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Acta Cryst. (2010). E66, o2804    [ doi:10.1107/S1600536810040122 ]

3-(6-Bromohexyl)-1,5-dimethyl-1H-1,5-benzodiazepine-2,4(3H,5H)-dione

R. Dardouri, F. Ouazzani Chahdi, N. Saffon, E. M. Essassi and S. W. Ng

Abstract top

The seven-membered ring in the title compound, C17H23BrN2O2, 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 bromohexyl substituent occupies an equatorial position, with the hexyl chain exhibiting an extended conformation. Weak intermolecular C-H...O hydrogen bonding is present in the crystal structure.

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 a dibromoalkane to form 3-substituted derivatives. In this study, the compound is reacted with 1,6-dibromohexane the title compound (Scheme I, Fig. 1).

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 1,6-dibromodohexane (0.40 ml, 2.88 mmol). Stirring was continued for 24 h. The reaction was monitored by thin layer chromatography. The mixture was filtered and the solution evaporated to give colorless crystals.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93–0.97 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2–1.5Ueq(C).

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
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C17H23BrN2O2 at the 50% probability level; hydrogen atoms are drawn as arbitrary radius.
3-(6-Bromohexyl)-1,5-dimethyl-1H-1,5-benzodiazepine- 2,4(3H,5H)-dione top
Crystal data top
C17H23BrN2O2F(000) = 760
Mr = 367.28Dx = 1.451 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5411 reflections
a = 7.5214 (1) Åθ = 2.3–26.0°
b = 9.3693 (2) ŵ = 2.45 mm−1
c = 23.8686 (5) ÅT = 293 K
β = 91.750 (1)°Prism, colorless
V = 1681.24 (6) Å30.30 × 0.20 × 0.10 mm
Z = 4
Data collection top
Bruker X8 APEXII
diffractometer		4897 independent reflections
Radiation source: fine-focus sealed tube3478 reflections with I > 2σ(I)
graphiteRint = 0.045
φ and ω scansθmax = 30.0°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→9
Tmin = 0.526, Tmax = 0.791k = −13→13
25590 measured reflectionsl = −28→33
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.153H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.082P)2 + 1.8005P]
where P = (Fo2 + 2Fc2)/3
4897 reflections(Δ/σ)max = 0.001
201 parametersΔρmax = 1.92 e Å−3
0 restraintsΔρmin = −0.68 e Å−3
Crystal data top
C17H23BrN2O2V = 1681.24 (6) Å3
Mr = 367.28Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.5214 (1) ŵ = 2.45 mm−1
b = 9.3693 (2) ÅT = 293 K
c = 23.8686 (5) Å0.30 × 0.20 × 0.10 mm
β = 91.750 (1)°
Data collection top
Bruker X8 APEXII
diffractometer		3478 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		Rint = 0.045
Tmin = 0.526, Tmax = 0.791θmax = 30.0°
25590 measured reflectionsStandard reflections: 0
4897 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.051H-atom parameters constrained
wR(F2) = 0.153Δρmax = 1.92 e Å−3
S = 1.01Δρmin = −0.68 e Å−3
4897 reflectionsAbsolute structure: ?
201 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br11.30982 (5)0.07856 (4)0.564211 (15)0.04567 (14)
O10.5859 (3)0.4826 (2)0.28329 (9)0.0297 (4)
O20.1496 (3)0.4797 (2)0.35848 (10)0.0351 (5)
N10.5074 (3)0.7166 (2)0.27741 (9)0.0211 (4)
N20.1710 (3)0.7124 (2)0.33415 (9)0.0231 (4)
C10.4344 (3)0.8410 (3)0.30158 (10)0.0199 (5)
C20.5247 (4)0.9710 (3)0.29605 (11)0.0247 (5)
H20.63310.97290.27830.030*
C30.4550 (4)1.0961 (3)0.31659 (12)0.0278 (6)
H30.51531.18180.31190.033*
C40.2944 (4)1.0944 (3)0.34434 (12)0.0266 (5)
H40.24761.17840.35850.032*
C50.2056 (4)0.9665 (3)0.35053 (11)0.0251 (5)
H50.09910.96510.36930.030*
C60.2725 (3)0.8394 (3)0.32918 (10)0.0203 (5)
C70.5848 (3)0.7301 (3)0.22189 (11)0.0244 (5)
H7A0.58750.63810.20420.037*
H7B0.70360.76670.22590.037*
H7C0.51370.79420.19920.037*
C80.5209 (3)0.5879 (3)0.30474 (11)0.0215 (5)
C90.4425 (4)0.5856 (3)0.36297 (11)0.0233 (5)
H90.47700.67350.38270.028*
C100.2407 (4)0.5863 (3)0.35245 (11)0.0237 (5)
C11−0.0223 (3)0.7209 (3)0.32308 (12)0.0281 (6)
H11A−0.06470.63130.30840.042*
H11B−0.04760.79510.29620.042*
H11C−0.08070.74190.35730.042*
C120.5012 (4)0.4579 (3)0.39872 (12)0.0291 (6)
H12A0.43950.46080.43380.035*
H12B0.46620.37090.37940.035*
C130.6995 (4)0.4532 (3)0.41145 (14)0.0363 (7)
H13A0.73880.54690.42390.044*
H13B0.76030.43120.37720.044*
C140.7533 (4)0.3430 (3)0.45629 (14)0.0372 (7)
H14A0.72020.37820.49270.045*
H14B0.68840.25510.44910.045*
C150.9504 (5)0.3118 (4)0.45750 (15)0.0462 (8)
H15A1.01430.40180.45880.055*
H15B0.97940.26460.42280.055*
C161.0164 (4)0.2199 (3)0.50614 (13)0.0360 (7)
H16A1.00140.27090.54110.043*
H16B0.94650.13310.50740.043*
C171.2095 (5)0.1827 (5)0.50011 (14)0.0469 (8)
H17A1.27680.26990.49530.056*
H17B1.22190.12530.46660.056*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0511 (2)0.0394 (2)0.0454 (2)0.00836 (15)−0.01604 (15)−0.00333 (14)
O10.0329 (10)0.0220 (9)0.0342 (10)0.0060 (8)0.0014 (8)−0.0021 (8)
O20.0311 (11)0.0260 (10)0.0482 (13)−0.0106 (8)0.0014 (9)0.0044 (9)
