2-Methyl-4-(pyridin-2-yl)-3H-1,5-benzodiazepine

El Ghayati, L.; Ramli, Y.; Moussaif, A.; Koubachi, J.; Taha, M.L.; Essassi, E.M.; Mague, J.T.

doi:10.1107/S2414314618009537

organic compounds

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ISSN: 2414-3146

Volume 3| Part 7| July 2018| x180953

https://doi.org/10.1107/S2414314618009537

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access

2-Methyl-4-(pyridin-2-yl)-3H-1,5-benzodiazepine

Lhoussaine El Ghayati,^a ^* Youssef Ramli,^b Ahmed Moussaif,^c Jamal Koubachi,^d Mohamed Labd Taha,^d El Mokhtar Essassi ^a and Joel T. Mague ^e

^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

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 3 July 2018; accepted 3 July 2018; online 6 July 2018)

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).

Table 1
Hydrogen-bond geometry (Å, °)

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.

Figure 1
The molecular structure of the title molecule with the labelling scheme and 50% probability ellipsoids.

Figure 2
Packing viewed along the a-axis direction with C—H⋯O hydrogen bonds shown as dashed lines.

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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₃N₃
M_r	235.28
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	5.9642 (6), 17.7004 (17), 11.3963 (11)
β (°)	100.695 (1)
V (Å³)	1182.2 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.27 × 0.20 × 0.07

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.84, 0.99
No. of measured, independent and observed [I > 2σ(I)] reflections	11157, 3013, 2144
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.108, 0.97
No. of reflections	3013
No. of parameters	215
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.20
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), Mercury (Macrae et al., 2008 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1853275

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314618009537/vm4036sup1.cif

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

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: 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).

2-Methyl-4-(pyridin-2-yl)-3H-1,5-benzodiazepine top

Crystal data top

C₁₅H₁₃N₃	F(000) = 496
M_r = 235.28	D_x = 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

Data collection top

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	R_int = 0.035
ω scans	θ_max = 29.2°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −8→8
T_min = 0.84, T_max = 0.99	k = −23→23
11157 measured reflections	l = −15→15

Refinement top

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(F_o²) + (0.0657P)²] where P = (F_o² + 2F_c²)/3
3013 reflections	(Δ/σ)_max < 0.001
215 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

References

Bruker (2016). APEX3, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Tjiou, E. M., Lhoussaine, E. G., Virieux, D. & Fruchier, A. (2005). Magn. Reson. Chem. 43, 557–562. Web of Science CrossRef Google Scholar
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ISSN: 2414-3146

Volume 3| Part 7| July 2018| x180953

https://doi.org/10.1107/S2414314618009537

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2-Methyl-4-(pyridin-2-yl)-3H-1,5-benzodiazepine

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds