2,4-Dioxo-1,5-benzodiazepino-15-crown-3

Cherif Alaoui, L.; Kandri Rodi, Y.; Haoudi, A.; Obbade, S.; Essassi, E.M.

doi:10.1107/S1600536807029753

2,4-Dioxo-1,5-benzodiazepino-15-crown-3

L. Cherif Alaoui, Y. Kandri Rodi, A. Haoudi, S. Obbade and E. M. Essassi

The title compound (systematic name: 4,7,10-trioxa-1,13-diazatricyclo[11.6.3.0^14,19]icosa-14,16,18-triene-20,22-dione), C₁₇H₂₂N₂O₅, is a macrocycle containing two roughly perpendicular parts, viz. the benzo-fused macrocycle and the dicarbonyl spacer. The carbonyl groups point out of the cavity, far away from the O atoms of the macrocycle, and so cannot be involved in coordination to a metal ion.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029753/dn2198sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029753/dn2198Isup2.hkl Contains datablock I

CCDC reference: 657762

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.003 Å
R factor = 0.049
wR factor = 0.150
Data-to-parameter ratio = 19.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C12    -   C13     ..       7.43 su

Alert level C
DIFMX01_ALERT_2_C  The maximum difference density is > 0.1*ZMAX*0.75
            _refine_diff_density_max given =      0.634
            Test value =      0.600
DIFMX02_ALERT_1_C  The maximum difference density is > 0.1*ZMAX*0.75
            The relevant atom site should be identified.
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.79
PLAT097_ALERT_2_C Maximum (Positive) Residual Density ............       0.63 e/A   
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.77 Ratio

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

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

Comment top

Since the pioneering work of Pederson (Pedersen, 1967), extensive research has been devoted to the preparation and study of the macrocyclic polyethers properties. Several types of ligands have been synthesized to enhance the stability of the cation-ligand complex and to achieve better selectivity (Izatt et al., 1991; Izatt et al., 1995; Veggel et al., 1991; Rothermel et al. 1992; Basak et al., 1998). These last years, research was focused on the synthesis of macrocycles being able to have potential applications in different fields such as the ionic and molecular recognition (Dietrich et al., 1991), chemical analysis (Cram & Ho, 1986), the extraction and the metal elements transport through pecific membranes (Izatt et al., 1987; Costero & Rodriguez, 1992; Chang et al., 1986, Bürger & Seebach, 1994). In addition, from a reactional point of view, this type of compound is used as well in the supramolecular catalysis (Sam & Simmons, 1972; Liotta & Harris, 1974) or in the separation of the pairs of ions while behaving as base (Takaki et al., 1972; Bourgoin et al., 1975). In this context, we prepared the 2,4-dioxo-1,5 benzodizepino-15-crown-3, obtained by condensation of the dichlorotetraethlene-glycol with the 1,5-benzodiazepine-2,4-dione by phase transfer catalysis conditions (Keïta et al., 2003; Lazrak et al., 2004)using dimethylformamide as solvent. (I).

The molecular structure of (I) is built up from a benzodiazepine fragment and a crown ether as a a spacer (Fig. 1). The bond lengths and angles are within the expected range for similar structures deposited in the Cambridge Structural Database, Version 5.27, 2006(Allen, 2002). The crystal structure is stabilized by Van der Waals forces.

Related literature top

For related literature, see: Allen (2002); Bürger & Seebach (1994); Basak & Shain (1998); Bourgoin et al. (1975); Chang et al. (1986); Costero & Rodriguez (1992); Cram & Ho (1986); Dietrich et al. (1991); Izatt et al. (1987, 1991, 1995); Keïta et al. (2003); Lazrak et al. (2004); Liotta & Harris (1974); Pedersen (1967); Rothermel et al. (1992); Sam & Simmons (1972); Takaki et al. (1972); Veggel et al. (1991).

Experimental top

With a solution of 11.10–3 mole of the 1,5-benzodiazepine-2,4-dione in 60 ml of dimethylformamide, one adds 33. 10–3 mole of potassium carbonate, 11. 10–3 mole of the di-chloro tetraethylene glycol and 6 10–3 mole of tetra-n-butylammonium bromide. Under agitation, the mixture is heated at a temperature between 80 and 90°C during 24 h. After filtration of salts, the filtrate is concentrated under reduced pressure (1.10–2 m mH g). The compound is purified by silica gel column chromatography (eluant/chloroform/methanol: 95/5).

Structure description top

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top

Fig. 1. : Molecular view of the title compound with the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii

4,7,10-Trioxa-1,13-diazatricyclo[11.6.3.0^14,19]icosa-14,16,18-triene- 20,22-dione top

Crystal data top

C₁₇H₂₂N₂O₅	F(000) = 712
M_r = 334.37	D_x = 1.327 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8091 reflections
a = 11.786 (3) Å	θ = 2.3–22.2°
b = 8.092 (2) Å	µ = 0.10 mm⁻¹
c = 18.062 (5) Å	T = 296 K
β = 103.692 (17)°	Block, colourless
V = 1673.8 (8) Å³	0.25 × 0.19 × 0.05 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	4249 independent reflections
Radiation source: fine-focus sealed tube	2847 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
φ and ω scans	θ_max = 28.6°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −15→15
T_min = 0.950, T_max = 0.994	k = −10→10
58268 measured reflections	l = −24→24

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.151	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0687P)² + 0.6508P] where P = (F_o² + 2F_c²)/3
4249 reflections	(Δ/σ)_max < 0.001
217 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₇H₂₂N₂O₅	V = 1673.8 (8) Å³
M_r = 334.37	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.786 (3) Å	µ = 0.10 mm⁻¹
b = 8.092 (2) Å	T = 296 K
c = 18.062 (5) Å	0.25 × 0.19 × 0.05 mm
β = 103.692 (17)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4249 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	2847 reflections with I > 2σ(I)
T_min = 0.950, T_max = 0.994	R_int = 0.056
58268 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.151	H-atom parameters constrained
S = 1.02	Δρ_max = 0.63 e Å⁻³
4249 reflections	Δρ_min = −0.23 e Å⁻³
217 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
N1	0.20967 (11)	0.18321 (16)	0.97933 (8)	0.0311 (3)
N2	0.30717 (12)	0.48339 (16)	0.93351 (8)	0.0346 (3)
O1	0.33317 (11)	−0.01059 (14)	0.95379 (9)	0.0491 (4)
O2	0.46850 (13)	0.39526 (18)	0.89713 (9)	0.0593 (4)
O3	−0.03654 (12)	0.00746 (18)	0.84001 (8)	0.0523 (4)
O4	0.11484 (14)	0.5203 (2)	0.78801 (8)	0.0608 (4)
O5	−0.02232 (14)	0.2477 (2)	0.71616 (9)	0.0708 (5)
C1	0.10071 (17)	0.4975 (3)	1.09477 (11)	0.0501 (5)
H1	0.0511	0.5030	1.1278	0.060*
C2	0.15493 (17)	0.6394 (3)	1.07702 (11)	0.0494 (5)
H2	0.1443	0.7393	1.0999	0.059*
C3	0.12066 (15)	0.3484 (2)	1.06322 (9)	0.0396 (4)
H3	0.0875	0.2525	1.0772	0.047*
C4	0.22434 (16)	0.6323 (2)	1.02571 (10)	0.0420 (4)
H4	0.2614	0.7276	1.0148	0.050*
C5	0.19048 (13)	0.3397 (2)	1.01025 (9)	0.0304 (3)
C6	0.24003 (14)	0.4840 (2)	0.98966 (9)	0.0322 (3)
C7	0.40197 (14)	0.3828 (2)	0.93951 (10)	0.0375 (4)
C8	0.31806 (14)	0.12811 (19)	0.97673 (10)	0.0333 (4)
C9	0.41718 (13)	0.2502 (2)	0.99990 (11)	0.0374 (4)
H9A	0.4161	0.2991	1.0488	0.045*