N10.0222 (10)0.0170 (9)0.0243 (10)0.0011 (8)0.0034 (8)−0.0001 (8)
N20.0189 (10)0.0223 (10)0.0283 (11)−0.0039 (8)0.0017 (8)0.0011 (8)
C10.0204 (11)0.0177 (11)0.0215 (11)0.0023 (9)−0.0003 (9)0.0006 (9)
C20.0231 (12)0.0213 (11)0.0299 (13)−0.0023 (10)0.0051 (10)0.0017 (10)
C30.0310 (14)0.0196 (12)0.0329 (14)−0.0041 (10)0.0022 (11)0.0000 (10)
C40.0279 (13)0.0209 (12)0.0309 (13)0.0027 (10)−0.0004 (10)−0.0027 (10)
C50.0220 (12)0.0259 (12)0.0276 (13)0.0017 (10)0.0024 (10)−0.0006 (10)
C60.0187 (11)0.0195 (11)0.0227 (11)−0.0019 (9)−0.0011 (9)0.0008 (9)
C70.0242 (12)0.0257 (12)0.0234 (12)0.0011 (10)0.0033 (9)−0.0011 (10)
C80.0193 (11)0.0171 (11)0.0281 (12)−0.0003 (9)−0.0020 (9)−0.0003 (9)
C90.0266 (12)0.0166 (11)0.0264 (12)−0.0020 (9)−0.0009 (10)0.0013 (9)
C100.0258 (12)0.0218 (12)0.0237 (12)−0.0042 (10)0.0029 (9)−0.0007 (9)
C110.0183 (11)0.0328 (14)0.0330 (14)−0.0036 (10)−0.0004 (10)−0.0013 (11)
C120.0359 (15)0.0201 (11)0.0311 (14)−0.0012 (11)−0.0019 (11)0.0030 (10)
C130.0343 (15)0.0339 (15)0.0403 (16)−0.0016 (13)−0.0050 (12)0.0139 (13)
C140.0436 (17)0.0312 (15)0.0365 (16)0.0045 (13)−0.0029 (13)0.0103 (12)
C150.0474 (19)0.054 (2)0.0369 (17)0.0059 (17)−0.0025 (14)0.0178 (15)
C160.0428 (17)0.0348 (15)0.0298 (14)−0.0013 (13)−0.0064 (12)0.0079 (12)
C170.0480 (19)0.059 (2)0.0334 (16)0.0098 (17)−0.0005 (14)0.0101 (15)
Geometric parameters (Å, °) top
Br1—C171.947 (3)C9—C121.527 (4)
O1—C81.221 (3)C9—C101.531 (4)
O2—C101.222 (3)C9—H90.9800
N1—C81.373 (3)C11—H11A0.9600
N1—C11.419 (3)C11—H11B0.9600
N1—C71.469 (3)C11—H11C0.9600
N2—C101.359 (3)C12—C131.514 (4)
N2—C61.420 (3)C12—H12A0.9700
N2—C111.472 (3)C12—H12B0.9700
C1—C61.402 (3)C13—C141.533 (4)
C1—C21.402 (4)C13—H13A0.9700
C2—C31.380 (4)C13—H13B0.9700
C2—H20.9300C14—C151.511 (5)
C3—C41.396 (4)C14—H14A0.9700
C3—H30.9300C14—H14B0.9700
C4—C51.382 (4)C15—C161.517 (4)
C4—H40.9300C15—H15A0.9700
C5—C61.395 (4)C15—H15B0.9700
C5—H50.9300C16—C171.505 (5)
C7—H7A0.9600C16—H16A0.9700
C7—H7B0.9600C16—H16B0.9700
C7—H7C0.9600C17—H17A0.9700
C8—C91.526 (4)C17—H17B0.9700
C8—N1—C1123.5 (2)N2—C11—H11A109.5
C8—N1—C7118.6 (2)N2—C11—H11B109.5
C1—N1—C7117.7 (2)H11A—C11—H11B109.5
C10—N2—C6123.5 (2)N2—C11—H11C109.5
C10—N2—C11118.3 (2)H11A—C11—H11C109.5
C6—N2—C11118.0 (2)H11B—C11—H11C109.5
C6—C1—C2118.9 (2)C13—C12—C9113.7 (2)
C6—C1—N1122.3 (2)C13—C12—H12A108.8
C2—C1—N1118.7 (2)C9—C12—H12A108.8
C3—C2—C1120.9 (2)C13—C12—H12B108.8
C3—C2—H2119.5C9—C12—H12B108.8
C1—C2—H2119.5H12A—C12—H12B107.7
C2—C3—C4120.2 (2)C12—C13—C14113.4 (3)
C2—C3—H3119.9C12—C13—H13A108.9
