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

Dardouri, R.; Kandri Rodi, Y.; Saffon, N.; Essassi, E.M.; Ng, S.W.

doi:10.1107/S1600536810047008

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3228

https://doi.org/10.1107/S1600536810047008

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

Rachid Dardouri,^a Youssef Kandri Rodi,^a Natalie Saffon,^b El Mokhtar Essassi ^a and Seik Weng Ng ^c ^*

^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 ).

Experimental

Crystal data

C₁₅H₁₁ClN₂O₂
M_r = 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 ) 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[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
Δρ_max = 1.36 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810047008/nk2074sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810047008/nk2074Isup2.hkl

checkCIF report

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.

Structure description top

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

	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.

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

Crystal data top

C₁₅H₁₁ClN₂O₂	F(000) = 592
M_r = 286.71	D_x = 1.420 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4883 reflections
a = 10.7755 (3) Å	θ = 2.5–28.0°
b = 7.6580 (2) Å	µ = 0.29 mm⁻¹
c = 16.7221 (5) Å	T = 293 K
β = 103.621 (1)°	Prism, yellow
V = 1341.08 (7) Å³	0.42 × 0.10 × 0.08 mm
Z = 4

Data collection top

Bruker X8 APEXII diffractometer	3359 independent reflections
Radiation source: fine-focus sealed tube	2679 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
φ and ω scans	θ_max = 28.6°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.889, T_max = 0.977	k = −10→10
17112 measured reflections	l = −22→22

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0732P)² + 1.9878P] where P = (F_o² + 2F_c²)/3
3359 reflections	(Δ/σ)_max = 0.001
189 parameters	Δρ_max = 1.36 e Å⁻³
2 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

