15a,15b-Dihydro-5H,7H,9H,14H,17H-15,16-methano­dibenzo[e]diazepino[2,3-c;3′,2′-e]imidazole-7,18-dione

The title compound, C₂₀H₁₈N₄O₂, is a mol­ecular clip based on the glycoluril framework. The two benzene rings are each fused to a seven-membered ring; these rings bind four of the N atoms from separate rings of the glycoluril system to form the sidewalls of the mol­ecular clip. The crystal packing is stabilized by non-classical C—H...O hydrogen bonds. There are no π–π stacking inter­actions in the crystal structure. The mol­ecule provides a model with approximate non-crystallographic C_2v symmetry.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C)= 0.003 Å
• R factor = 0.053
• wR factor = 0.127
• Data-to-parameter ratio = 15.5

checkCIF/PLATON results

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No errors found in this datablock

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S1. Comment

The glycoluril skeleton has served as an important building block for the preparation of a wide variety of supramolecular systems, including molecular clips (Rowan et al., 1999; Yin et al., 2006; Li et al., 2006), the cucurbit[n]uril family (Freeman et al., 1981), and molecular capsules (Rebek,2005). In addition, Isaacs and co-workers have synthesized many methlene-bridged glycouril dimers from the title compound (Wu et al., 2002).

The molecular structure of the title compound is shown in Fig. 1. The crystal packing is stabilized by inversion-related intermolecular C19—H19···O1 hydrogen bonds, forming dimers. These dimers are linked by additional C7—H7A···O2 hydrogen bonds (Table 1). Many examples of π···π interactions between the molecular clips are observed in the crystal structures presented by Wang et al. (2006), however, there are no such interactions observed in our example structure.

Related literature

For the preparation of the title compound, see: Wang et al. (2006). For historical background of the title compound, see: Rowan et al. (1999); Yin et al. (2006); Li et al. (2006); Freeman et al. (1981); Rebek (2005); Wu et al. (2002).

S2. Experimental

The title compound was synthesized according to the procedure of Wang et al. (2006) in 42% isolated yield. Crystals of the title compound suitable for X-ray data collection were obtained by slow evaporation of a chloroform and methaol solution in ratio of 100:1 at 293 K.

S3. Refinement

All H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined using a riding model, with U_iso(H) = 1.2 U_eq(C) (1.5U_eq(C) for methly) of the parent atoms.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

Fig. 1. View of the title molecule showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 10% probability level. H atoms are represented by spheres of arbitrary radius.

15a,15b-Dihydro-5H,7H,9H,14H,17H-15,16-methanodibenzo[e]diazepino[2,3 - c;3',2'-e]imidazole-7,18-dione

Crystal data

C20H18N4O2	F(000) = 728
Mr = 346.38	Dx = 1.379 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1842 reflections
a = 10.2660 (16) Å	θ = 2.3–20.2°
b = 11.2985 (18) Å	µ = 0.09 mm^−1
c = 14.522 (2) Å	T = 292 K
β = 97.923 (3)°	Plate, colorless
V = 1668.3 (4) Å^3	0.20 × 0.10 × 0.04 mm
Z = 4

Data collection

Bruker SMART 4K CCD area-detector diffractometer	2139 reflections with I > 2σ(I)'
Radiation source: fine-focus sealed tube	Rint = 0.056
Graphite monochromator	θmax = 27.0°, θmin = 2.3°
φ and ω scans	h = −12→13
13800 measured reflections	k = −14→14
3632 independent reflections	l = −18→18

