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

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ISSN: 2056-9890

7-Chloro-1,5-dipropargyl-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 9 November 2010; accepted 12 November 2010; online 20 November 2010)

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[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
  • C15H11ClN2O2

  • Mr = 286.71

  • Monoclinic, P 21 /n

  • 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.889, Tmax = 0.977

  • 17112 measured reflections

  • 3359 independent reflections

  • 2679 reflections with I > 2σ(I)

  • Rint = 0.036

Refinement
  • R[F2 > 2σ(F2)] = 0.058

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C9—H9⋯O1i 0.95 (3) 2.24 (3) 3.176 (3) 171 (3)
Symmetry code: (i) [x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z-{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). 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

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).

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 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 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). 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.

Structure description top

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).

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

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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. Displacement ellipsoid plot of C15H11ClN2O2 at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
[Figure 2] Fig. 2. The hydrogen-bonded chain structure.
7-Chloro-1,5-dipropargyl-1H-1,5-benzodiazepine- 2,4(3H,5H)-dione top
Crystal data top
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 top
Bruker X8 APEXII
diffractometer
3359 independent reflections
Radiation source: fine-focus sealed tube2679 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
φ and ω scansθmax = 28.6°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1414
Tmin = 0.889, Tmax = 0.977k = 1010
17112 measured reflectionsl = 2222
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)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.172H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 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
Crystal data top
C15H11ClN2O2V = 1341.08 (7) Å3
Mr = 286.71Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.7755 (3) ŵ = 0.29 mm1
b = 7.6580 (2) ÅT = 293 K
c = 16.7221 (5) Å0.42 × 0.10 × 0.08 mm
β = 103.621 (1)°
Data collection top
Bruker X8 APEXII
diffractometer
3359 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2679 reflections with I > 2σ(I)
Tmin = 0.889, Tmax = 0.977Rint = 0.036
17112 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0582 restraints
wR(F2) = 0.172H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 1.36 e Å3
3359 reflectionsΔρmin = 0.55 e Å3
189 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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)
H7A0.24560.08940.27900.028*
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)
H11A0.67700.16510.36480.037*
H11B0.65950.02880.29260.037*
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) top
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, º) top
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—C2136.1 (2)C10—N2—C6—C147.3 (3)
C13—N1—C1—C235.0 (3)C7—N2—C6—C1135.5 (2)
C12—N1—C1—C647.5 (3)C10—N2—C7—C880.8 (3)
C13—N1—C1—C6141.4 (2)C6—N2—C7—C896.6 (2)
C6—C1—C2—C31.1 (3)C6—N2—C10—O2178.7 (2)
N1—C1—C2—C3175.4 (2)C7—N2—C10—O21.5 (4)
C1—C2—C3—C41.4 (4)C6—N2—C10—C113.5 (3)
C1—C2—C3—Cl1178.89 (18)C7—N2—C10—C11179.3 (2)
C2—C3—C4—C50.1 (4)O2—C10—C11—C12106.1 (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—C11.6 (4)C13—N1—C12—O14.9 (4)
C4—C5—C6—N2174.4 (2)C1—N1—C12—C116.2 (3)
C2—C1—C6—C50.3 (3)C13—N1—C12—C11177.5 (2)
N1—C1—C6—C5176.7 (2)C10—C11—C12—O1107.6 (3)
C2—C1—C6—N2175.5 (2)C10—C11—C12—N169.9 (3)
N1—C1—C6—N20.9 (3)C12—N1—C13—C1483.2 (3)
C10—N2—C6—C5136.9 (2)C1—N1—C13—C1488.6 (3)
C7—N2—C6—C540.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9···O1i0.95 (3)2.24 (3)3.176 (3)171 (3)
Symmetry code: (i) x1/2, y1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC15H11ClN2O2
Mr286.71
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)10.7755 (3), 7.6580 (2), 16.7221 (5)
β (°) 103.621 (1)
V3)1341.08 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.29
Crystal size (mm)0.42 × 0.10 × 0.08
Data collection
DiffractometerBruker X8 APEXII
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.889, 0.977
No. of measured, independent and
observed [I > 2σ(I)] reflections
17112, 3359, 2679
Rint0.036
(sin θ/λ)max1)0.673
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.172, 1.07
No. of reflections3359
No. of parameters189
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)1.36, 0.55

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), 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
C9—H9···O1i0.95 (3)2.24 (3)3.176 (3)171 (3)
Symmetry code: (i) x1/2, y1/2, z1/2.
 

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 Google Scholar
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
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 Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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