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Acta Cryst. (2010). E66, o3039    [ doi:10.1107/S1600536810044120 ]

Ethyl {4-[(1,5-dimethyl-2,4-dioxo-2,3,4,5-tetrahydro-1H-1,5-benzodiazepin-3-yl)methyl]-1,2,3-triazol-1-yl}acetate

R. Dardouri, Y. Kandri Rodi, S. Ladeira, E. M. Essassi and S. W. Ng

Abstract top

In the title compound, C18H21N5O4, the diazepine ring adopts a boat conformation with the triazolylmethyl-bearing C atom as the prow and the C atoms at the ring junction as the stern.

Comment top

1,5-Dimethyl-3-propargyl-1,5-benzodiazepine-2,4-dione, whose synthesis was reported recently (Dardouri et al., 2010), possess an acetylenic linkage that can be exploited for the synthesis of other 1,5-benzodiazepine-2,4-dione derivatives. In this study, the compound is reacted with ethyl 2-azidoacetate to yield the title compound (Scheme I, Fig. 1). The ester provides three nitrogen atoms necessary for the formation of the triazolyl ring.

Related literature top

For the structure of 1,5-dimethyl-3-propargyl-1,5-benzodiazepine-2,4-dione, see: Dardouri et al. (2010).

Experimental top

To a solution of 3-propargyl-1,5-dimethyl-1,5-benzodiazepine-2,4-dione (0.23 g,1 mmol) in a t-butyl alcohol/water mixture (1:2, 8 ml) was added copper sulfate pentahydrate (0.25 g,1 mmol), sodium ascorbate (0.29 g, 2 mmol) and ethyl 2-azidoacetate (0.64 g, 5 mmol). The mixture was stirred for two hours. Water (20 ml) was added and the organic compound was extracted with ethyl acetate (2 x 20 ml). The extracts were washed with brine and then dried over sodium sulfate. The compound was recrystallized from an n-hexane/ethyl acetate mixture to give colorless crystals.

