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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2805.
Published online 2010 October 13. doi:  10.1107/S1600536810040134
PMCID: PMC3009360

3-(12-Bromo­dodec­yl)-1,5-dimethyl-1H-1,5-benzodiazepine-2,4(3H,5H)-dione

Abstract

The seven-membered ring in the title compound, C23H35BrN2O2, 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 bromo­dodecyl substituent occupies an equatorial position, with the dodecyl 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 [triangle]). For the structure of a similar compound, 3-(6-bromo­hex­yl)-1,5-dimethyl-1,5-benzodiazepine-2,4-dione, see: Dardouri et al. (2010 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2805-scheme1.jpg

Experimental

Crystal data

  • C23H35BrN2O2
  • M r = 451.44
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2805-efi1.jpg
  • a = 7.5971 (1) Å
  • b = 10.5032 (2) Å
  • c = 28.7129 (5) Å
  • β = 95.213 (1)°
  • V = 2281.64 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.82 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 [triangle]) T min = 0.611, T max = 0.839
  • 24581 measured reflections
  • 6634 independent reflections
  • 4370 reflections with I > 2σ(I)
  • R int = 0.037

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.099
  • S = 0.99
  • 6634 reflections
  • 255 parameters
  • H-atom parameters constrained
  • Δρmax = 0.61 e Å−3
  • Δρmin = −0.23 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810040134/xu5050sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810040134/xu5050Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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 1,12-dibromododecane the title compound (Scheme I, Fig. 1).

Experimental

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 1,12-dibromododecane (0.94 g, 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

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).

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of C23H35BrN2O2 at the 50% probability level; hydrogen atoms are drawn as arbitrary radius.

Crystal data

C23H35BrN2O2F(000) = 952
Mr = 451.44Dx = 1.314 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5655 reflections
a = 7.5971 (1) Åθ = 2.4–25.4°
b = 10.5032 (2) ŵ = 1.82 mm1
c = 28.7129 (5) ÅT = 293 K
β = 95.213 (1)°Prism, colorless
V = 2281.64 (7) Å30.30 × 0.20 × 0.10 mm
Z = 4

Data collection

Bruker X8 APEXII diffractometer6634 independent reflections
Radiation source: fine-focus sealed tube4370 reflections with I > 2σ(I)
graphiteRint = 0.037
[var phi] and ω scansθmax = 30.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −10→10
Tmin = 0.611, Tmax = 0.839k = −14→12
24581 measured reflectionsl = −40→40

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-atom parameters constrained
S = 0.99w = 1/[σ2(Fo2) + (0.0518P)2] where P = (Fo2 + 2Fc2)/3
6634 reflections(Δ/σ)max = 0.001
255 parametersΔρmax = 0.61 e Å3
0 restraintsΔρmin = −0.23 e Å3

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

xyzUiso*/Ueq
Br11.65169 (3)1.558652 (19)0.586300 (7)0.04634 (9)
N10.0090 (2)0.57047 (12)0.26467 (5)0.0294 (3)
N2−0.32138 (19)0.57806 (12)0.30691 (5)0.0291 (3)
O10.08035 (17)0.77902 (11)0.26153 (4)0.0368 (3)
O2−0.35919 (17)0.78733 (11)0.32234 (5)0.0411 (3)
C1−0.0532 (2)0.46396 (15)0.28941 (6)0.0276 (4)
C20.0475 (2)0.35221 (16)0.29190 (7)0.0350 (4)
H20.15510.34970.27880.042*
C3−0.0126 (3)0.24597 (17)0.31369 (7)0.0411 (5)
H30.05490.17200.31540.049*
C4−0.1723 (3)0.24865 (17)0.33297 (7)0.0407 (5)
H4−0.21310.17620.34720.049*
C5−0.2713 (3)0.35867 (16)0.33120 (7)0.0347 (4)
H5−0.37810.36050.34470.042*
C6−0.2126 (2)0.46761 (15)0.30930 (6)0.0266 (4)
C70.0742 (3)0.54706 (17)0.21882 (6)0.0355 (4)
H7A0.06590.62400.20070.053*
H7B0.00410.48190.20270.053*
H7C0.19530.52000.22310.053*
C80.0180 (2)0.69084 (15)0.28235 (6)0.0285 (4)
C9−0.0598 (2)0.70942 (15)0.32913 (6)0.0273 (4)
H9−0.01650.64120.35050.033*
C10−0.2600 (2)0.69690 (16)0.31965 (6)0.0292 (4)
C11−0.5119 (2)0.56279 (17)0.29472 (7)0.0350 (4)
H11A−0.55920.63970.28050.053*
H11B−0.56900.54540.32250.053*
H11C−0.53200.49330.27320.053*
C12−0.0055 (2)0.83761 (16)0.35126 (7)0.0327 (4)
H12A−0.02000.90370.32760.039*
H12B−0.08230.85760.37550.039*
C130.1849 (2)0.83595 (15)0.37232 (6)0.0329 (4)
H13A0.25970.80920.34850.039*
H13B0.19650.77320.39720.039*
C140.2511 (2)0.96386 (16)0.39196 (7)0.0328 (4)
H14A0.24371.02620.36690.039*
H14B0.17450.99210.41520.039*
C150.4398 (3)0.95858 (15)0.41418 (7)0.0335 (4)
H15A0.51420.92290.39180.040*
H15B0.44460.90150.44080.040*
C160.5151 (3)1.08722 (16)0.43040 (7)0.0348 (4)
H16A0.51331.14390.40370.042*
H16B0.43981.12390.45240.042*
C170.7028 (3)1.07876 (15)0.45343 (7)0.0354 (4)
H17A0.77791.04310.43120.043*
H17B0.70451.02060.47970.043*
C180.7796 (3)1.20563 (16)0.47064 (7)0.0365 (4)
H18A0.78191.26290.44420.044*
H18B0.70251.24270.49210.044*
C190.9648 (3)1.19565 (16)0.49503 (7)0.0383 (4)
H19A1.04181.15930.47340.046*
H19B0.96251.13730.52120.046*
C201.0436 (3)1.32136 (16)0.51308 (7)0.0362 (4)
H20A1.04391.38080.48720.043*
H20B0.96961.35680.53570.043*
C211.2304 (3)1.30689 (16)0.53584 (7)0.0370 (4)
H21A1.30131.26510.51390.044*
H21B1.22781.25160.56280.044*
C221.3211 (3)1.43160 (15)0.55161 (7)0.0365 (4)
H22A1.32161.48940.52530.044*
H22B1.25691.47180.57530.044*
C231.5070 (3)1.40468 (18)0.57104 (7)0.0409 (5)
H23A1.56431.35420.54850.049*
H23B1.50381.35390.59920.049*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.05160 (15)0.04100 (12)0.04792 (14)−0.01138 (9)0.01260 (10)−0.00678 (9)
N10.0297 (8)0.0275 (7)0.0323 (8)−0.0030 (6)0.0092 (6)−0.0026 (6)
N20.0229 (7)0.0252 (7)0.0392 (8)0.0003 (5)0.0030 (6)−0.0004 (6)
O10.0387 (7)0.0305 (6)0.0421 (7)−0.0073 (5)0.0089 (6)0.0033 (5)
O20.0327 (7)0.0307 (7)0.0598 (9)0.0082 (6)0.0037 (6)−0.0064 (6)
C10.0281 (9)0.0249 (8)0.0300 (9)−0.0010 (7)0.0030 (7)−0.0014 (6)
C20.0304 (10)0.0325 (9)0.0428 (11)0.0046 (7)0.0072 (8)−0.0037 (8)
C30.0466 (12)0.0276 (9)0.0492 (12)0.0100 (8)0.0057 (9)0.0017 (8)
C40.0507 (12)0.0294 (9)0.0433 (11)−0.0005 (8)0.0114 (9)0.0078 (8)
C50.0340 (10)0.0311 (9)0.0405 (10)−0.0021 (7)0.0116 (8)0.0013 (7)
C60.0257 (9)0.0238 (8)0.0305 (9)0.0006 (6)0.0029 (7)−0.0015 (6)
C70.0343 (10)0.0403 (10)0.0331 (10)−0.0048 (8)0.0097 (8)−0.0036 (8)
C80.0230 (9)0.0274 (8)0.0348 (9)−0.0007 (7)0.0002 (7)−0.0007 (7)
C90.0255 (9)0.0239 (8)0.0323 (9)0.0008 (6)0.0015 (7)−0.0024 (6)
C100.0286 (9)0.0275 (8)0.0317 (9)0.0023 (7)0.0041 (7)−0.0009 (7)
C110.0254 (9)0.0361 (9)0.0431 (11)−0.0003 (8)0.0002 (8)−0.0007 (8)
C120.0322 (10)0.0257 (8)0.0402 (10)0.0003 (7)0.0031 (8)−0.0054 (7)
C130.0360 (10)0.0253 (8)0.0371 (10)−0.0006 (7)0.0017 (8)−0.0047 (7)
C140.0375 (10)0.0258 (8)0.0351 (10)−0.0005 (7)0.0034 (8)−0.0030 (7)
C150.0396 (11)0.0257 (9)0.0345 (10)−0.0019 (7)0.0000 (8)−0.0036 (7)
C160.0414 (11)0.0252 (9)0.0378 (10)−0.0010 (7)0.0038 (8)−0.0046 (7)
C170.0426 (11)0.0263 (9)0.0366 (10)−0.0045 (7)−0.0009 (8)−0.0050 (7)
C180.0429 (11)0.0252 (9)0.0412 (10)−0.0027 (8)0.0024 (9)−0.0049 (7)
C190.0449 (11)0.0287 (9)0.0400 (11)−0.0014 (8)−0.0025 (9)−0.0040 (8)
C200.0419 (11)0.0281 (9)0.0384 (10)−0.0033 (8)0.0028 (8)−0.0039 (7)
C210.0454 (11)0.0271 (9)0.0377 (10)−0.0014 (8)−0.0006 (9)−0.0021 (7)
C220.0435 (11)0.0272 (9)0.0384 (10)−0.0023 (8)0.0023 (9)−0.0027 (7)
C230.0442 (12)0.0322 (9)0.0457 (11)−0.0041 (8)0.0003 (9)−0.0067 (8)