C₁₅H₁₁ClN₂O₂	V = 1341.08 (7) Å³
M_r = 286.71	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.7755 (3) Å	µ = 0.29 mm⁻¹
b = 7.6580 (2) Å	T = 293 K
c = 16.7221 (5) Å	0.42 × 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)
T_min = 0.889, T_max = 0.977	R_int = 0.036
17112 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	2 restraints
wR(F²) = 0.172	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 1.36 e Å⁻³
3359 reflections	Δρ_min = −0.55 e Å⁻³
189 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.57023 (7)	0.66801 (10)	0.13231 (5)	0.0407 (2)
O1	0.6840 (2)	0.0626 (3)	0.47422 (12)	0.0409 (5)
O2	0.44544 (18)	−0.2487 (2)	0.33490 (13)	0.0369 (5)
N1	0.59018 (19)	0.2396 (3)	0.36901 (12)	0.0224 (4)
N2	0.41244 (18)	0.0024 (3)	0.26154 (12)	0.0222 (4)
C1	0.5433 (2)	0.2716 (3)	0.28363 (14)	0.0206 (5)
C2	0.5776 (2)	0.4280 (3)	0.25108 (15)	0.0245 (5)
H2	0.6347	0.5038	0.2845	0.029*
C3	0.5270 (2)	0.4702 (3)	0.16968 (16)	0.0275 (5)
C4	0.4440 (3)	0.3598 (4)	0.11757 (16)	0.0309 (6)
H4	0.4107	0.3895	0.0628	0.037*
C5	0.4119 (2)	0.2030 (3)	0.14941 (16)	0.0270 (5)
H5	0.3575	0.1262	0.1148	0.032*
C6	0.4589 (2)	0.1576 (3)	0.23202 (14)	0.0210 (5)
C7	0.2750 (2)	−0.0392 (3)	0.23355 (15)	0.0232 (5)
H7A	0.2456	−0.0894	0.2790	0.028*
H7B	0.2279	0.0682	0.2176	0.028*
C8	0.2469 (2)	−0.1612 (3)	0.16395 (16)	0.0252 (5)
C9	0.2219 (3)	−0.2596 (4)	0.10749 (17)	0.0323 (6)
C10	0.4874 (2)	−0.1152 (3)	0.31164 (16)	0.0263 (5)
C11	0.6273 (2)	−0.0655 (3)	0.33946 (18)	0.0304 (6)
H11A	0.6770	−0.1651	0.3648	0.037*
H11B	0.6595	−0.0288	0.2926	0.037*
C12	0.6388 (2)	0.0817 (3)	0.40064 (16)	0.0273 (5)
C13	0.6048 (2)	0.3883 (3)	0.42683 (16)	0.0272 (5)
H13A	0.5387	0.4737	0.4057	0.033*
H13B	0.5928	0.3471	0.4793	0.033*
C14	0.7301 (3)	0.4731 (3)	0.43968 (16)	0.0298 (5)
C15	0.8290 (3)	0.5466 (4)	0.4487 (2)	0.0416 (7)
H9	0.204 (3)	−0.342 (4)	0.0641 (16)	0.050 (10)*
H15	0.906 (2)	0.611 (4)	0.457 (2)	0.057 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0390 (4)	0.0351 (4)	0.0491 (4)	−0.0006 (3)	0.0124 (3)	0.0178 (3)
O1	0.0477 (12)	0.0307 (10)	0.0343 (10)	−0.0038 (9)	−0.0102 (9)	0.0106 (8)
O2	0.0341 (10)	0.0184 (9)	0.0518 (12)	−0.0044 (7)	−0.0027 (9)	0.0070 (8)
N1	0.0227 (9)	0.0176 (9)	0.0237 (10)	−0.0010 (7)	−0.0011 (7)	0.0009 (7)
N2	0.0183 (9)	0.0161 (9)	0.0303 (10)	−0.0016 (7)	0.0017 (8)	−0.0010 (8)
C1	0.0173 (10)	0.0184 (10)	0.0255 (11)	0.0020 (8)	0.0041 (8)	0.0019 (8)
C2	0.0220 (11)	0.0196 (11)	0.0312 (12)	−0.0015 (9)	0.0051 (9)	0.0020 (9)
C3	0.0253 (12)	0.0252 (12)	0.0346 (13)	0.0026 (9)	0.0121 (10)	0.0092 (10)
C4	0.0299 (13)	0.0353 (14)	0.0276 (12)	0.0053 (11)	0.0070 (10)	0.0063 (10)
C5	0.0267 (12)	0.0269 (12)	0.0269 (12)	0.0007 (10)	0.0054 (10)	−0.0025 (9)
C6	0.0197 (10)	0.0173 (10)	0.0267 (11)	0.0008 (8)	0.0068 (9)	−0.0005 (9)
C7	0.0183 (11)	0.0194 (11)	0.0310 (12)	0.0003 (8)	0.0039 (9)	−0.0027 (9)
C8	0.0212 (11)	0.0212 (11)	0.0321 (12)	−0.0026 (9)	0.0040 (9)	0.0006 (9)
C9	0.0345 (14)	0.0296 (14)	0.0319 (14)	−0.0037 (11)	0.0062 (11)	−0.0052 (11)
C10	0.0245 (11)	0.0154 (11)	0.0352 (13)	0.0015 (9)	−0.0007 (10)	−0.0015 (9)
C11	0.0223 (12)	0.0169 (11)	0.0466 (15)	0.0027 (9)	−0.0029 (10)	0.0005 (10)
C12	0.0225 (11)	0.0211 (12)	0.0337 (13)	−0.0020 (9)	−0.0025 (10)	0.0049 (10)
C13	0.0272 (12)	0.0247 (12)	0.0276 (12)	−0.0006 (10)	0.0022 (10)	−0.0039 (10)
C14	0.0353 (14)	0.0217 (12)	0.0287 (12)	0.0010 (10)	0.0001 (10)	−0.0026 (10)
C15	0.0342 (15)	0.0341 (15)	0.0510 (18)	−0.0059 (12)	−0.0007 (13)	−0.0018 (13)

Geometric parameters (Å, º) top

Cl1—C3	1.743 (3)	C5—C6	1.399 (3)
O1—C12	1.221 (3)	C5—H5	0.9300
O2—C10	1.219 (3)	C7—C8	1.467 (3)
N1—C12	1.373 (3)	C7—H7A	0.9700
N1—C1	1.419 (3)	C7—H7B	0.9700
N1—C13	1.478 (3)	C8—C9	1.188 (4)
N2—C10	1.359 (3)	C9—H9	0.95 (3)
N2—C6	1.422 (3)	C10—C11	1.517 (3)
N2—C7	1.479 (3)	C11—C12	1.508 (4)
C1—C2	1.401 (3)	C11—H11A	0.9700
C1—C6	1.402 (3)	C11—H11B	0.9700
C2—C3	1.380 (3)	C13—C14	1.468 (4)
C2—H2	0.9300	C13—H13A	0.9700
C3—C4	1.381 (4)	C13—H13B	0.9700
C4—C5	1.390 (4)	C14—C15	1.183 (4)
C4—H4	0.9300	C15—H15	0.95 (3)

C12—N1—C1	123.5 (2)	N2—C7—H7A	109.0
C12—N1—C13	117.0 (2)	C8—C7—H7B	109.0
C1—N1—C13	118.91 (19)	N2—C7—H7B	109.0
C10—N2—C6	124.11 (19)	H7A—C7—H7B	107.8
C10—N2—C7	117.3 (2)	C9—C8—C7	178.9 (3)
C6—N2—C7	118.57 (19)	C8—C9—H9	177 (2)
C2—C1—C6	119.1 (2)	O2—C10—N2	122.8 (2)
C2—C1—N1	118.3 (2)	O2—C10—C11	121.9 (2)
C6—C1—N1	122.5 (2)	N2—C10—C11	115.2 (2)
C3—C2—C1	120.3 (2)	C12—C11—C10	108.2 (2)
C3—C2—H2	119.9	C12—C11—H11A	110.1
C1—C2—H2	119.9	C10—C11—H11A	110.1
C2—C3—C4	121.7 (2)	C12—C11—H11B	110.1
C2—C3—Cl1	118.7 (2)	C10—C11—H11B	110.1
C4—C3—Cl1	119.6 (2)	H11A—C11—H11B	108.4
C3—C4—C5	118.0 (2)	O1—C12—N1	121.3 (2)
C3—C4—H4	121.0	O1—C12—C11	122.9 (2)
C5—C4—H4	121.0	N1—C12—C11	115.7 (2)
C4—C5—C6	121.9 (2)	C14—C13—N1	112.9 (2)
C4—C5—H5	119.1	C14—C13—H13A	109.0
C6—C5—H5	119.1	N1—C13—H13A	109.0
C5—C6—C1	119.0 (2)	C14—C13—H13B	109.0
C5—C6—N2	118.4 (2)	N1—C13—H13B	109.0
C1—C6—N2	122.5 (2)	H13A—C13—H13B	107.8
C8—C7—N2	113.11 (19)	C15—C14—C13	177.7 (3)
C8—C7—H7A	109.0	C14—C15—H15	177 (2)

C12—N1—C1—C2	−136.1 (2)	C10—N2—C6—C1	−47.3 (3)
C13—N1—C1—C2	35.0 (3)	C7—N2—C6—C1	135.5 (2)
C12—N1—C1—C6	47.5 (3)	C10—N2—C7—C8	−80.8 (3)
C13—N1—C1—C6	−141.4 (2)	C6—N2—C7—C8	96.6 (2)
C6—C1—C2—C3	1.1 (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—C11	3.5 (3)
C1—C2—C3—Cl1	178.89 (18)	C7—N2—C10—C11	−179.3 (2)
C2—C3—C4—C5	0.1 (4)	O2—C10—C11—C12	−106.1 (3)
Cl1—C3—C4—C5	179.86 (19)	N2—C10—C11—C12	71.8 (3)
C3—C4—C5—C6	1.4 (4)	C1—N1—C12—O1	176.3 (2)
C4—C5—C6—C1	−1.6 (4)	C13—N1—C12—O1	4.9 (4)
C4—C5—C6—N2	174.4 (2)	C1—N1—C12—C11	−6.2 (3)
C2—C1—C6—C5	0.3 (3)	C13—N1—C12—C11	−177.5 (2)
N1—C1—C6—C5	176.7 (2)	C10—C11—C12—O1	107.6 (3)
C2—C1—C6—N2	−175.5 (2)	C10—C11—C12—N1	−69.9 (3)
N1—C1—C6—N2	0.9 (3)	C12—N1—C13—C14	83.2 (3)
C10—N2—C6—C5	136.9 (2)	C1—N1—C13—C14	−88.6 (3)
C7—N2—C6—C5	−40.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1ⁱ	0.95 (3)	2.24 (3)	3.176 (3)	171 (3)

Symmetry code: (i) x−1/2, −y−1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₁ClN₂O₂
M_r	286.71
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	10.7755 (3), 7.6580 (2), 16.7221 (5)
β (°)	103.621 (1)
V (Å³)	1341.08 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.42 × 0.10 × 0.08

Data collection
Diffractometer	Bruker X8 APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.889, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	17112, 3359, 2679
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.673

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.172, 1.07
No. of reflections	3359
No. of parameters	189
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
C9—H9···O1ⁱ	0.95 (3)	2.24 (3)	3.176 (3)	171 (3)

Symmetry code: (i) 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

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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. CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar