3-Benzoyl-1,5-dimethyl-1H-1,5-benzodiazepine-2,4(3H,5H)-dione

Dardouri, R.; Rodi, Y.K.; Ladeira, S.; Essassi, E.M.; Ng, S.W.

doi:10.1107/S160053681100866X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o849

doi:10.1107/S160053681100866X

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3-Benzoyl-1,5-dimethyl-1H-1,5-benzodiazepine-2,4(3H,5H)-dione

Rachida Dardouri,^a Youssef Kandri Rodi,^a Sonia Ladeira,^b El Mokhtar Essassi ^c and Seik Weng Ng ^d ^*

^aLaboratoire de Chimie Organique Appliquée, Faculté des Sciences et Techniques Université Sidi Mohamed Ben Abdallah, Fés, Morocco, ^bService Commun Rayons-X FR2599, Université Paul Sabatier, Bâtiment 2R1, 118 route de Narbonne, Toulouse, France, ^cLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Université Mohammed V-Agdal, BP 1014 Avenue Ibn Batout, Rabat, Morocco, and ^dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 6 March 2011; accepted 7 March 2011; online 12 March 2011)

The seven-membered ring of the title compound, C₁₈H₁₆N₂O₃, adopts a boat-shaped conformation (with the C atoms of the fused ring as the stern and the methine C atom as the prow). The substituent at the 3-position occupies an axial position, and the aromatic ring of the substituent is arched over the seven-membered ring in a parasol-like manner, the dihedral angle between the phenylene and phenyl rings being 28.7 (1)°.

Related literature

For the crystal structure of the 3,3-dimethyl substituted derivative, see: Dardouri et al. (2011 ).

Experimental

Crystal data

C₁₈H₁₆N₂O₃
M_r = 308.33
Monoclinic, P 2₁ /n
a = 7.7827 (1) Å
b = 23.7595 (4) Å
c = 8.6315 (2) Å
β = 105.614 (1)°
V = 1537.18 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.22 × 0.12 × 0.04 mm

Data collection

Bruker X8 APEXII diffractometer
18802 measured reflections
4592 independent reflections
3089 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.128
S = 1.01
4592 reflections
210 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681100866X/bt5487sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681100866X/bt5487Isup2.hkl

checkCIF report

Comment top

The methylene part of 1,5-dimethyl-1,5-benzodiazepine-2,4-dione is relatively acidic, and one proton can be abstracted by using potassium t-butoxide; the resulting carbanion can undergo a nucleophlilic substitution with an alkyl halide to form 3-substituted derivatives. A previous study reported the crystal structure of the 3,3-dimethyl-substituted derivative, which was synthesized by a slight variation of the synthetic route (Dardouri et al., 2011). The title compound was obtained by using benzoyl chloride as reactant. The seven-membered ring of C₁₈H₁₆N₂O₃ adopts a boat-shaped conformation (with the C atoms of the fused-ring as the stern and the methine C atom as the prow) (Scheme I, Fig. 1). The substituent at the 3-position occupies an axial position. The unfavorable the 3-position forces the phenyl ring to arch over the phenylene ring of the fused-ring in a parasol-like manner [the dihedral angle between the two rings is 28.7 (1) °]. The distance between the two centroids is 4.225 Å (Fig. 2). Severe strain is also evident from the non-linearity of the benzoyl C₆H₅C(O)– portion of the molecule.

Related literature top

For the crystal structure of the 3,3-dimethyl substituted derivative, see: Dardouri et al. (2011).

Experimental top

To a solution of potassium t-butoxide (0.42 g, 3.6 mmol) in DMF (15 ml) was added 1,5-dimethyl-1,5-benzodiazepine-2,4-dione (0.50 g, 2.4 mmol) and benzoyl chloride (0.33 ml, 2.88 mmol). Stirring was continued for 24 h. The reaction was monitored by thin layer chromatography. The mixture was filtered; slow evaporation of the solvent gave colorless crystals.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Displacement ellipsoid plot (Barbour, 2001) of C₁₈H₁₆N₂O₃ at the 70% probability level; hydrogen atoms are drawn as arbitrary radius.
	Fig. 2. Van der Waals surfaces of the carbon atoms of the aromatic rings.