Refinement top

H-atoms were placed in calculated positions (C—H 0.93–0.98 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2–1.5Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C18H21N5O4 at the 50% probability level; hydrogen atoms are drawn as arbitrary radius.
Ethyl {4-[(1,5-dimethyl-2,4-dioxo-2,3,4,5-tetrahydro-1H-1,5- benzodiazepin-3-yl)methyl]-1,2,3-triazol-1-yl}acetate top
Crystal data top
C18H21N5O4F(000) = 784
Mr = 371.40Dx = 1.354 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3798 reflections
a = 8.5452 (2) Åθ = 2.5–26.4°
b = 15.9993 (5) ŵ = 0.10 mm−1
c = 13.9215 (4) ÅT = 293 K
β = 106.853 (1)°Prism, colorless
V = 1821.56 (9) Å30.40 × 0.10 × 0.05 mm
Z = 4
Data collection top
Bruker X8 APEXII
diffractometer		2909 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.037
graphiteθmax = 27.5°, θmin = 2.8°
φ and ω scansh = −10→10
15511 measured reflectionsk = −20→20
4129 independent reflectionsl = −18→18
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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.052P)2 + 0.6008P]
where P = (Fo2 + 2Fc2)/3
4129 reflections(Δ/σ)max = 0.001
247 parametersΔρmax = 0.30 e Å−3
0 restraintsΔρmin = −0.31 e Å−3
Crystal data top
C18H21N5O4V = 1821.56 (9) Å3
Mr = 371.40Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.5452 (2) ŵ = 0.10 mm−1
b = 15.9993 (5) ÅT = 293 K
c = 13.9215 (4) Å0.40 × 0.10 × 0.05 mm
β = 106.853 (1)°
Data collection top
Bruker X8 APEXII
diffractometer		Rint = 0.037
15511 measured reflectionsθmax = 27.5°
4129 independent reflectionsStandard reflections: 0
2909 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.124Δρmax = 0.30 e Å−3
S = 1.03Δρmin = −0.31 e Å−3
4129 reflectionsAbsolute structure: ?
247 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.56199 (17)0.18555 (8)0.67466 (9)0.0438 (3)
O20.81954 (18)0.21921 (9)0.49678 (10)0.0505 (4)
O30.41269 (16)0.12018 (9)−0.04809 (9)0.0440 (3)
O40.25337 (19)0.10260 (14)0.05096 (12)0.0829 (7)
N10.78013 (17)0.10102 (8)0.73772 (10)0.0285 (3)
N20.96549 (17)0.11692 (10)0.59493 (10)0.0344 (4)
N30.52214 (17)0.02996 (9)0.35097 (10)0.0314 (3)
N40.52862 (17)0.02234 (9)0.25819 (10)0.0328 (3)
N50.52498 (17)0.10028 (9)0.22117 (10)0.0291 (3)
C10.88147 (19)0.03536 (10)0.72159 (12)0.0271 (4)
C20.8961 (2)−0.03761 (11)0.77820 (13)0.0347 (4)
H20.8390−0.04260.82550.042*
C30.9939 (2)−0.10250 (12)0.76516 (15)0.0421 (5)
H31.0037−0.15050.80420.050*
C41.0772 (2)−0.09629 (13)0.69423 (15)0.0449 (5)
H41.1407−0.14070.68400.054*
C51.0662 (2)−0.02442 (13)0.63862 (13)0.0395 (5)
H51.1237−0.02050.59140.047*
C60.97042 (19)0.04275 (11)0.65161 (12)0.0300 (4)
C70.7764 (2)0.11896 (12)0.84068 (13)0.0385 (4)
H7A0.76590.17810.84860.058*
H7B0.87580.09960.88750.058*
H7C0.68490.09090.85310.058*
C80.6620 (2)0.13566 (10)0.66069 (12)0.0301 (4)
C90.6685 (2)0.11352 (10)0.55590 (11)0.0263 (3)
H90.67980.05280.55140.032*
C100.8228 (2)0.15520 (11)0.54480 (12)0.0332 (4)
C111.1183 (2)0.15061 (15)0.58176 (15)0.0499 (5)
H11A1.12090.21010.59090.075*
H11B1.12370.13780.51540.075*
H11C1.21000.12580.63040.075*
C120.5152 (2)0.14153 (11)0.47517 (12)0.0314 (4)
H12A0.41950.11940.49040.038*
H12B0.50830.20200.47550.038*
