(4Z)-4-(2-Oxo­propyl­idene)-2,3,4,5-tetra­hydro-1H-1,5-benzodiazepin-2-one

Sebhaoui, J.; El Bakri, Y.; Essassi, E.M.; Mague, J.T.

doi:10.1107/S2414314617010574

organic compounds

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ISSN: 2414-3146

Volume 2| Part 7| July 2017| x171057

https://doi.org/10.1107/S2414314617010574

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(4Z)-4-(2-Oxopropylidene)-2,3,4,5-tetrahydro-1H-1,5-benzodiazepin-2-one

Jihad Sebhaoui,^a ^* Youness El Bakri,^a El Mokhtar Essassi ^a and Joel T. Mague ^b

^aLaboratoire de Chimie Organique Hétérocyclique, Centre de Recherche des Sciences des Médicaments, URAC 21, Pôle de Compétence Pharmacochimie, Av Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco, and ^bDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: jihadita.chimiste@gmail.com

Edited by J. Simpson, University of Otago, New Zealand (Received 4 July 2017; accepted 17 July 2017; online 21 July 2017)

In the title compound, C₁₂H₁₂N₂O₂, the seven-membered ring adopts a boat conformation. The orientation of the acetyl substituent on this ring is partly determined by an intramolecular N—H⋯O hydrogen bond. In the crystal, wrinkled sheets stacked along the a-axis direction are formed by pairwise N—H⋯O and C—H⋯O hydrogen bonds. The sheets are connected through additional N—H⋯O and C—H⋯O hydrogen bonds stacking the molecules along the a-axis direction. The structure was refined as a three-component twin.

Keywords: crystal structure; benzodiazepine; hydrogen bond.

CCDC reference: 1562781

Structure description

1,5-Benzodiazepine derivatives are very useful as they are found in many biologically active compounds. Applications of these derivatives include use as anti-inflammatory (Romal et al., 1991 ), anticonvulsant, antianxiety, and hypnotic agents (Randall et al., 1973 ; Smiley et al., 1979 ). As a continuation of our studies on benzodiazepine derivatives (Sebhaoui et al., 2017 ), we report here the synthesis and the crystal structure of the title compound that was synthesized by condensation of o-phenylenediamine with dehydroacetic acid (3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione) in refluxing xylene.

In the title molecule, the seven-membered heterocyclic ring adopts a boat conformation. A puckering analysis of this conformation gave the parameters Q(2) = 0.777 (4) Å, Q(3) = 0.257 (4) Å, φ(2) = 209.0 (3)° and φ(3) = 307.6 (9)°. The dihedral angle between the C1–C6 plane and that defined by C1/C6/N1/N2 is 6.0 (2)°. The rotational orientation of the acyl substituent on this ring is partially determined by an intramolecular N1—H1A⋯O2 hydrogen bond (Table 1 and Fig. 1). Pairwise N2—H2A⋯O1 and C12—H12A⋯O1 hydrogen bonds (Table 1 and Fig. 2) form zigzag chains along the b-axis direction that are elaborated into wrinkled sheets stacked in the a-axis direction through N2—H2A⋯O1 and C8—H8B⋯O1 hydrogen bonds (Table 1 and Figs. 3 and 4).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2	0.85 (6)	2.06 (6)	2.693 (5)	131 (5)
N1—H1A⋯O2ⁱ	0.85 (6)	2.55 (5)	3.291 (5)	146 (5)
N2—H2A⋯O1ⁱⁱ	0.89 (6)	2.02 (6)	2.876 (4)	161 (6)
C8—H8B⋯O1ⁱⁱⁱ	1.00 (5)	2.58 (5)	3.469 (5)	149 (4)
C12—H12A⋯O1^iv	0.97 (6)	2.57 (6)	3.483 (5)	157 (5)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+2, -y+2, -z+1; (iii) x-1, y, z; (iv) -x+2, -y+1, -z+1.

Figure 1
The title molecule with labeling scheme and 50% probability ellipsoids. The intramolecular hydrogen bond is shown by a dashed line.

Figure 2
Detail of the intermolecular N—H⋯O and C—H⋯O hydrogen bonding (blue and black dashed lines, respectively). [Symmetry codes: (i) −x + 1, −y + 1, −z; (ii) −x + 2, −y + 2, −z + 1; (iii) −x, y, z; (iv) −x + 2, −y + 1, −z.]

Figure 3
Packing viewed along the a-axis direction, showing the wrinkled sheets of molecules in the bc plane.

Figure 4
Overall packing viewed along a.

Synthesis and crystallization

A mixture of o-phenylendiamine (80 mmol) and dehydroacetic acid (40 mmol) in 40 ml of xylene was heated under reflux for 2 h and the water was removed with a Dean–Stark trap by azeotropic distillation. After cooling, the residue obtained was washed with ethanol. The solid isolated was recrystallized from N,N-dimethylformamide solution to give colourless crystals of the title compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The structure was refined as a three-component twin.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₂O₂
M_r	216.24
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	4.5801 (9), 10.870 (2), 10.971 (2)
α, β, γ (°)	101.043 (3), 98.854 (3), 99.868 (3)
V (Å³)	518.20 (18)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.44 × 0.26 × 0.11

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (TWINABS; Sheldrick, 2009 )
T_min, T_max	0.96, 0.99
No. of measured, independent and observed [I > 2σ(I)] reflections	26238, 26238, 19750
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.090, 0.281, 1.03
No. of reflections	26238
No. of parameters	195
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.36
Computer programs: APEX3 and SAINT (Bruker, 2016 ), CELL_NOW (Sheldrick, 2008a ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008b ).

Structural data

CCDC reference: 1562781

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617010574/sj4127sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617010574/sj4127Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617010574/sj4127Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314617010574/sj4127Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016), CELL_NOW (Sheldrick, 2008a); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

(4Z)-4-(2-Oxopropylidene)-2,3,4,5-tetrahydro-1H-1,5-benzodiazepin-2-one top

Crystal data top

C₁₂H₁₂N₂O₂	Z = 2
M_r = 216.24	F(000) = 228
Triclinic, P1	D_x = 1.386 Mg m⁻³
a = 4.5801 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.870 (2) Å	Cell parameters from 8186 reflections
c = 10.971 (2) Å	θ = 2.4–28.6°
α = 101.043 (3)°	µ = 0.10 mm⁻¹
β = 98.854 (3)°	T = 100 K
γ = 99.868 (3)°	Thick plate, colourless
V = 518.20 (18) Å³	0.44 × 0.26 × 0.11 mm

Data collection top

Bruker SMART APEX CCD diffractometer	26238 independent reflections
Radiation source: fine-focus sealed tube	19750 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 8.3333 pixels mm^-1	θ_max = 28.7°, θ_min = 1.9°
φ and ω scans	h = −6→6
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009)	k = −14→14
T_min = 0.96, T_max = 0.99	l = −14→14
26238 measured reflections

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)] = 0.090	Hydrogen site location: difference Fourier map
wR(F²) = 0.281	All H-atom parameters refined
S = 1.03	w = 1/[σ²(F_o²) + (0.0477P)² + 1.0312P] where P = (F_o² + 2F_c²)/3
26238 reflections	(Δ/σ)_max < 0.001
195 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Special details top

Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5° in ω, colllected at φ = 0.00, 90.00 and 180.00° and 2 sets of 800 frames, each of width 0.45° in φ, collected at ω = –30.00 and 210.00°. The scan time was 20 sec/frame. Analysis of 1142 reflections having I/σ(I) > 12 and chosen from the full data set with CELL_NOW (Sheldrick, 2008) showed the crystal to belong to the triclinic system and to be consist of three components. The raw data were processed using the multi-component version of SAINT under control of the 3-component orientation file generated by CELL_NOW.

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. Refined as a 3-component twin.