3-Benzoyl-1,5-dimethyl-1H-1,5-benzodiazepine-2,4(3H,5H)-dione top

Crystal data top

C₁₈H₁₆N₂O₃	F(000) = 648
M_r = 308.33	D_x = 1.332 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4206 reflections
a = 7.7827 (1) Å	θ = 2.6–28.3°
b = 23.7595 (4) Å	µ = 0.09 mm⁻¹
c = 8.6315 (2) Å	T = 295 K
β = 105.614 (1)°	Prism, colorless
V = 1537.18 (5) Å³	0.22 × 0.12 × 0.04 mm
Z = 4

Data collection top

Bruker X8 APEXII diffractometer	3089 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.038
Graphite monochromator	θ_max = 30.5°, θ_min = 2.6°
ϕ and ω scans	h = −10→9
18802 measured reflections	k = −33→30
4592 independent reflections	l = −12→11

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0632P)² + 0.2366P] where P = (F_o² + 2F_c²)/3
4592 reflections	(Δ/σ)_max = 0.001
210 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₈H₁₆N₂O₃	V = 1537.18 (5) Å³
M_r = 308.33	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.7827 (1) Å	µ = 0.09 mm⁻¹
b = 23.7595 (4) Å	T = 295 K
c = 8.6315 (2) Å	0.22 × 0.12 × 0.04 mm
β = 105.614 (1)°

Data collection top

Bruker X8 APEXII diffractometer	3089 reflections with I > 2σ(I)
18802 measured reflections	R_int = 0.038
4592 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.01	Δρ_max = 0.31 e Å⁻³
4592 reflections	Δρ_min = −0.22 e Å⁻³
210 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
O1	1.24318 (14)	0.44276 (5)	0.90455 (13)	0.0423 (3)
O2	0.83292 (13)	0.51285 (4)	0.61289 (12)	0.0311 (2)
O3	1.09190 (15)	0.33492 (5)	0.61730 (13)	0.0385 (3)
N1	1.01821 (15)	0.38528 (5)	0.92487 (13)	0.0268 (3)
N2	0.71073 (14)	0.43944 (5)	0.71264 (13)	0.0245 (2)
C1	0.85958 (18)	0.35496 (6)	0.85124 (15)	0.0250 (3)
C2	0.8500 (2)	0.29767 (6)	0.88450 (18)	0.0353 (3)
H2	0.9505	0.2793	0.9467	0.042*
C3	0.6934 (3)	0.26792 (7)	0.82626 (19)	0.0428 (4)
H3	0.6882	0.2300	0.8512	0.051*
C4	0.5446 (2)	0.29455 (7)	0.73107 (19)	0.0415 (4)
H4	0.4385	0.2747	0.6934	0.050*
C5	0.5533 (2)	0.35047 (7)	0.69189 (17)	0.0333 (3)
H5	0.4536	0.3678	0.6250	0.040*
C6	0.70996 (17)	0.38152 (5)	0.75123 (15)	0.0237 (3)
C7	0.5560 (2)	0.47429 (7)	0.7181 (2)	0.0381 (4)
H7A	0.5945	0.5122	0.7462	0.057*
H7B	0.5021	0.4594	0.7972	0.057*
H7C	0.4706	0.4740	0.6145	0.057*
C8	0.84081 (17)	0.46368 (5)	0.65773 (15)	0.0225 (3)
C9	1.00564 (16)	0.42783 (5)	0.66442 (15)	0.0231 (3)
H9	1.0844	0.4514	0.6204	0.028*
C10	1.10278 (18)	0.41905 (6)	0.84130 (16)	0.0272 (3)
C11	1.1054 (2)	0.37505 (8)	1.09563 (17)	0.0407 (4)
H11A	1.0189	0.3616	1.1478	0.061*
H11B	1.1567	0.4095	1.1455	0.061*
H11C	1.1976	0.3474	1.1053	0.061*
C12	0.98410 (18)	0.37241 (5)	0.56927 (16)	0.0246 (3)
C13	0.84063 (18)	0.36688 (5)	0.41676 (16)	0.0246 (3)
C14	0.77679 (19)	0.41305 (6)	0.31835 (16)	0.0290 (3)
H14	0.8199	0.4489	0.3503	0.035*
C15	0.6493 (2)	0.40561 (7)	0.17305 (18)	0.0370 (4)
H15	0.6087	0.4363	0.1065	0.044*
C16	0.5825 (2)	0.35255 (8)	0.12720 (19)	0.0404 (4)
H16	0.4957	0.3477	0.0303	0.048*
C17	0.6441 (2)	0.30642 (7)	0.2249 (2)	0.0418 (4)
H17	0.5981	0.2708	0.1938	0.050*
C18	0.7740 (2)	0.31344 (6)	0.36851 (18)	0.0335 (3)
H18	0.8169	0.2824	0.4330	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0235 (5)	0.0623 (8)	0.0383 (6)	−0.0123 (5)	0.0034 (5)	0.0014 (5)
O2	0.0369 (6)	0.0235 (5)	0.0353 (5)	0.0024 (4)	0.0137 (4)	0.0040 (4)
O3	0.0413 (6)	0.0364 (6)	0.0379 (6)	0.0173 (5)	0.0107 (5)	0.0034 (4)
N1	0.0231 (6)	0.0338 (6)	0.0230 (5)	−0.0002 (5)	0.0052 (4)	0.0028 (4)
N2	0.0203 (5)	0.0269 (6)	0.0278 (6)	0.0017 (4)	0.0093 (4)	0.0025 (4)
C1	0.0277 (7)	0.0265 (6)	0.0237 (6)	−0.0017 (5)	0.0118 (5)	0.0008 (5)
C2	0.0484 (9)	0.0274 (7)	0.0357 (8)	0.0038 (6)	0.0210 (7)	0.0055 (6)
C3	0.0678 (12)	0.0260 (7)	0.0434 (9)	−0.0143 (7)	0.0303 (9)	−0.0051 (6)
C4	0.0504 (10)	0.0427 (9)	0.0365 (8)	−0.0250 (8)	0.0206 (8)	−0.0122 (7)
C5	0.0293 (7)	0.0438 (9)	0.0276 (7)	−0.0116 (6)	0.0094 (6)	−0.0047 (6)
C6	0.0246 (7)	0.0259 (6)	0.0229 (6)	−0.0038 (5)	0.0106 (5)	−0.0007 (5)
C7	0.0279 (8)	0.0460 (9)	0.0451 (9)	0.0127 (6)	0.0179 (7)	0.0107 (7)
C8	0.0226 (6)	0.0246 (6)	0.0200 (6)	−0.0014 (5)	0.0052 (5)	−0.0009 (5)
C9	0.0201 (6)	0.0250 (6)	0.0256 (6)	−0.0009 (5)	0.0087 (5)	0.0020 (5)
C10	0.0209 (6)	0.0335 (7)	0.0275 (6)	0.0002 (5)	0.0070 (5)	0.0003 (5)
C11	0.0335 (8)	0.0628 (11)	0.0243 (7)	0.0016 (7)	0.0053 (6)	0.0088 (7)
C12	0.0252 (6)	0.0251 (6)	0.0267 (6)	0.0020 (5)	0.0122 (5)	0.0030 (5)
C13	0.0260 (7)	0.0240 (6)	0.0273 (6)	0.0021 (5)	0.0134 (5)	−0.0016 (5)
C14	0.0341 (8)	0.0254 (7)	0.0282 (7)	0.0041 (6)	0.0093 (6)	−0.0007 (5)
C15	0.0393 (9)	0.0431 (9)	0.0274 (7)	0.0141 (7)	0.0070 (6)	−0.0026 (6)
C16	0.0312 (8)	0.0568 (10)	0.0326 (8)	0.0029 (7)	0.0077 (6)	−0.0165 (7)
C17	0.0424 (9)	0.0387 (9)	0.0473 (9)	−0.0129 (7)	0.0173 (8)	−0.0181 (7)
C18	0.0417 (8)	0.0252 (7)	0.0374 (8)	−0.0012 (6)	0.0171 (7)	−0.0035 (6)