C130.51605 (19)0.11257 (10)0.37318 (12)0.0274 (3)
C140.5173 (2)0.15758 (11)0.29023 (12)0.0295 (4)
H140.51360.21540.28300.035*
C150.5444 (2)0.11311 (12)0.12218 (12)0.0339 (4)
H15A0.61630.07030.10960.041*
H15B0.59630.16680.12070.041*
C160.3849 (2)0.11069 (11)0.03967 (13)0.0366 (4)
C170.2699 (3)0.11868 (14)−0.13697 (14)0.0487 (5)
H17A0.19600.0748−0.12940.058*
H17B0.30510.1058−0.19560.058*
C180.1815 (2)0.19999 (12)−0.15270 (14)0.0435 (5)
H18A0.09000.1969−0.21210.065*
H18B0.25420.2436−0.16030.065*
H18C0.14310.2120−0.09580.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0564 (9)0.0414 (7)0.0342 (7)0.0164 (6)0.0141 (6)−0.0056 (6)
O20.0584 (9)0.0477 (8)0.0410 (8)−0.0153 (7)0.0074 (7)0.0153 (6)
O30.0389 (7)0.0690 (9)0.0205 (6)0.0060 (6)0.0030 (5)−0.0024 (6)
O40.0371 (9)0.1597 (19)0.0459 (10)−0.0232 (10)0.0022 (7)0.0413 (11)
N10.0337 (8)0.0327 (7)0.0201 (7)−0.0024 (6)0.0091 (6)−0.0031 (5)
N20.0301 (8)0.0491 (9)0.0242 (7)−0.0106 (7)0.0080 (6)0.0014 (6)
N30.0320 (8)0.0344 (8)0.0264 (7)−0.0013 (6)0.0063 (6)0.0015 (6)
N40.0352 (8)0.0332 (8)0.0274 (7)−0.0031 (6)0.0050 (6)0.0005 (6)
N50.0287 (7)0.0341 (8)0.0223 (7)−0.0019 (6)0.0040 (5)0.0016 (6)
C10.0246 (8)0.0334 (8)0.0217 (8)−0.0037 (7)0.0043 (6)−0.0038 (6)
C20.0307 (9)0.0398 (10)0.0312 (9)−0.0051 (7)0.0053 (7)0.0024 (7)
C30.0365 (10)0.0369 (10)0.0446 (11)0.0011 (8)−0.0013 (8)0.0032 (8)
C40.0312 (10)0.0519 (12)0.0437 (11)0.0111 (8)−0.0017 (8)−0.0094 (9)
C50.0256 (9)0.0631 (13)0.0273 (9)0.0038 (8)0.0035 (7)−0.0092 (9)
C60.0239 (8)0.0429 (10)0.0203 (8)−0.0053 (7)0.0018 (6)−0.0034 (7)
C70.0472 (11)0.0469 (11)0.0227 (9)−0.0019 (9)0.0119 (8)−0.0072 (8)
C80.0376 (10)0.0269 (8)0.0262 (8)−0.0007 (7)0.0098 (7)−0.0017 (6)
C90.0310 (9)0.0263 (8)0.0214 (8)0.0005 (7)0.0069 (6)−0.0008 (6)
C100.0395 (10)0.0387 (9)0.0204 (8)−0.0080 (8)0.0069 (7)−0.0015 (7)
C110.0375 (11)0.0799 (15)0.0324 (10)−0.0239 (10)0.0104 (8)0.0009 (10)
C120.0314 (9)0.0361 (9)0.0259 (8)0.0072 (7)0.0072 (7)0.0018 (7)
C130.0229 (8)0.0319 (8)0.0255 (8)0.0013 (6)0.0042 (6)0.0024 (7)
C140.0299 (9)0.0296 (8)0.0272 (8)0.0010 (7)0.0051 (7)0.0016 (7)
C150.0329 (9)0.0448 (10)0.0225 (8)−0.0031 (8)0.0055 (7)0.0001 (7)
C160.0348 (10)0.0418 (10)0.0293 (9)−0.0072 (8)0.0033 (7)0.0055 (7)
C170.0509 (12)0.0617 (13)0.0231 (9)0.0071 (10)−0.0056 (8)−0.0067 (9)
C180.0438 (11)0.0441 (11)0.0352 (10)−0.0068 (9)−0.0002 (8)0.0007 (8)
Geometric parameters (Å, °) top
O1—C81.225 (2)C5—H50.9300
O2—C101.219 (2)C7—H7A0.9600
O3—C161.319 (2)C7—H7B0.9600
O3—C171.464 (2)C7—H7C0.9600
O4—C161.186 (2)C8—C91.518 (2)
N1—C81.360 (2)C9—C121.525 (2)
N1—C11.420 (2)C9—C101.524 (2)
N1—C71.471 (2)C9—H90.9800
N2—C101.362 (2)C11—H11A0.9600
N2—C61.419 (2)C11—H11B0.9600
N2—C111.473 (2)C11—H11C0.9600
N3—N41.3145 (19)C12—C131.495 (2)
N3—C131.362 (2)C12—H12A0.9700
N4—N51.3462 (19)C12—H12B0.9700
N5—C141.344 (2)C13—C141.364 (2)
N5—C151.450 (2)C14—H140.9300
C1—C21.394 (2)C15—C161.507 (2)
C1—C61.404 (2)C15—H15A0.9700
C2—C31.377 (3)C15—H15B0.9700
C2—H20.9300C17—C181.489 (3)
C3—C41.378 (3)C17—H17A0.9700
C3—H30.9300C17—H17B0.9700
C4—C51.374 (3)C18—H18A0.9600
C4—H40.9300C18—H18B0.9600
C5—C61.394 (3)C18—H18C0.9600
C16—O3—C17116.81 (15)C10—C9—H9108.9
