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

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

doi:10.1107/S1600536811007501

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o783

doi:10.1107/S1600536811007501

Open

access

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

Rachida Dardouri,^a Youssef Kandri Rodi,^a Natalie Saffon,^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 27 February 2011; accepted 28 February 2011; online 5 March 2011)

The seven-membered ring in the title compound, C₁₃H₁₆N₂O₂, adopts a boat-shaped conformation (with the C atoms of the fused-ring as the stern and the C atom bearing two methyl groups) as the prow.

Related literature

For the crystal structure of 1,5-dimethyl-1,5-benzodiazepin-2,4-dione, see: Mondieig et al. (2005 ).

Experimental

Crystal data

C₁₃H₁₆N₂O₂
M_r = 232.28
Monoclinic, P 2₁ /c
a = 7.5112 (1) Å
b = 10.1731 (2) Å
c = 15.8697 (3) Å
β = 103.675 (1)°
V = 1178.26 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.32 × 0.20 × 0.18 mm

Data collection

Bruker X8 APEXII diffractometer
20993 measured reflections
2719 independent reflections
2130 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.108
S = 1.04
2719 reflections
158 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.20 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/S1600536811007501/bt5483sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811007501/bt5483Isup2.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 subsitution with haloalkane to form 3-substituted derivatives. Previous studies have largely described the mono-substituted derivatives only. 1,12-Dibromodocane yielded the mono-substituted 12-bromodeyl derivative. In this study, the compound is reacted with methyl iodide to yield the di-methylated compound (Scheme I). The seven-membered ring adopts a boat-shaped conformation (with the C atoms of the fused-ring as the stern and the C atom bearing two methyl groups) as the prow (Fig. 1). The methyl group occupying the axial position hovers over the seven-membered ring, and the methyl group appears to be stopped from tipping over because of the π-system of the phenylene ring (Fig. 2).

Related literature top

For the crystal structure of 1,5-dimethyl-1,5-benzodiazepin-2,4-dione, see: Mondieig et al. (2005).

Experimental top

To a solution of the 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 methyl iodide (0.68 g, 4.80 mmol). Stirring was continued for 24 h. The reaction was monitored by thin layer ch romatography. The mixture was filtered and the solution evaporated to give 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. Thermal ellipsoid plot (Barbour, 2001) of C₁₃H₁₆N₂O₂ at the 50% probability level; hydrogen atoms are drawn as arbitrary radius.
	Fig. 2. Thermal ellipsoid plot (Barbour, 2001) showing van der Waals surfaces for the carbon atoms of the phenylene ring as well as the van der Waals surface for one of the methyl hydrogen atoms.

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

Crystal data top

C₁₃H₁₆N₂O₂	F(000) = 496
M_r = 232.28	D_x = 1.309 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4653 reflections
a = 7.5112 (1) Å	θ = 2.4–32.5°
b = 10.1731 (2) Å	µ = 0.09 mm⁻¹
c = 15.8697 (3) Å	T = 295 K
β = 103.675 (1)°	Block, colorless
V = 1178.26 (4) Å³	0.32 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker X8 APEXII diffractometer	2130 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.042
Graphite monochromator	θ_max = 27.5°, θ_min = 2.4°
ϕ and ω scans	h = −9→9
20993 measured reflections	k = −13→13
2719 independent reflections	l = −20→20

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0537P)² + 0.280P] where P = (F_o² + 2F_c²)/3
2719 reflections	(Δ/σ)_max = 0.001
158 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₃H₁₆N₂O₂	V = 1178.26 (4) Å³
M_r = 232.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.5112 (1) Å	µ = 0.09 mm⁻¹
b = 10.1731 (2) Å	T = 295 K
c = 15.8697 (3) Å	0.32 × 0.20 × 0.18 mm
β = 103.675 (1)°

