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

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.058
• wR factor = 0.172
• Data-to-parameter ratio = 17.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW .gt. 10 Outliers .          1

Alert level C
DIFMX01_ALERT_2_C  The maximum difference density is > 0.1*ZMAX*0.75
            _refine_diff_density_max given =      1.362
            Test value =      1.275
DIFMX02_ALERT_1_C  The maximum difference density is > 0.1*ZMAX*0.75
            The relevant atom site should be identified.
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.49
PLAT097_ALERT_2_C Large Reported Max.  (Positive) Residual Density       1.36 eA-3
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         27
PLAT918_ALERT_3_C Reflection(s) # with I(obs) much smaller I(calc)          1
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         49

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. 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).

Related literature

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

S2. 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.

S3. 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 1.2–1.5U_eq(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.

Computing details

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

	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

Crystal data

C15H11ClN2O2	F(000) = 592
Mr = 286.71	Dx = 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) Å^3	0.42 × 0.10 × 0.08 mm
Z = 4

Data collection

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

Refinement

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

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

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1^i	0.95 (3)	2.24 (3)	3.176 (3)	171 (3)

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