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

	x	y	z	U_iso*/U_eq
O1	0.9985 (6)	0.8467 (3)	0.5387 (3)	0.0245 (7)
O2	0.5860 (6)	0.4238 (3)	0.0933 (3)	0.0260 (7)
N1	0.4186 (7)	0.6333 (3)	0.2127 (3)	0.0211 (7)
H1A	0.412 (12)	0.586 (5)	0.141 (5)	0.042 (15)*
N2	0.6861 (7)	0.8902 (3)	0.3797 (3)	0.0208 (7)
H2A	0.816 (13)	0.965 (6)	0.395 (5)	0.053 (17)*
C1	0.4276 (8)	0.8655 (4)	0.2830 (4)	0.0196 (8)
C2	0.3141 (9)	0.9716 (4)	0.2584 (4)	0.0228 (8)
H2	0.412 (10)	1.056 (5)	0.312 (4)	0.024 (11)*
C3	0.0710 (9)	0.9579 (4)	0.1619 (4)	0.0243 (9)
H3	0.002 (11)	1.031 (5)	0.145 (5)	0.035 (13)*
C4	−0.0668 (9)	0.8358 (4)	0.0887 (4)	0.0240 (9)
H4	−0.251 (10)	0.824 (5)	0.021 (4)	0.031 (12)*
C5	0.0461 (9)	0.7304 (4)	0.1113 (4)	0.0222 (8)
H5	−0.044 (11)	0.646 (5)	0.060 (5)	0.034 (13)*
C6	0.2965 (8)	0.7433 (4)	0.2065 (4)	0.0195 (8)
C7	0.5517 (8)	0.6022 (4)	0.3171 (4)	0.0200 (8)
C8	0.5476 (9)	0.6884 (4)	0.4413 (4)	0.0216 (8)
H8A	0.609 (9)	0.648 (4)	0.513 (4)	0.022 (11)*
H8B	0.343 (11)	0.708 (5)	0.439 (4)	0.029 (12)*
C9	0.7631 (9)	0.8150 (4)	0.4580 (4)	0.0204 (8)
C10	0.6880 (9)	0.4980 (4)	0.3145 (4)	0.0214 (8)
H10	0.784 (9)	0.483 (4)	0.394 (4)	0.022 (11)*
C11	0.7009 (9)	0.4115 (4)	0.1992 (4)	0.0219 (8)
C12	0.8585 (11)	0.3019 (4)	0.2103 (4)	0.0275 (9)
H12A	0.871 (13)	0.280 (6)	0.292 (6)	0.055 (17)*
H12B	0.759 (13)	0.228 (6)	0.140 (6)	0.059 (18)*
H12C	1.061 (14)	0.326 (6)	0.200 (6)	0.061 (18)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0277 (15)	0.0222 (14)	0.0211 (15)	0.0053 (12)	0.0020 (11)	0.0007 (11)
O2	0.0316 (16)	0.0233 (15)	0.0218 (15)	0.0096 (12)	0.0024 (12)	0.0010 (12)
N1	0.0251 (17)	0.0188 (16)	0.0183 (17)	0.0053 (13)	0.0046 (13)	0.0006 (13)
N2	0.0224 (17)	0.0182 (16)	0.0207 (17)	0.0035 (13)	0.0047 (13)	0.0015 (13)
C1	0.0212 (18)	0.0203 (18)	0.0179 (18)	0.0049 (15)	0.0074 (14)	0.0025 (14)
C2	0.027 (2)	0.0208 (19)	0.022 (2)	0.0058 (16)	0.0095 (16)	0.0015 (16)
C3	0.030 (2)	0.023 (2)	0.025 (2)	0.0127 (17)	0.0105 (16)	0.0066 (16)
C4	0.024 (2)	0.027 (2)	0.021 (2)	0.0081 (16)	0.0056 (16)	0.0042 (16)
C5	0.0218 (19)	0.023 (2)	0.020 (2)	0.0041 (16)	0.0058 (15)	0.0020 (16)
C6	0.0201 (18)	0.0198 (18)	0.0197 (19)	0.0062 (14)	0.0077 (14)	0.0022 (15)
C7	0.0202 (18)	0.0178 (18)	0.0200 (19)	0.0002 (14)	0.0052 (15)	0.0018 (15)
C8	0.026 (2)	0.0214 (19)	0.0184 (19)	0.0051 (16)	0.0080 (15)	0.0028 (15)
C9	0.0251 (19)	0.0197 (18)	0.0166 (18)	0.0067 (15)	0.0089 (15)	−0.0009 (14)
C10	0.0235 (19)	0.0197 (18)	0.021 (2)	0.0049 (15)	0.0043 (15)	0.0040 (15)
C11	0.0222 (19)	0.0191 (18)	0.023 (2)	0.0029 (15)	0.0040 (15)	0.0039 (15)
C12	0.036 (2)	0.023 (2)	0.026 (2)	0.0123 (18)	0.0059 (18)	0.0049 (17)

Geometric parameters (Å, º) top

O1—C9	1.236 (5)	C4—H4	1.01 (5)
O2—C11	1.242 (4)	C5—C6	1.395 (5)
N1—C7	1.343 (5)	C5—H5	0.96 (5)
N1—C6	1.412 (5)	C7—C10	1.382 (6)
N1—H1A	0.85 (6)	C7—C8	1.503 (5)
N2—C9	1.344 (5)	C8—C9	1.511 (5)
N2—C1	1.412 (5)	C8—H8A	1.00 (4)
N2—H2A	0.89 (6)	C8—H8B	1.00 (5)
C1—C2	1.399 (5)	C10—C11	1.440 (6)
C1—C6	1.405 (5)	C10—H10	0.97 (4)
C2—C3	1.379 (6)	C11—C12	1.509 (6)
C2—H2	0.98 (5)	C12—H12A	0.97 (6)
C3—C4	1.397 (6)	C12—H12B	0.98 (6)
C3—H3	0.95 (5)	C12—H12C	0.95 (6)
C4—C5	1.383 (6)

C7—N1—C6	127.0 (3)	N1—C7—C10	123.5 (4)
C7—N1—H1A	119 (4)	N1—C7—C8	116.2 (4)
C6—N1—H1A	114 (4)	C10—C7—C8	120.3 (4)
C9—N2—C1	127.9 (3)	C7—C8—C9	109.8 (3)
C9—N2—H2A	113 (4)	C7—C8—H8A	111 (3)
C1—N2—H2A	119 (4)	C9—C8—H8A	109 (2)
C2—C1—C6	119.5 (4)	C7—C8—H8B	109 (3)
C2—C1—N2	116.7 (3)	C9—C8—H8B	106 (3)
C6—C1—N2	123.6 (3)	H8A—C8—H8B	112 (4)
C3—C2—C1	121.0 (4)	O1—C9—N2	122.0 (4)
C3—C2—H2	121 (3)	O1—C9—C8	121.6 (4)
C1—C2—H2	118 (3)	N2—C9—C8	116.4 (3)
C2—C3—C4	119.5 (4)	C7—C10—C11	123.3 (4)
C2—C3—H3	120 (3)	C7—C10—H10	119 (3)
C4—C3—H3	121 (3)	C11—C10—H10	118 (3)
C5—C4—C3	119.9 (4)	O2—C11—C10	122.4 (4)
C5—C4—H4	120 (3)	O2—C11—C12	119.9 (4)
C3—C4—H4	120 (3)	C10—C11—C12	117.7 (4)
C4—C5—C6	121.2 (4)	C11—C12—H12A	114 (4)
C4—C5—H5	121 (3)	C11—C12—H12B	109 (4)
C6—C5—H5	118 (3)	H12A—C12—H12B	112 (5)
C5—C6—C1	118.7 (4)	C11—C12—H12C	109 (4)
C5—C6—N1	117.3 (3)	H12A—C12—H12C	106 (5)
C1—C6—N1	123.8 (3)	H12B—C12—H12C	107 (5)

C9—N2—C1—C2	148.6 (4)	C7—N1—C6—C1	38.2 (6)
C9—N2—C1—C6	−36.0 (6)	C6—N1—C7—C10	−174.5 (4)
C6—C1—C2—C3	1.4 (6)	C6—N1—C7—C8	5.3 (5)
N2—C1—C2—C3	177.0 (3)	N1—C7—C8—C9	−72.2 (4)
C1—C2—C3—C4	0.9 (6)	C10—C7—C8—C9	107.6 (4)
C2—C3—C4—C5	−1.7 (6)	C1—N2—C9—O1	179.2 (4)
C3—C4—C5—C6	0.1 (6)	C1—N2—C9—C8	−0.1 (6)
C4—C5—C6—C1	2.2 (6)	C7—C8—C9—O1	−111.1 (4)
C4—C5—C6—N1	−172.4 (3)	C7—C8—C9—N2	68.3 (5)
C2—C1—C6—C5	−3.0 (5)	N1—C7—C10—C11	−0.2 (6)
N2—C1—C6—C5	−178.2 (3)	C8—C7—C10—C11	−179.9 (3)
C2—C1—C6—N1	171.3 (3)	C7—C10—C11—O2	−0.9 (6)
N2—C1—C6—N1	−4.0 (6)	C7—C10—C11—C12	179.7 (4)
C7—N1—C6—C5	−147.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.85 (6)	2.06 (6)	2.693 (5)	131 (5)
N1—H1A···O2ⁱ	0.85 (6)	2.55 (5)	3.291 (5)	146 (5)
N2—H2A···O1ⁱⁱ	0.89 (6)	2.02 (6)	2.876 (4)	161 (6)
C8—H8B···O1ⁱⁱⁱ	1.00 (5)	2.58 (5)	3.469 (5)	149 (4)
C12—H12A···O1^iv	0.97 (6)	2.57 (6)	3.483 (5)	157 (5)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+2, −z+1; (iii) x−1, y, z; (iv) −x+2, −y+1, −z+1.

Acknowledgements

JTM thanks Tulane University for support of the Tulane Crystallography Laboratory.

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