C8—N1—C1121.62 (13)O2—C10—N2122.21 (16)
C8—N1—C7117.89 (14)O2—C10—C9122.71 (16)
C1—N1—C7119.01 (14)N2—C10—C9115.05 (15)
C10—N2—C6122.59 (14)N2—C11—H11A109.5
C10—N2—C11117.80 (16)N2—C11—H11B109.5
C6—N2—C11119.40 (15)H11A—C11—H11B109.5
N4—N3—C13109.17 (13)N2—C11—H11C109.5
N3—N4—N5106.71 (13)H11A—C11—H11C109.5
C14—N5—N4111.01 (13)H11B—C11—H11C109.5
C14—N5—C15128.78 (14)C13—C12—C9111.66 (13)
N4—N5—C15119.93 (14)C13—C12—H12A109.3
C2—C1—C6119.01 (15)C9—C12—H12A109.3
C2—C1—N1119.29 (15)C13—C12—H12B109.3
C6—C1—N1121.68 (15)C9—C12—H12B109.3
C3—C2—C1121.03 (17)H12A—C12—H12B107.9
C3—C2—H2119.5C14—C13—N3108.06 (15)
C1—C2—H2119.5C14—C13—C12130.07 (15)
C2—C3—C4119.94 (18)N3—C13—C12121.82 (14)
C2—C3—H3120.0N5—C14—C13105.05 (15)
C4—C3—H3120.0N5—C14—H14127.5
C5—C4—C3119.93 (18)C13—C14—H14127.5
C5—C4—H4120.0N5—C15—C16113.16 (14)
C3—C4—H4120.0N5—C15—H15A108.9
C4—C5—C6121.26 (17)C16—C15—H15A108.9
C4—C5—H5119.4N5—C15—H15B108.9
C6—C5—H5119.4C16—C15—H15B108.9
C5—C6—C1118.78 (16)H15A—C15—H15B107.8
C5—C6—N2119.78 (15)O4—C16—O3124.56 (17)
C1—C6—N2121.44 (15)O4—C16—C15125.75 (17)
N1—C7—H7A109.5O3—C16—C15109.69 (15)
N1—C7—H7B109.5O3—C17—C18111.90 (16)
H7A—C7—H7B109.5O3—C17—H17A109.2
N1—C7—H7C109.5C18—C17—H17A109.2
H7A—C7—H7C109.5O3—C17—H17B109.2
H7B—C7—H7C109.5C18—C17—H17B109.2
O1—C8—N1122.20 (15)H17A—C17—H17B107.9
O1—C8—C9121.75 (15)C17—C18—H18A109.5
N1—C8—C9115.91 (14)C17—C18—H18B109.5
C8—C9—C12112.12 (13)H18A—C18—H18B109.5
C8—C9—C10105.62 (13)C17—C18—H18C109.5
C12—C9—C10112.32 (14)H18A—C18—H18C109.5
C8—C9—H9108.9H18B—C18—H18C109.5
C12—C9—H9108.9
C13—N3—N4—N5−0.60 (17)O1—C8—C9—C10107.96 (18)
N3—N4—N5—C140.41 (17)N1—C8—C9—C10−67.92 (18)
N3—N4—N5—C15174.79 (13)C6—N2—C10—O2179.53 (16)
C8—N1—C1—C2−127.81 (17)C11—N2—C10—O2−5.9 (3)
C7—N1—C1—C238.0 (2)C6—N2—C10—C91.3 (2)
C8—N1—C1—C653.7 (2)C11—N2—C10—C9175.88 (15)
C7—N1—C1—C6−140.50 (16)C8—C9—C10—O2−103.15 (18)
C6—C1—C2—C3−1.1 (2)C12—C9—C10—O219.4 (2)
N1—C1—C2—C3−179.65 (15)C8—C9—C10—N275.09 (17)
C1—C2—C3—C4−0.9 (3)C12—C9—C10—N2−162.40 (14)
C2—C3—C4—C51.8 (3)C8—C9—C12—C13−174.76 (14)
C3—C4—C5—C6−0.7 (3)C10—C9—C12—C1366.48 (18)
C4—C5—C6—C1−1.3 (2)N4—N3—C13—C140.58 (18)
C4—C5—C6—N2178.22 (15)N4—N3—C13—C12−177.28 (14)
C2—C1—C6—C52.2 (2)C9—C12—C13—C14−117.25 (19)
N1—C1—C6—C5−179.29 (15)C9—C12—C13—N360.1 (2)
C2—C1—C6—N2−177.35 (14)N4—N5—C14—C13−0.06 (18)
N1—C1—C6—N21.2 (2)C15—N5—C14—C13−173.80 (15)
C10—N2—C6—C5131.51 (17)N3—C13—C14—N5−0.31 (18)
C11—N2—C6—C5−43.0 (2)C12—C13—C14—N5177.32 (16)
C10—N2—C6—C1−49.0 (2)C14—N5—C15—C16−97.7 (2)
C11—N2—C6—C1136.53 (17)N4—N5—C15—C1689.08 (19)
C1—N1—C8—O1171.63 (16)C17—O3—C16—O4−1.3 (3)
C7—N1—C8—O15.6 (2)C17—O3—C16—C15179.53 (16)
C1—N1—C8—C9−12.5 (2)N5—C15—C16—O42.8 (3)
C7—N1—C8—C9−178.49 (14)N5—C15—C16—O3−178.05 (15)
O1—C8—C9—C12−14.7 (2)C16—O3—C17—C1879.5 (2)
N1—C8—C9—C12169.44 (14)
Acknowledgements top

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

references
References top

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

Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Dardouri, R., Ouazzani Chahdi, F., Saffon, N., Essassi, E. M. & Ng, S. W. (2010). Acta Cryst. E66, o1797.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.