H9B	0.4914	0.1946	1.0046	0.045*
C10	0.10919 (14)	0.0749 (2)	0.94951 (10)	0.0355 (4)
H10A	0.0443	0.1072	0.9709	0.043*
H10B	0.1296	−0.0384	0.9645	0.043*
C11	0.07348 (16)	0.0865 (3)	0.86399 (11)	0.0474 (5)
H11A	0.0676	0.2013	0.8481	0.057*
H11B	0.1308	0.0324	0.8416	0.057*
C12	0.28953 (19)	0.6158 (2)	0.87579 (11)	0.0466 (5)
H12A	0.3647	0.6648	0.8760	0.056*
H12B	0.2413	0.7012	0.8904	0.056*
C13	0.2335 (2)	0.5609 (3)	0.79602 (13)	0.0600 (6)
H13A	0.2397	0.6486	0.7606	0.072*
H13B	0.2747	0.4652	0.7834	0.072*
C14	−0.0747 (2)	−0.0112 (3)	0.75962 (13)	0.0693 (7)
H14A	−0.1371	−0.0923	0.7487	0.083*
H14B	−0.0105	−0.0540	0.7402	0.083*
C15	−0.1168 (2)	0.1426 (4)	0.71898 (15)	0.0842 (9)
H15A	−0.1599	0.1168	0.6676	0.101*
H15B	−0.1693	0.1986	0.7447	0.101*
C16	0.0551 (3)	0.5107 (3)	0.70931 (13)	0.0714 (7)
H16A	0.1052	0.4583	0.6806	0.086*
H16B	0.0369	0.6211	0.6892	0.086*
C17	−0.0534 (2)	0.4149 (4)	0.70047 (13)	0.0763 (8)
H17A	−0.0980	0.4550	0.7355	0.092*
H17B	−0.1009	0.4260	0.6489	0.092*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0283 (6)	0.0268 (7)	0.0385 (7)	−0.0017 (5)	0.0088 (5)	0.0010 (5)
N2	0.0387 (7)	0.0269 (7)	0.0406 (8)	−0.0030 (6)	0.0144 (6)	0.0008 (6)
O1	0.0446 (7)	0.0277 (6)	0.0760 (10)	0.0037 (5)	0.0165 (7)	−0.0054 (6)
O2	0.0534 (8)	0.0561 (9)	0.0809 (11)	−0.0055 (7)	0.0410 (8)	−0.0002 (8)
O3	0.0448 (7)	0.0668 (9)	0.0454 (7)	−0.0242 (7)	0.0106 (6)	−0.0088 (6)
O4	0.0686 (10)	0.0751 (10)	0.0376 (7)	−0.0089 (8)	0.0106 (7)	0.0001 (7)
O5	0.0629 (10)	0.0820 (12)	0.0626 (10)	−0.0037 (9)	0.0053 (8)	0.0052 (9)
C1	0.0423 (10)	0.0748 (14)	0.0338 (9)	0.0152 (10)	0.0104 (8)	−0.0082 (9)
C2	0.0498 (11)	0.0513 (11)	0.0448 (10)	0.0172 (9)	0.0065 (8)	−0.0129 (9)
C3	0.0343 (8)	0.0531 (11)	0.0317 (8)	0.0013 (8)	0.0086 (7)	0.0026 (7)
C4	0.0429 (9)	0.0334 (9)	0.0470 (10)	0.0066 (7)	0.0050 (8)	−0.0062 (7)
C5	0.0282 (7)	0.0325 (8)	0.0296 (7)	0.0037 (6)	0.0048 (6)	0.0006 (6)
C6	0.0308 (8)	0.0313 (8)	0.0338 (8)	0.0042 (6)	0.0061 (6)	−0.0003 (6)
C7	0.0333 (8)	0.0314 (8)	0.0507 (10)	−0.0078 (7)	0.0161 (7)	−0.0073 (7)
C8	0.0330 (8)	0.0269 (8)	0.0404 (9)	0.0018 (6)	0.0091 (7)	0.0043 (7)
C9	0.0265 (7)	0.0337 (9)	0.0513 (10)	0.0031 (7)	0.0078 (7)	−0.0041 (7)
C10	0.0323 (8)	0.0303 (8)	0.0448 (9)	−0.0066 (7)	0.0112 (7)	0.0036 (7)
C11	0.0379 (9)	0.0599 (12)	0.0456 (10)	−0.0163 (9)	0.0121 (8)	−0.0031 (9)
C12	0.0590 (11)	0.0300 (9)	0.0537 (11)	−0.0079 (8)	0.0187 (9)	0.0070 (8)
C13	0.0777 (15)	0.0543 (12)	0.0555 (12)	0.0009 (11)	0.0306 (11)	0.0118 (10)
C14	0.0695 (15)	0.0887 (18)	0.0486 (12)	−0.0384 (14)	0.0122 (11)	−0.0221 (12)
C15	0.0585 (14)	0.133 (3)	0.0515 (14)	−0.0227 (16)	−0.0061 (11)	0.0033 (15)
C16	0.109 (2)	0.0618 (15)	0.0395 (12)	0.0099 (14)	0.0106 (12)	0.0042 (10)
C17	0.0862 (18)	0.0896 (19)	0.0407 (12)	0.0155 (16)	−0.0099 (11)	−0.0094 (12)

