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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

aLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Université Mohammed V-Agdal, BP 1014 Avenue Ibn Batout, Rabat, Morocco, bService Commun Rayons-X FR2599, Université Paul Sabatier, Bâtiment 2R1, 118 route de Narbonne, Toulouse, France, and cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my

(Received 6 October 2010; accepted 7 October 2010; online 13 October 2010)

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.

Related literature

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

[Scheme 1]

Experimental

Crystal data
  • C17H23BrN2O2

  • Mr = 367.28

  • Monoclinic, P 21 /n

  • a = 7.5214 (1) Å

  • b = 9.3693 (2) Å

  • c = 23.8686 (5) Å

  • β = 91.750 (1)°

  • V = 1681.24 (6) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 2.45 mm−1

  • T = 293 K

  • 0.30 × 0.20 × 0.10 mm

Data collection
  • Bruker X8 APEXII diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.526, Tmax = 0.791

  • 25590 measured reflections

  • 4897 independent reflections

  • 3478 reflections with I > 2σ(I)

  • Rint = 0.045

Refinement
  • R[F2 > 2σ(F2)] = 0.051

  • wR(F2) = 0.153

  • S = 1.01

  • 4897 reflections

  • 201 parameters

  • H-atom parameters constrained

  • Δρmax = 1.92 e Å−3

  • Δρmin = −0.68 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C7—H7B⋯O1i 0.96 2.58 3.430 (3) 147
C7—H7C⋯O2ii 0.96 2.51 3.471 (3) 174
C11—H11B⋯O1ii 0.96 2.60 3.551 (3) 173
Symmetry codes: (i) [-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) [-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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 m3
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 mm1
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)
Graphite monochromatorRint = 0.045
ϕ and ω scansθmax = 30.0°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 109
Tmin = 0.526, Tmax = 0.791k = 1313
25590 measured reflectionsl = 2833
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 Å3
0 restraintsΔρmin = 0.68 e Å3
Crystal data top
C17H23BrN2O2V = 1681.24 (6) Å3
Mr = 367.28Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.5214 (1) ŵ = 2.45 mm1
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
4897 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
3478 reflections with I > 2σ(I)
Tmin = 0.526, Tmax = 0.791Rint = 0.045
25590 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.153H-atom parameters constrained
S = 1.01Δρmax = 1.92 e Å3
4897 reflectionsΔρmin = 0.68 e Å3
201 parameters
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)
C110.0223 (3)0.7209 (3)0.32308 (12)0.0281 (6)
H11A0.06470.63130.30840.042*
H11B0.04760.79510.29620.042*
H11C0.08070.74190.35730.042*
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, º) 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—C647.6 (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—C240.6 (3)N1—C8—C9—C12164.4 (2)
C6—C1—C2—C31.0 (4)O1—C8—C9—C10104.4 (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—C50.6 (4)C11—N2—C10—O22.0 (4)
C3—C4—C5—C60.6 (4)C6—N2—C10—C95.0 (4)
C4—C5—C6—C10.9 (4)C11—N2—C10—C9179.9 (2)
C4—C5—C6—N2176.7 (2)C12—C9—C10—O218.6 (4)
C2—C1—C6—C50.2 (4)C8—C9—C10—O2105.2 (3)
N1—C1—C6—C5178.1 (2)C12—C9—C10—N2163.5 (2)
C2—C1—C6—N2177.4 (2)C8—C9—C10—N272.7 (3)
N1—C1—C6—N20.5 (4)C8—C9—C12—C1362.5 (3)
C10—N2—C6—C5133.0 (3)C10—C9—C12—C13178.9 (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—C1135.5 (3)C13—C14—C15—C16171.7 (3)
C1—N1—C8—O1179.2 (2)C14—C15—C16—C17174.1 (3)
C7—N1—C8—O14.1 (4)C15—C16—C17—Br1175.0 (3)
Hydrogen-bond geometry (Å, º) 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.

Experimental details

Crystal data
Chemical formulaC17H23BrN2O2
Mr367.28
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)7.5214 (1), 9.3693 (2), 23.8686 (5)
β (°) 91.750 (1)
V3)1681.24 (6)
Z4
Radiation typeMo Kα
µ (mm1)2.45
Crystal size (mm)0.30 × 0.20 × 0.10
Data collection
DiffractometerBruker X8 APEXII
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.526, 0.791
No. of measured, independent and
observed [I > 2σ(I)] reflections
25590, 4897, 3478
Rint0.045
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.153, 1.01
No. of reflections4897
No. of parameters201
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.92, 0.68

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

Hydrogen-bond geometry (Å, º) 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

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

References

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS
First citationBruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationMondieig, 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
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
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