Geometric parameters (Å, º) top

O1—C10	1.2199 (17)	C7—H7C	0.9600
O2—C8	1.2271 (16)	C8—C9	1.5280 (17)
O3—C12	1.2173 (16)	C9—C10	1.5247 (18)
N1—C10	1.3613 (17)	C9—C12	1.5369 (18)
N1—C1	1.4229 (18)	C9—H9	0.9800
N1—C11	1.4675 (18)	C11—H11A	0.9600
N2—C8	1.3562 (16)	C11—H11B	0.9600
N2—C6	1.4163 (17)	C11—H11C	0.9600
N2—C7	1.4725 (17)	C12—C13	1.4851 (19)
C1—C2	1.3974 (19)	C13—C18	1.3922 (19)
C1—C6	1.3993 (19)	C13—C14	1.3945 (19)
C2—C3	1.381 (2)	C14—C15	1.385 (2)
C2—H2	0.9300	C14—H14	0.9300
C3—C4	1.380 (3)	C15—C16	1.380 (2)
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.377 (2)	C16—C17	1.387 (2)
C4—H4	0.9300	C16—H16	0.9300
C5—C6	1.3986 (19)	C17—C18	1.383 (2)
C5—H5	0.9300	C17—H17	0.9300
C7—H7A	0.9600	C18—H18	0.9300
C7—H7B	0.9600

C10—N1—C1	123.15 (11)	C8—C9—C12	119.19 (11)
C10—N1—C11	118.11 (12)	C10—C9—H9	105.8
C1—N1—C11	118.41 (11)	C8—C9—H9	105.8
C8—N2—C6	123.07 (11)	C12—C9—H9	105.8
C8—N2—C7	117.79 (11)	O1—C10—N1	122.53 (13)
C6—N2—C7	118.91 (11)	O1—C10—C9	121.87 (12)
C2—C1—C6	118.98 (13)	N1—C10—C9	115.53 (11)
C2—C1—N1	119.29 (13)	N1—C11—H11A	109.5
C6—C1—N1	121.68 (12)	N1—C11—H11B	109.5
C3—C2—C1	120.95 (15)	H11A—C11—H11B	109.5
C3—C2—H2	119.5	N1—C11—H11C	109.5
C1—C2—H2	119.5	H11A—C11—H11C	109.5
C4—C3—C2	119.93 (14)	H11B—C11—H11C	109.5
C4—C3—H3	120.0	O3—C12—C13	121.46 (12)
C2—C3—H3	120.0	O3—C12—C9	118.61 (12)
C3—C4—C5	119.98 (14)	C13—C12—C9	119.82 (11)
C3—C4—H4	120.0	C18—C13—C14	119.49 (13)
C5—C4—H4	120.0	C18—C13—C12	118.46 (12)
C4—C5—C6	120.98 (15)	C14—C13—C12	122.00 (12)
C4—C5—H5	119.5	C15—C14—C13	120.13 (13)
C6—C5—H5	119.5	C15—C14—H14	119.9
C5—C6—C1	119.11 (13)	C13—C14—H14	119.9
C5—C6—N2	119.00 (12)	C16—C15—C14	119.93 (15)
C1—C6—N2	121.85 (11)	C16—C15—H15	120.0
N2—C7—H7A	109.5	C14—C15—H15	120.0
N2—C7—H7B	109.5	C15—C16—C17	120.36 (14)
H7A—C7—H7B	109.5	C15—C16—H16	119.8
N2—C7—H7C	109.5	C17—C16—H16	119.8
H7A—C7—H7C	109.5	C18—C17—C16	119.94 (14)
H7B—C7—H7C	109.5	C18—C17—H17	120.0
O2—C8—N2	122.40 (12)	C16—C17—H17	120.0
O2—C8—C9	120.86 (11)	C17—C18—C13	120.12 (14)
N2—C8—C9	116.62 (11)	C17—C18—H18	119.9
C10—C9—C8	107.40 (10)	C13—C18—H18	119.9
C10—C9—C12	111.80 (11)