Data collection top

Bruker X8 APEXII diffractometer	2130 reflections with I > 2σ(I)
20993 measured reflections	R_int = 0.042
2719 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.04	Δρ_max = 0.26 e Å⁻³
2719 reflections	Δρ_min = −0.20 e Å⁻³
158 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.16162 (14)	0.16773 (10)	0.73262 (7)	0.0395 (3)
O2	0.56946 (14)	0.16400 (10)	0.59503 (7)	0.0400 (3)
N1	0.25294 (15)	0.37740 (11)	0.72907 (7)	0.0288 (3)
N2	0.54245 (14)	0.37284 (11)	0.63540 (7)	0.0275 (2)
C1	0.29905 (16)	0.49020 (12)	0.68579 (8)	0.0253 (3)
C2	0.20477 (18)	0.60726 (13)	0.68935 (9)	0.0307 (3)
H2	0.1123	0.6096	0.7193	0.037*
C3	0.24611 (19)	0.71969 (14)	0.64933 (9)	0.0327 (3)
H3	0.1835	0.7974	0.6535	0.039*
C4	0.38090 (19)	0.71718 (13)	0.60286 (9)	0.0328 (3)
H4	0.4079	0.7924	0.5750	0.039*
C5	0.47450 (18)	0.60146 (13)	0.59851 (9)	0.0303 (3)
H5	0.5643	0.5994	0.5670	0.036*
C6	0.43742 (16)	0.48743 (12)	0.64028 (8)	0.0250 (3)
C7	0.2047 (2)	0.39958 (15)	0.81279 (9)	0.0351 (3)
H7A	0.2283	0.3211	0.8472	0.053*
H7B	0.0771	0.4217	0.8027	0.053*
H7C	0.2771	0.4704	0.8430	0.053*
C8	0.22299 (17)	0.25474 (13)	0.69423 (9)	0.0289 (3)
C9	0.26599 (18)	0.22616 (13)	0.60544 (9)	0.0313 (3)
C10	0.47116 (18)	0.25147 (13)	0.61116 (8)	0.0288 (3)
C11	0.73932 (18)	0.39067 (15)	0.64072 (10)	0.0350 (3)
H11A	0.8050	0.3139	0.6661	0.052*
H11B	0.7832	0.4660	0.6760	0.052*
H11C	0.7582	0.4038	0.5836	0.052*
C12	0.13980 (19)	0.30489 (16)	0.53176 (9)	0.0371 (3)
H12A	0.1699	0.2846	0.4777	0.056*
H12B	0.1566	0.3973	0.5433	0.056*
H12C	0.0144	0.2818	0.5284	0.056*
C13	0.2302 (2)	0.07970 (15)	0.58570 (12)	0.0487 (4)
H13A	0.3049	0.0282	0.6313	0.073*
H13B	0.2599	0.0586	0.5317	0.073*
H13C	0.1033	0.0606	0.5817	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0423 (6)	0.0378 (6)	0.0421 (6)	−0.0102 (4)	0.0170 (5)	0.0065 (4)
O2	0.0431 (6)	0.0331 (5)	0.0469 (6)	0.0082 (4)	0.0170 (5)	−0.0008 (4)
N1	0.0306 (6)	0.0327 (6)	0.0261 (5)	−0.0038 (4)	0.0128 (5)	0.0013 (4)
N2	0.0234 (5)	0.0299 (6)	0.0312 (6)	0.0015 (4)	0.0104 (4)	0.0019 (4)
C1	0.0250 (6)	0.0291 (6)	0.0226 (6)	−0.0028 (5)	0.0071 (5)	0.0006 (5)
C2	0.0272 (6)	0.0367 (7)	0.0305 (7)	0.0017 (5)	0.0111 (5)	−0.0016 (5)
C3	0.0329 (7)	0.0306 (7)	0.0347 (7)	0.0053 (5)	0.0079 (6)	−0.0004 (5)
C4	0.0375 (7)	0.0294 (7)	0.0323 (7)	−0.0014 (5)	0.0096 (6)	0.0042 (5)
C5	0.0298 (6)	0.0344 (7)	0.0299 (6)	−0.0017 (5)	0.0134 (5)	0.0027 (5)
C6	0.0232 (6)	0.0285 (6)	0.0237 (6)	−0.0003 (5)	0.0064 (5)	−0.0002 (5)
C7	0.0373 (7)	0.0449 (8)	0.0271 (7)	−0.0061 (6)	0.0156 (6)	−0.0004 (6)
C8	0.0243 (6)	0.0331 (7)	0.0300 (6)	−0.0028 (5)	0.0077 (5)	0.0030 (5)
C9	0.0333 (7)	0.0306 (7)	0.0313 (7)	−0.0053 (5)	0.0106 (5)	−0.0029 (5)
C10	0.0326 (7)	0.0302 (7)	0.0252 (6)	0.0036 (5)	0.0102 (5)	0.0039 (5)
C11	0.0241 (6)	0.0429 (8)	0.0401 (8)	0.0028 (5)	0.0119 (6)	0.0001 (6)
C12	0.0315 (7)	0.0512 (9)	0.0277 (7)	−0.0038 (6)	0.0053 (6)	−0.0045 (6)
C13	0.0576 (10)	0.0360 (8)	0.0571 (10)	−0.0134 (7)	0.0227 (8)	−0.0103 (7)

Geometric parameters (Å, º) top

O1—C8	1.2248 (15)	C5—H5	0.9300
O2—C10	1.2214 (15)	C7—H7A	0.9600
N1—C8	1.3619 (17)	C7—H7B	0.9600
N1—C1	1.4217 (15)	C7—H7C	0.9600
N1—C7	1.4749 (16)	C8—C9	1.5457 (18)
N2—C10	1.3645 (17)	C9—C13	1.533 (2)
N2—C6	1.4199 (16)	C9—C10	1.5438 (18)
N2—C11	1.4722 (16)	C9—C12	1.544 (2)
C1—C2	1.3934 (18)	C11—H11A	0.9600
C1—C6	1.3992 (16)	C11—H11B	0.9600
C2—C3	1.3788 (19)	C11—H11C	0.9600
C2—H2	0.9300	C12—H12A	0.9600
C3—C4	1.3866 (19)	C12—H12B	0.9600
C3—H3	0.9300	C12—H12C	0.9600
C4—C5	1.3813 (19)	C13—H13A	0.9600
C4—H4	0.9300	C13—H13B	0.9600
C5—C6	1.3964 (17)	C13—H13C	0.9600

C8—N1—C1	125.39 (10)	O1—C8—N1	120.38 (12)
C8—N1—C7	116.99 (11)	O1—C8—C9	120.12 (12)
C1—N1—C7	116.84 (11)	N1—C8—C9	119.50 (11)
C10—N2—C6	124.90 (11)	C13—C9—C10	107.37 (12)
C10—N2—C11	116.72 (11)	C13—C9—C12	107.62 (12)
C6—N2—C11	117.33 (11)	C10—C9—C12	112.55 (11)
C2—C1—C6	118.99 (11)	C13—C9—C8	107.74 (11)
C2—C1—N1	119.09 (10)	C10—C9—C8	109.63 (11)
C6—C1—N1	121.92 (11)	C12—C9—C8	111.70 (11)
C3—C2—C1	121.22 (12)	O2—C10—N2	120.12 (12)
C3—C2—H2	119.4	O2—C10—C9	120.71 (12)
C1—C2—H2	119.4	N2—C10—C9	119.16 (11)
C2—C3—C4	120.13 (13)	N2—C11—H11A	109.5
C2—C3—H3	119.9	N2—C11—H11B	109.5
C4—C3—H3	119.9	H11A—C11—H11B	109.5
C5—C4—C3	119.11 (12)	N2—C11—H11C	109.5
C5—C4—H4	120.4	H11A—C11—H11C	109.5
C3—C4—H4	120.4	H11B—C11—H11C	109.5
C4—C5—C6	121.56 (12)	C9—C12—H12A	109.5
C4—C5—H5	119.2	C9—C12—H12B	109.5
C6—C5—H5	119.2	H12A—C12—H12B	109.5
C5—C6—C1	118.96 (11)	C9—C12—H12C	109.5
C5—C6—N2	118.71 (11)	H12A—C12—H12C	109.5
C1—C6—N2	122.33 (11)	H12B—C12—H12C	109.5
N1—C7—H7A	109.5	C9—C13—H13A	109.5
N1—C7—H7B	109.5	C9—C13—H13B	109.5
H7A—C7—H7B	109.5	H13A—C13—H13B	109.5
N1—C7—H7C	109.5	C9—C13—H13C	109.5
H7A—C7—H7C	109.5	H13A—C13—H13C	109.5
H7B—C7—H7C	109.5	H13B—C13—H13C	109.5

C8—N1—C1—C2	132.49 (13)	C7—N1—C8—O1	−1.24 (19)
C7—N1—C1—C2	−37.06 (17)	C1—N1—C8—C9	8.88 (19)
C8—N1—C1—C6	−48.03 (18)	C7—N1—C8—C9	178.41 (12)
C7—N1—C1—C6	142.42 (12)	O1—C8—C9—C13	−3.72 (18)
C6—C1—C2—C3	−0.31 (19)	N1—C8—C9—C13	176.63 (13)
N1—C1—C2—C3	179.18 (12)	O1—C8—C9—C10	−120.26 (13)
C1—C2—C3—C4	1.4 (2)	N1—C8—C9—C10	60.09 (16)
C2—C3—C4—C5	−1.0 (2)	O1—C8—C9—C12	114.27 (14)
C3—C4—C5—C6	−0.5 (2)	N1—C8—C9—C12	−65.38 (16)
C4—C5—C6—C1	1.5 (2)	C6—N2—C10—O2	167.89 (12)
C4—C5—C6—N2	−178.11 (12)	C11—N2—C10—O2	−0.06 (18)
C2—C1—C6—C5	−1.14 (18)	C6—N2—C10—C9	−12.78 (18)
N1—C1—C6—C5	179.38 (12)	C11—N2—C10—C9	179.28 (11)
C2—C1—C6—N2	178.50 (12)	C13—C9—C10—O2	4.75 (18)
N1—C1—C6—N2	−0.98 (18)	C12—C9—C10—O2	−113.51 (14)
C10—N2—C6—C5	−128.94 (13)	C8—C9—C10—O2	121.52 (13)
C11—N2—C6—C5	38.94 (17)	C13—C9—C10—N2	−174.59 (12)
C10—N2—C6—C1	51.42 (18)	C12—C9—C10—N2	67.16 (16)
C11—N2—C6—C1	−140.70 (12)	C8—C9—C10—N2	−57.81 (15)
C1—N1—C8—O1	−170.77 (12)

Experimental details

Crystal data
Chemical formula	C₁₃H₁₆N₂O₂
M_r	232.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	7.5112 (1), 10.1731 (2), 15.8697 (3)
β (°)	103.675 (1)
V (Å³)	1178.26 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.32 × 0.20 × 0.18

Data collection
Diffractometer	Bruker X8 APEXII diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	20993, 2719, 2130
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.108, 1.04
No. of reflections	2719
No. of parameters	158
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.20

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.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Mondieig, M., Négrier, Ph., Léger, J. M., Benali, B., Lazar, Z., Elassyry, A., Jarmouni, C., Lakhrissi, B. & Massoui, M. (2005). Anal. Sci. X-Ray Struct. Anal. Online, 21, x145–x146. CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar