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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3228.
Published online 2010 November 20. doi:  10.1107/S1600536810047008
PMCID: PMC3011384

7-Chloro-1,5-dipropargyl-1H-1,5-benzodiazepine-2,4(3H,5H)-dione

Abstract

The seven-membered ring of the title compound, C15H11ClN2O2, adopts a boat-shaped conformation (with the C atoms of the fused-ring as the stern and the methyl­ene C atom as the prow). The N atoms exists in a trigonal–planar coordination; one of the acetyl­enic H atoms forms a C—H(...)O hydrogen bond to the O atom of an adjacent mol­ecule, generating a linear chain along a body diagonal.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-66-o3228-scheme1.jpg

Experimental

Crystal data

  • C15H11ClN2O2
  • M r = 286.71
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3228-efi1.jpg
  • a = 10.7755 (3) Å
  • b = 7.6580 (2) Å
  • c = 16.7221 (5) Å
  • β = 103.621 (1)°
  • V = 1341.08 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.29 mm−1
  • T = 293 K
  • 0.42 × 0.10 × 0.08 mm

Data collection

  • Bruker X8 APEXII diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.889, T max = 0.977
  • 17112 measured reflections
  • 3359 independent reflections
  • 2679 reflections with I > 2σ(I)
  • R int = 0.036

Refinement

  • R[F 2 > 2σ(F 2)] = 0.058
  • wR(F 2) = 0.172
  • S = 1.07
  • 3359 reflections
  • 189 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 1.36 e Å−3
  • Δρmin = −0.55 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [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/S1600536810047008/nk2074sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810047008/nk2074Isup2.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

We have reported the alkylation of 1,5-benzodiazepine-2,4-dione by alkylating agents in the presence of tetra-n-butylammonium bromide as catalyst (Mondieig et al., 2005). In the present study, the amino H atoms are replaced by propargyl groups in the substituted 1,5-benzodiazepin-2,4-dione. The seven-membered ring of C15H11ClN2O2 (Scheme I, Fig. 1) adopts a boat-shaped conformation (with the C atoms of the fused-ring as the stern and the methylene C atom as the prow). The nitrogen atoms exists in a trigonal-planar coordination; one of the acetylenic H atoms forms a C–H···O hydrogen bond to the oxygen atom of an adjacent molecule to generate a linear chain (Fig. 2).

Experimental

To a solution of the 7-chloro-1,5-benzodiazepine-2,4-dione (0.5 g, 2.38 mmol) in DMF (15 ml) was added potassium carbonate (0.98 g, 7.14 mmol), propargyl bromide (0.45 ml, 5.24 mmol) and tetra-n-butylammonium bromide (0.007 g, 0.25 mmol). Stirring was continued under reflux and the reaction was monitored by thin layer chromatography. On completion of the reactin, the mixture was filtered and the solvent removed under reduced pressure. The residue was separated by chromatography on a column of silica gel with ethyl acetate-hexane (1:1) as eluent. Yellow crystals were isolated when the solvent was allowed to evaporate.

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). The final difference Fourier map had a peak in the vicinity of H4, and is 1.51 Å from C4. Attempts to treat this peak as a disorder component of the chlorine atom were unsuccessful. Furthermore, lowering to 2θ limit to 50 ° lead to a peak that has only 1 e Å-3 only.

Figures

Fig. 1.
Displacement ellipsoid plot of C15H11ClN2O2 at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
Fig. 2.
The hydrogen-bonded chain structure.

Crystal data

C15H11ClN2O2F(000) = 592
Mr = 286.71Dx = 1.420 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4883 reflections
a = 10.7755 (3) Åθ = 2.5–28.0°
b = 7.6580 (2) ŵ = 0.29 mm1
c = 16.7221 (5) ÅT = 293 K
β = 103.621 (1)°Prism, yellow
V = 1341.08 (7) Å30.42 × 0.10 × 0.08 mm
Z = 4

Data collection

Bruker X8 APEXII diffractometer3359 independent reflections
Radiation source: fine-focus sealed tube2679 reflections with I > 2σ(I)
graphiteRint = 0.036
[var phi] and ω scansθmax = 28.6°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −14→14
Tmin = 0.889, Tmax = 0.977k = −10→10
17112 measured reflectionsl = −22→22

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)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.172H atoms treated by a mixture of independent and constrained refinement
S = 1.07w = 1/[σ2(Fo2) + (0.0732P)2 + 1.9878P] where P = (Fo2 + 2Fc2)/3
3359 reflections(Δ/σ)max = 0.001
189 parametersΔρmax = 1.36 e Å3
2 restraintsΔρmin = −0.55 e Å3

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

xyzUiso*/Ueq
Cl10.57023 (7)0.66801 (10)0.13231 (5)0.0407 (2)
O10.6840 (2)0.0626 (3)0.47422 (12)0.0409 (5)
O20.44544 (18)−0.2487 (2)0.33490 (13)0.0369 (5)
N10.59018 (19)0.2396 (3)0.36901 (12)0.0224 (4)
N20.41244 (18)0.0024 (3)0.26154 (12)0.0222 (4)
C10.5433 (2)0.2716 (3)0.28363 (14)0.0206 (5)
C20.5776 (2)0.4280 (3)0.25108 (15)0.0245 (5)
H20.63470.50380.28450.029*
C30.5270 (2)0.4702 (3)0.16968 (16)0.0275 (5)
C40.4440 (3)0.3598 (4)0.11757 (16)0.0309 (6)
H40.41070.38950.06280.037*
C50.4119 (2)0.2030 (3)0.14941 (16)0.0270 (5)
H50.35750.12620.11480.032*
C60.4589 (2)0.1576 (3)0.23202 (14)0.0210 (5)
C70.2750 (2)−0.0392 (3)0.23355 (15)0.0232 (5)
H7A0.2456−0.08940.27900.028*
H7B0.22790.06820.21760.028*
C80.2469 (2)−0.1612 (3)0.16395 (16)0.0252 (5)
C90.2219 (3)−0.2596 (4)0.10749 (17)0.0323 (6)
C100.4874 (2)−0.1152 (3)0.31164 (16)0.0263 (5)
C110.6273 (2)−0.0655 (3)0.33946 (18)0.0304 (6)
H11A0.6770−0.16510.36480.037*
H11B0.6595−0.02880.29260.037*
C120.6388 (2)0.0817 (3)0.40064 (16)0.0273 (5)
C130.6048 (2)0.3883 (3)0.42683 (16)0.0272 (5)
H13A0.53870.47370.40570.033*
H13B0.59280.34710.47930.033*
C140.7301 (3)0.4731 (3)0.43968 (16)0.0298 (5)
C150.8290 (3)0.5466 (4)0.4487 (2)0.0416 (7)
H90.204 (3)−0.342 (4)0.0641 (16)0.050 (10)*
H150.906 (2)0.611 (4)0.457 (2)0.057 (11)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0390 (4)0.0351 (4)0.0491 (4)−0.0006 (3)0.0124 (3)0.0178 (3)
O10.0477 (12)0.0307 (10)0.0343 (10)−0.0038 (9)−0.0102 (9)0.0106 (8)
O20.0341 (10)0.0184 (9)0.0518 (12)−0.0044 (7)−0.0027 (9)0.0070 (8)
N10.0227 (9)0.0176 (9)0.0237 (10)−0.0010 (7)−0.0011 (7)0.0009 (7)
N20.0183 (9)0.0161 (9)0.0303 (10)−0.0016 (7)0.0017 (8)−0.0010 (8)
C10.0173 (10)0.0184 (10)0.0255 (11)0.0020 (8)0.0041 (8)0.0019 (8)
C20.0220 (11)0.0196 (11)0.0312 (12)−0.0015 (9)0.0051 (9)0.0020 (9)
C30.0253 (12)0.0252 (12)0.0346 (13)0.0026 (9)0.0121 (10)0.0092 (10)
C40.0299 (13)0.0353 (14)0.0276 (12)0.0053 (11)0.0070 (10)0.0063 (10)
C50.0267 (12)0.0269 (12)0.0269 (12)0.0007 (10)0.0054 (10)−0.0025 (9)
C60.0197 (10)0.0173 (10)0.0267 (11)0.0008 (8)0.0068 (9)−0.0005 (9)
C70.0183 (11)0.0194 (11)0.0310 (12)0.0003 (8)0.0039 (9)−0.0027 (9)
C80.0212 (11)0.0212 (11)0.0321 (12)−0.0026 (9)0.0040 (9)0.0006 (9)
C90.0345 (14)0.0296 (14)0.0319 (14)−0.0037 (11)0.0062 (11)−0.0052 (11)
C100.0245 (11)0.0154 (11)0.0352 (13)0.0015 (9)−0.0007 (10)−0.0015 (9)
C110.0223 (12)0.0169 (11)0.0466 (15)0.0027 (9)−0.0029 (10)0.0005 (10)
C120.0225 (11)0.0211 (12)0.0337 (13)−0.0020 (9)−0.0025 (10)0.0049 (10)
C130.0272 (12)0.0247 (12)0.0276 (12)−0.0006 (10)0.0022 (10)−0.0039 (10)
C140.0353 (14)0.0217 (12)0.0287 (12)0.0010 (10)0.0001 (10)−0.0026 (10)
C150.0342 (15)0.0341 (15)0.0510 (18)−0.0059 (12)−0.0007 (13)−0.0018 (13)