Geometric parameters (Å, °)

Br1—C231.9818 (19)C13—C141.525 (2)
N1—C81.362 (2)C13—H13A0.9700
N1—C11.428 (2)C13—H13B0.9700
N1—C71.469 (2)C14—C151.516 (3)
N2—C101.371 (2)C14—H14A0.9700
N2—C61.423 (2)C14—H14B0.9700
N2—C111.466 (2)C15—C161.523 (2)
O1—C81.221 (2)C15—H15A0.9700
O2—C101.219 (2)C15—H15B0.9700
C1—C61.386 (2)C16—C171.519 (3)
C1—C21.399 (2)C16—H16A0.9700
C2—C31.377 (3)C16—H16B0.9700
C2—H20.9300C17—C181.519 (2)
C3—C41.378 (3)C17—H17A0.9700
C3—H30.9300C17—H17B0.9700
C4—C51.377 (3)C18—C191.517 (3)
C4—H40.9300C18—H18A0.9700
C5—C61.398 (2)C18—H18B0.9700
C5—H50.9300C19—C201.521 (2)
C7—H7A0.9600C19—H19A0.9700
C7—H7B0.9600C19—H19B0.9700
C7—H7C0.9600C20—C211.515 (3)
C8—C91.528 (2)C20—H20A0.9700
C9—C101.526 (2)C20—H20B0.9700
C9—C121.529 (2)C21—C221.529 (2)
C9—H90.9800C21—H21A0.9700
C11—H11A0.9600C21—H21B0.9700
C11—H11B0.9600C22—C231.497 (3)
C11—H11C0.9600C22—H22A0.9700
C12—C131.516 (3)C22—H22B0.9700
C12—H12A0.9700C23—H23A0.9700
C12—H12B0.9700C23—H23B0.9700
C8—N1—C1123.32 (14)C15—C14—C13113.01 (14)
C8—N1—C7118.69 (14)C15—C14—H14A109.0
C1—N1—C7117.93 (13)C13—C14—H14A109.0
C10—N2—C6123.20 (14)C15—C14—H14B109.0
C10—N2—C11117.90 (14)C13—C14—H14B109.0
C6—N2—C11118.61 (13)H14A—C14—H14B107.8
C6—C1—C2119.76 (15)C14—C15—C16114.23 (14)
C6—C1—N1121.61 (15)C14—C15—H15A108.7
C2—C1—N1118.59 (15)C16—C15—H15A108.7
C3—C2—C1120.02 (17)C14—C15—H15B108.7
C3—C2—H2120.0C16—C15—H15B108.7
C1—C2—H2120.0H15A—C15—H15B107.6
C2—C3—C4120.41 (17)C17—C16—C15113.12 (14)
C2—C3—H3119.8C17—C16—H16A109.0
C4—C3—H3119.8C15—C16—H16A109.0
C5—C4—C3120.00 (17)C17—C16—H16B109.0
C5—C4—H4120.0C15—C16—H16B109.0
C3—C4—H4120.0H16A—C16—H16B107.8
C4—C5—C6120.50 (17)C16—C17—C18114.08 (14)
C4—C5—H5119.7C16—C17—H17A108.7
C6—C5—H5119.7C18—C17—H17A108.7
C1—C6—C5119.30 (15)C16—C17—H17B108.7
C1—C6—N2121.91 (14)C18—C17—H17B108.7
C5—C6—N2118.76 (15)H17A—C17—H17B107.6
N1—C7—H7A109.5C19—C18—C17113.72 (15)
N1—C7—H7B109.5C19—C18—H18A108.8
H7A—C7—H7B109.5C17—C18—H18A108.8
N1—C7—H7C109.5C19—C18—H18B108.8
H7A—C7—H7C109.5C17—C18—H18B108.8
H7B—C7—H7C109.5H18A—C18—H18B107.7
O1—C8—N1122.01 (16)C18—C19—C20114.64 (15)
O1—C8—C9122.12 (15)C18—C19—H19A108.6
N1—C8—C9115.85 (14)C20—C19—H19A108.6
C10—C9—C8106.92 (14)C18—C19—H19B108.6
C10—C9—C12112.15 (14)C20—C19—H19B108.6
C8—C9—C12111.47 (14)H19A—C19—H19B107.6
C10—C9—H9108.7C21—C20—C19112.58 (15)
C8—C9—H9108.7C21—C20—H20A109.1
C12—C9—H9108.7C19—C20—H20A109.1
O2—C10—N2121.92 (16)C21—C20—H20B109.1
O2—C10—C9122.23 (15)C19—C20—H20B109.1
N2—C10—C9115.83 (14)H20A—C20—H20B107.8
N2—C11—H11A109.5C20—C21—C22114.90 (15)
N2—C11—H11B109.5C20—C21—H21A108.5
H11A—C11—H11B109.5C22—C21—H21A108.5
N2—C11—H11C109.5C20—C21—H21B108.5
H11A—C11—H11C109.5C22—C21—H21B108.5
H11B—C11—H11C109.5H21A—C21—H21B107.5
C13—C12—C9111.55 (14)C23—C22—C21109.44 (14)
C13—C12—H12A109.3C23—C22—H22A109.8
C9—C12—H12A109.3C21—C22—H22A109.8
C13—C12—H12B109.3C23—C22—H22B109.8
C9—C12—H12B109.3C21—C22—H22B109.8
H12A—C12—H12B108.0H22A—C22—H22B108.2
C12—C13—C14114.09 (14)C22—C23—Br1114.43 (12)
C12—C13—H13A108.7C22—C23—H23A108.7
C14—C13—H13A108.7Br1—C23—H23A108.7
C12—C13—H13B108.7C22—C23—H23B108.7
C14—C13—H13B108.7Br1—C23—H23B108.7
H13A—C13—H13B107.6H23A—C23—H23B107.6
C8—N1—C1—C650.6 (2)N1—C8—C9—C10−70.41 (18)
C7—N1—C1—C6−132.37 (17)O1—C8—C9—C12−15.1 (2)
C8—N1—C1—C2−131.72 (18)N1—C8—C9—C12166.69 (15)
C7—N1—C1—C245.3 (2)C6—N2—C10—O2−171.56 (16)
C6—C1—C2—C30.6 (3)C11—N2—C10—O22.2 (3)
N1—C1—C2—C3−177.09 (17)C6—N2—C10—C99.8 (2)
C1—C2—C3—C40.3 (3)C11—N2—C10—C9−176.45 (15)
C2—C3—C4—C5−1.1 (3)C8—C9—C10—O2−111.04 (18)
C3—C4—C5—C61.0 (3)C12—C9—C10—O211.4 (2)
C2—C1—C6—C5−0.7 (3)C8—C9—C10—N267.61 (18)
N1—C1—C6—C5176.96 (16)C12—C9—C10—N2−169.93 (15)
C2—C1—C6—N2−178.75 (16)C10—C9—C12—C13164.64 (15)
N1—C1—C6—N2−1.1 (3)C8—C9—C12—C13−75.51 (19)
C4—C5—C6—C1−0.1 (3)C9—C12—C13—C14175.98 (15)
C4—C5—C6—N2178.02 (17)C12—C13—C14—C15178.16 (16)
C10—N2—C6—C1−51.4 (2)C13—C14—C15—C16175.04 (15)
C11—N2—C6—C1134.90 (17)C14—C15—C16—C17178.80 (16)
C10—N2—C6—C5130.52 (18)C15—C16—C17—C18−179.03 (16)
C11—N2—C6—C5−43.2 (2)C16—C17—C18—C19178.06 (17)
C1—N1—C8—O1176.05 (16)C17—C18—C19—C20−179.30 (17)
C7—N1—C8—O1−0.9 (3)C18—C19—C20—C21−178.30 (16)
C1—N1—C8—C9−5.7 (2)C19—C20—C21—C22175.93 (17)
C7—N1—C8—C9177.33 (15)C20—C21—C22—C23−177.00 (16)
O1—C8—C9—C10107.82 (18)C21—C22—C23—Br1173.24 (13)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2···O1i0.932.523.424 (2)164
C7—H7B···O2ii0.962.403.340 (2)166
C11—H11C···O1ii0.962.483.407 (2)164

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU5050).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
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