Geometric parameters (Å, º) top

N1—C8	1.364 (2)	C7—C9	1.510 (3)
N1—C5	1.423 (2)	C8—C9	1.511 (2)
N1—C10	1.469 (2)	C9—H9A	0.9700
N2—C7	1.366 (2)	C9—H9B	0.9700
N2—C6	1.426 (2)	C10—C11	1.505 (3)
N2—C12	1.475 (2)	C10—H10A	0.9700
O1—C8	1.2240 (19)	C10—H10B	0.9700
O2—C7	1.223 (2)	C11—H11A	0.9700
O3—C11	1.419 (2)	C11—H11B	0.9700
O3—C14	1.423 (3)	C12—C13	1.503 (3)
O4—C13	1.410 (3)	C12—H12A	0.9700
O4—C16	1.431 (3)	C12—H12B	0.9700
O5—C15	1.411 (3)	C13—H13A	0.9700
O5—C17	1.413 (3)	C13—H13B	0.9700
C1—C3	1.378 (3)	C14—C15	1.470 (4)
C1—C2	1.388 (3)	C14—H14A	0.9700
C1—H1	0.9300	C14—H14B	0.9700
C2—C4	1.375 (3)	C15—H15A	0.9700
C2—H2	0.9300	C15—H15B	0.9700
C3—C5	1.404 (2)	C16—C17	1.471 (4)
C3—H3	0.9300	C16—H16A	0.9700
C4—C6	1.398 (2)	C16—H16B	0.9700
C4—H4	0.9300	C17—H17A	0.9700
C5—C6	1.395 (2)	C17—H17B	0.9700

C8—N1—C5	122.77 (13)	H10A—C10—H10B	108.1
C8—N1—C10	118.20 (13)	O3—C11—C10	107.38 (14)
C5—N1—C10	119.03 (13)	O3—C11—H11A	110.2
C7—N2—C6	121.80 (14)	C10—C11—H11A	110.2
C7—N2—C12	117.70 (15)	O3—C11—H11B	110.2
C6—N2—C12	119.39 (14)	C10—C11—H11B	110.2
C11—O3—C14	113.89 (15)	H11A—C11—H11B	108.5
C13—O4—C16	110.95 (18)	N2—C12—C13	114.77 (16)
C15—O5—C17	114.5 (2)	N2—C12—H12A	108.6
C3—C1—C2	119.72 (17)	C13—C12—H12A	108.6
C3—C1—H1	120.1	N2—C12—H12B	108.6
C2—C1—H1	120.1	C13—C12—H12B	108.6
C4—C2—C1	120.10 (17)	H12A—C12—H12B	107.6
C4—C2—H2	120.0	O4—C13—C12	111.57 (17)
C1—C2—H2	120.0	O4—C13—H13A	109.3
C1—C3—C5	120.71 (17)	C12—C13—H13A	109.3
C1—C3—H3	119.6	O4—C13—H13B	109.3
C5—C3—H3	119.6	C12—C13—H13B	109.3
C2—C4—C6	120.98 (18)	H13A—C13—H13B	108.0
C2—C4—H4	119.5	O3—C14—C15	114.1 (2)
C6—C4—H4	119.5	O3—C14—H14A	108.7
C6—C5—C3	119.31 (15)	C15—C14—H14A	108.7
C6—C5—N1	121.65 (13)	O3—C14—H14B	108.7
C3—C5—N1	119.03 (15)	C15—C14—H14B	108.7
C5—C6—C4	118.99 (15)	H14A—C14—H14B	107.6
C5—C6—N2	121.60 (14)	O5—C15—C14	110.6 (2)
C4—C6—N2	119.41 (15)	O5—C15—H15A	109.5
O2—C7—N2	122.34 (17)	C14—C15—H15A	109.5
O2—C7—C9	121.79 (16)	O5—C15—H15B	109.5
N2—C7—C9	115.83 (14)	C14—C15—H15B	109.5
O1—C8—N1	121.59 (15)	H15A—C15—H15B	108.1
O1—C8—C9	121.89 (15)	O4—C16—C17	110.3 (2)
N1—C8—C9	116.45 (14)	O4—C16—H16A	109.6
C7—C9—C8	108.22 (14)	C17—C16—H16A	109.6
C7—C9—H9A	110.1	O4—C16—H16B	109.6
C8—C9—H9A	110.1	C17—C16—H16B	109.6
C7—C9—H9B	110.1	H16A—C16—H16B	108.1
C8—C9—H9B	110.1	O5—C17—C16	107.8 (2)
H9A—C9—H9B	108.4	O5—C17—H17A	110.2
N1—C10—C11	110.15 (13)	C16—C17—H17A	110.2
N1—C10—H10A	109.6	O5—C17—H17B	110.2
C11—C10—H10A	109.6	C16—C17—H17B	110.2
N1—C10—H10B	109.6	H17A—C17—H17B	108.5
C11—C10—H10B	109.6

Experimental details

Crystal data
Chemical formula	C₁₇H₂₂N₂O₅
M_r	334.37
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	11.786 (3), 8.092 (2), 18.062 (5)
β (°)	103.692 (17)
V (Å³)	1673.8 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.25 × 0.19 × 0.05

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.950, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	58268, 4249, 2847
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.673

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.151, 1.02
No. of reflections	4249
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.23

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.

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