C10—N1—C1—C2	130.65 (14)	N2—C8—C9—C12	60.87 (15)
C11—N1—C1—C2	−42.59 (18)	C1—N1—C10—O1	−176.50 (13)
C10—N1—C1—C6	−51.95 (18)	C11—N1—C10—O1	−3.2 (2)
C11—N1—C1—C6	134.80 (14)	C1—N1—C10—C9	6.51 (18)
C6—C1—C2—C3	−3.0 (2)	C11—N1—C10—C9	179.78 (12)
N1—C1—C2—C3	174.49 (13)	C8—C9—C10—O1	−107.48 (15)
C1—C2—C3—C4	1.3 (2)	C12—C9—C10—O1	120.01 (14)
C2—C3—C4—C5	1.2 (2)	C8—C9—C10—N1	69.54 (14)
C3—C4—C5—C6	−2.0 (2)	C12—C9—C10—N1	−62.97 (15)
C4—C5—C6—C1	0.3 (2)	C10—C9—C12—O3	−26.52 (16)
C4—C5—C6—N2	−177.66 (13)	C8—C9—C12—O3	−152.84 (12)
C2—C1—C6—C5	2.15 (19)	C10—C9—C12—C13	157.22 (11)
N1—C1—C6—C5	−175.25 (12)	C8—C9—C12—C13	30.89 (16)
C2—C1—C6—N2	−179.97 (12)	O3—C12—C13—C18	30.37 (19)
N1—C1—C6—N2	2.63 (19)	C9—C12—C13—C18	−153.48 (12)
C8—N2—C6—C5	−131.99 (13)	O3—C12—C13—C14	−146.95 (14)
C7—N2—C6—C5	42.36 (17)	C9—C12—C13—C14	29.20 (18)
C8—N2—C6—C1	50.13 (18)	C18—C13—C14—C15	−0.6 (2)
C7—N2—C6—C1	−135.52 (13)	C12—C13—C14—C15	176.69 (13)
C6—N2—C8—O2	174.18 (12)	C13—C14—C15—C16	1.4 (2)
C7—N2—C8—O2	−0.23 (19)	C14—C15—C16—C17	−0.9 (2)
C6—N2—C8—C9	−9.73 (17)	C15—C16—C17—C18	−0.4 (2)
C7—N2—C8—C9	175.85 (12)	C16—C17—C18—C13	1.2 (2)
O2—C8—C9—C10	108.64 (13)	C14—C13—C18—C17	−0.7 (2)
N2—C8—C9—C10	−67.51 (14)	C12—C13—C18—C17	−178.09 (13)
O2—C8—C9—C12	−122.98 (13)

Experimental details

Crystal data
Chemical formula	C₁₈H₁₆N₂O₃
M_r	308.33
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	7.7827 (1), 23.7595 (4), 8.6315 (2)
β (°)	105.614 (1)
V (Å³)	1537.18 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.22 × 0.12 × 0.04

Data collection
Diffractometer	Bruker X8 APEXII diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	18802, 4592, 3089
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.128, 1.01
No. of reflections	4592
No. of parameters	210
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.22

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

We thank Université Sidi Mohamed Ben Abdallah, Université Mohammed V-Agdal and the University of Malaya for supporting this study.

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