Geometric parameters (Å, °)

Cl1—C31.743 (3)C5—C61.399 (3)
O1—C121.221 (3)C5—H50.9300
O2—C101.219 (3)C7—C81.467 (3)
N1—C121.373 (3)C7—H7A0.9700
N1—C11.419 (3)C7—H7B0.9700
N1—C131.478 (3)C8—C91.188 (4)
N2—C101.359 (3)C9—H90.95 (3)
N2—C61.422 (3)C10—C111.517 (3)
N2—C71.479 (3)C11—C121.508 (4)
C1—C21.401 (3)C11—H11A0.9700
C1—C61.402 (3)C11—H11B0.9700
C2—C31.380 (3)C13—C141.468 (4)
C2—H20.9300C13—H13A0.9700
C3—C41.381 (4)C13—H13B0.9700
C4—C51.390 (4)C14—C151.183 (4)
C4—H40.9300C15—H150.95 (3)
C12—N1—C1123.5 (2)N2—C7—H7A109.0
C12—N1—C13117.0 (2)C8—C7—H7B109.0
C1—N1—C13118.91 (19)N2—C7—H7B109.0
C10—N2—C6124.11 (19)H7A—C7—H7B107.8
C10—N2—C7117.3 (2)C9—C8—C7178.9 (3)
C6—N2—C7118.57 (19)C8—C9—H9177 (2)
C2—C1—C6119.1 (2)O2—C10—N2122.8 (2)
C2—C1—N1118.3 (2)O2—C10—C11121.9 (2)
C6—C1—N1122.5 (2)N2—C10—C11115.2 (2)
C3—C2—C1120.3 (2)C12—C11—C10108.2 (2)
C3—C2—H2119.9C12—C11—H11A110.1
C1—C2—H2119.9C10—C11—H11A110.1
C2—C3—C4121.7 (2)C12—C11—H11B110.1
C2—C3—Cl1118.7 (2)C10—C11—H11B110.1
C4—C3—Cl1119.6 (2)H11A—C11—H11B108.4
C3—C4—C5118.0 (2)O1—C12—N1121.3 (2)
C3—C4—H4121.0O1—C12—C11122.9 (2)
C5—C4—H4121.0N1—C12—C11115.7 (2)
C4—C5—C6121.9 (2)C14—C13—N1112.9 (2)
C4—C5—H5119.1C14—C13—H13A109.0
C6—C5—H5119.1N1—C13—H13A109.0
C5—C6—C1119.0 (2)C14—C13—H13B109.0
C5—C6—N2118.4 (2)N1—C13—H13B109.0
C1—C6—N2122.5 (2)H13A—C13—H13B107.8
C8—C7—N2113.11 (19)C15—C14—C13177.7 (3)
C8—C7—H7A109.0C14—C15—H15177 (2)
C12—N1—C1—C2−136.1 (2)C10—N2—C6—C1−47.3 (3)
C13—N1—C1—C235.0 (3)C7—N2—C6—C1135.5 (2)
C12—N1—C1—C647.5 (3)C10—N2—C7—C8−80.8 (3)
C13—N1—C1—C6−141.4 (2)C6—N2—C7—C896.6 (2)
C6—C1—C2—C31.1 (3)C6—N2—C10—O2−178.7 (2)
N1—C1—C2—C3−175.4 (2)C7—N2—C10—O2−1.5 (4)
C1—C2—C3—C4−1.4 (4)C6—N2—C10—C113.5 (3)
C1—C2—C3—Cl1178.89 (18)C7—N2—C10—C11−179.3 (2)
C2—C3—C4—C50.1 (4)O2—C10—C11—C12−106.1 (3)
Cl1—C3—C4—C5179.86 (19)N2—C10—C11—C1271.8 (3)
C3—C4—C5—C61.4 (4)C1—N1—C12—O1176.3 (2)
C4—C5—C6—C1−1.6 (4)C13—N1—C12—O14.9 (4)
C4—C5—C6—N2174.4 (2)C1—N1—C12—C11−6.2 (3)
C2—C1—C6—C50.3 (3)C13—N1—C12—C11−177.5 (2)
N1—C1—C6—C5176.7 (2)C10—C11—C12—O1107.6 (3)
C2—C1—C6—N2−175.5 (2)C10—C11—C12—N1−69.9 (3)
N1—C1—C6—N20.9 (3)C12—N1—C13—C1483.2 (3)
C10—N2—C6—C5136.9 (2)C1—N1—C13—C14−88.6 (3)
C7—N2—C6—C5−40.3 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C9—H9···O1i0.95 (3)2.24 (3)3.176 (3)171 (3)

Symmetry codes: (i) 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: NK2074).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • 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.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). J. Appl. Cryst.43, 920–925.

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