C4—C3—H3119.9C14—C13—H13A108.9
C5—C4—C3119.3 (2)C12—C13—H13B108.9
C5—C4—H4120.4C14—C13—H13B108.9
C3—C4—H4120.4H13A—C13—H13B107.7
C4—C5—C6121.4 (2)C15—C14—C13112.4 (3)
C4—C5—H5119.3C15—C14—H14A109.1
C6—C5—H5119.3C13—C14—H14A109.1
C5—C6—C1119.4 (2)C15—C14—H14B109.1
C5—C6—N2118.9 (2)C13—C14—H14B109.1
C1—C6—N2121.7 (2)H14A—C14—H14B107.9
N1—C7—H7A109.5C14—C15—C16115.0 (3)
N1—C7—H7B109.5C14—C15—H15A108.5
H7A—C7—H7B109.5C16—C15—H15A108.5
N1—C7—H7C109.5C14—C15—H15B108.5
H7A—C7—H7C109.5C16—C15—H15B108.5
H7B—C7—H7C109.5H15A—C15—H15B107.5
O1—C8—N1122.4 (2)C17—C16—C15110.6 (3)
O1—C8—C9122.8 (2)C17—C16—H16A109.5
N1—C8—C9114.8 (2)C15—C16—H16A109.5
C12—C9—C8114.0 (2)C17—C16—H16B109.5
C12—C9—C10111.3 (2)C15—C16—H16B109.5
C8—C9—C10105.0 (2)H16A—C16—H16B108.1
C12—C9—H9108.8C16—C17—Br1113.1 (2)
C8—C9—H9108.8C16—C17—H17A109.0
C10—C9—H9108.8Br1—C17—H17A109.0
O2—C10—N2122.4 (3)C16—C17—H17B109.0
O2—C10—C9122.3 (2)Br1—C17—H17B109.0
N2—C10—C9115.3 (2)H17A—C17—H17B107.8
C8—N1—C1—C6−47.6 (3)C1—N1—C8—C92.9 (3)
C7—N1—C1—C6137.3 (2)C7—N1—C8—C9177.9 (2)
C8—N1—C1—C2134.5 (3)O1—C8—C9—C1217.7 (4)
C7—N1—C1—C2−40.6 (3)N1—C8—C9—C12−164.4 (2)
C6—C1—C2—C3−1.0 (4)O1—C8—C9—C10−104.4 (3)
N1—C1—C2—C3177.0 (2)N1—C8—C9—C1073.5 (3)
C1—C2—C3—C41.3 (4)C6—N2—C10—O2177.1 (3)
C2—C3—C4—C5−0.6 (4)C11—N2—C10—O22.0 (4)
C3—C4—C5—C6−0.6 (4)C6—N2—C10—C9−5.0 (4)
C4—C5—C6—C10.9 (4)C11—N2—C10—C9179.9 (2)
C4—C5—C6—N2−176.7 (2)C12—C9—C10—O2−18.6 (4)
C2—C1—C6—C5−0.2 (4)C8—C9—C10—O2105.2 (3)
N1—C1—C6—C5−178.1 (2)C12—C9—C10—N2163.5 (2)
C2—C1—C6—N2177.4 (2)C8—C9—C10—N2−72.7 (3)
N1—C1—C6—N2−0.5 (4)C8—C9—C12—C1362.5 (3)
C10—N2—C6—C5−133.0 (3)C10—C9—C12—C13−178.9 (2)
C11—N2—C6—C542.1 (3)C9—C12—C13—C14168.8 (3)
C10—N2—C6—C149.5 (4)C12—C13—C14—C15164.8 (3)
C11—N2—C6—C1−135.5 (3)C13—C14—C15—C16171.7 (3)
C1—N1—C8—O1−179.2 (2)C14—C15—C16—C17174.1 (3)
C7—N1—C8—O1−4.1 (4)C15—C16—C17—Br1175.0 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C7—H7B···O1i0.962.583.430 (3)147
C7—H7C···O2ii0.962.513.471 (3)174
C11—H11B···O1ii0.962.603.551 (3)173
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C7—H7B···O1i0.962.583.430 (3)147
C7—H7C···O2ii0.962.513.471 (3)174
C11—H11B···O1ii0.962.603.551 (3)173
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2.
Acknowledgements top

We thank Université Mohammed V-Agdal and the University of Malaya for supporting this study.

references
References top

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Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.