—C8—H8A | 107.9 (7) | N3—C15—H15 | 116.2 (8) |
C7—C8—H8A | 108.4 (7) | C14—C15—H15 | 120.0 (8) |
C9—N2—C1—C2 | 147.82 (11) | C10—C7—C8—C9 | 106.51 (11) |
C9—N2—C1—C6 | −39.40 (16) | C1—N2—C9—C11 | 173.32 (9) |
N2—C1—C2—C3 | 177.04 (11) | C1—N2—C9—C8 | −4.15 (16) |
C6—C1—C2—C3 | 3.79 (17) | C7—C8—C9—N2 | 71.43 (14) |
C1—C2—C3—C4 | −3.46 (18) | C7—C8—C9—C11 | −105.99 (11) |
C2—C3—C4—C5 | −0.03 (18) | C15—N3—C11—C12 | −0.86 (16) |
C3—C4—C5—C6 | 3.16 (18) | C15—N3—C11—C9 | 177.18 (10) |
C4—C5—C6—N1 | −175.86 (10) | N2—C9—C11—N3 | −166.77 (10) |
C4—C5—C6—C1 | −2.76 (17) | C8—C9—C11—N3 | 10.75 (15) |
C7—N1—C6—C5 | −146.53 (11) | N2—C9—C11—C12 | 11.31 (16) |
C7—N1—C6—C1 | 40.87 (16) | C8—C9—C11—C12 | −171.17 (10) |
N2—C1—C6—C5 | −173.28 (10) | N3—C11—C12—C13 | 1.07 (17) |
C2—C1—C6—C5 | −0.68 (16) | C9—C11—C12—C13 | −176.89 (10) |
N2—C1—C6—N1 | −0.82 (17) | C11—C12—C13—C14 | −0.47 (17) |
C2—C1—C6—N1 | 171.78 (11) | C12—C13—C14—C15 | −0.25 (18) |
C6—N1—C7—C10 | −174.01 (10) | C11—N3—C15—C14 | 0.08 (18) |
C6—N1—C7—C8 | 3.42 (16) | C13—C14—C15—N3 | 0.47 (19) |
N1—C7—C8—C9 | −70.98 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15···N3i | 0.989 (13) | 2.590 (13) | 3.4900 (16) | 151.3 (10) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Acknowledgements
JTM thanks Tulane University for support of the Tulane Crystallography Laboratory.
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