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.054P)^2] where P = (Fo^2 + 2Fc^2)/3
3632 reflections	(Δ/σ)max = 0.001
235 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.16 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.09320 (19)	0.78732 (18)	0.33914 (14)	0.0469 (5)
C2	0.0178 (2)	0.6858 (2)	0.32550 (18)	0.0608 (6)
H2	0.0016	0.6526	0.2664	0.073*
C3	−0.0341 (2)	0.6327 (2)	0.3985 (2)	0.0768 (8)
H3	−0.0834	0.5636	0.3887	0.092*
C4	−0.0123 (2)	0.6827 (3)	0.4847 (2)	0.0790 (8)
H4	−0.0470	0.6479	0.5340	0.095*
C5	0.0606 (2)	0.7841 (2)	0.49881 (16)	0.0645 (7)
H5	0.0733	0.8181	0.5577	0.077*
C6	0.11589 (19)	0.83734 (18)	0.42791 (14)	0.0464 (5)
C7	0.1984 (2)	0.94700 (19)	0.44777 (15)	0.0559 (6)
H7A	0.1569	1.0117	0.4109	0.067*
H7B	0.2004	0.9678	0.5127	0.067*
C8	0.1512 (2)	0.8415 (2)	0.25890 (14)	0.0574 (6)
H8A	0.1235	0.7954	0.2033	0.069*
H8B	0.1165	0.9209	0.2482	0.069*
C9	0.4266 (2)	0.87315 (16)	0.48619 (14)	0.0470 (5)
C10	0.3746 (2)	0.76527 (19)	0.24463 (13)	0.0471 (5)
C11	0.3627 (2)	0.93601 (17)	0.33387 (13)	0.0468 (5)
H11	0.3530	1.0153	0.3065	0.056*
C12	0.5054 (2)	0.89188 (17)	0.34320 (13)	0.0476 (5)
H12	0.5668	0.9555	0.3330	0.057*
C13	0.6453 (2)	0.78303 (18)	0.47387 (14)	0.0549 (6)
H13A	0.6546	0.7842	0.5412	0.066*
H13B	0.7210	0.8233	0.4553	0.066*
C14	0.6128 (2)	0.7208 (2)	0.27315 (14)	0.0582 (6)
H14A	0.6925	0.7679	0.2787	0.070*
H14B	0.6040	0.6817	0.2131	0.070*
C15	0.62998 (19)	0.62694 (18)	0.34763 (14)	0.0457 (5)
C16	0.64605 (19)	0.65618 (17)	0.44180 (14)	0.0444 (5)
C17	0.6686 (2)	0.5659 (2)	0.50689 (16)	0.0564 (6)
H17	0.6789	0.5845	0.5699	0.068*
C18	0.6759 (2)	0.4489 (2)	0.48021 (19)	0.0656 (7)
H18	0.6920	0.3898	0.5249	0.079*
C19	0.6596 (2)	0.4205 (2)	0.3879 (2)	0.0677 (7)
H19	0.6643	0.3420	0.3694	0.081*
C20	0.6363 (2)	0.5086 (2)	0.32287 (17)	0.0600 (6)
H20	0.6243	0.4885	0.2602	0.072*
N1	0.33311 (17)	0.93432 (14)	0.42804 (11)	0.0477 (4)
N2	0.29307 (17)	0.84723 (15)	0.27388 (11)	0.0487 (4)
N3	0.52758 (17)	0.84800 (14)	0.43754 (11)	0.0489 (5)
N4	0.50216 (17)	0.80036 (15)	0.27382 (11)	0.0493 (4)
O1	0.42173 (16)	0.84965 (13)	0.56762 (10)	0.0608 (4)
O2	0.34199 (15)	0.67820 (14)	0.19698 (10)	0.0660 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0418 (12)	0.0504 (13)	0.0468 (12)	0.0045 (10)	−0.0002 (9)	−0.0011 (10)
C2	0.0425 (13)	0.0628 (15)	0.0758 (17)	−0.0016 (11)	0.0035 (12)	−0.0180 (13)
C3	0.0443 (15)	0.0651 (17)	0.120 (2)	−0.0110 (13)	0.0065 (15)	0.0016 (17)
C4	0.0596 (17)	0.093 (2)	0.084 (2)	−0.0135 (15)	0.0100 (14)	0.0250 (16)
C5	0.0598 (16)	0.0816 (19)	0.0520 (14)	−0.0043 (14)	0.0078 (12)	0.0053 (12)
C6	0.0488 (13)	0.0438 (12)	0.0464 (12)	0.0040 (10)	0.0055 (10)	0.0007 (10)
C7	0.0733 (17)	0.0474 (13)	0.0477 (13)	0.0014 (11)	0.0107 (11)	−0.0061 (10)
C8	0.0573 (15)	0.0741 (16)	0.0379 (12)	0.0006 (12)	−0.0040 (10)	−0.0028 (11)
C9	0.0732 (15)	0.0272 (10)	0.0391 (12)	−0.0098 (10)	0.0025 (11)	−0.0047 (9)
C10	0.0588 (15)	0.0515 (13)	0.0296 (10)	−0.0040 (11)	0.0006 (10)	0.0026 (10)
C11	0.0641 (15)	0.0334 (11)	0.0424 (12)	−0.0049 (10)	0.0062 (10)	0.0054 (9)
C12	0.0599 (14)	0.0391 (11)	0.0425 (12)	−0.0105 (10)	0.0030 (10)	0.0020 (9)
C13	0.0672 (15)	0.0483 (13)	0.0447 (12)	−0.0040 (11)	−0.0082 (11)	−0.0066 (10)
C14	0.0581 (15)	0.0751 (16)	0.0413 (12)	0.0033 (13)	0.0067 (10)	−0.0051 (11)
C15	0.0386 (12)	0.0485 (13)	0.0493 (13)	−0.0022 (10)	0.0037 (9)	−0.0076 (10)
C16	0.0412 (12)	0.0414 (12)	0.0499 (12)	−0.0027 (9)	0.0039 (9)	−0.0027 (10)
C17	0.0536 (14)	0.0557 (14)	0.0611 (15)	0.0025 (11)	0.0125 (11)	0.0040 (12)
C18	0.0592 (16)	0.0475 (14)	0.092 (2)	0.0033 (12)	0.0186 (14)	0.0134 (13)
C19	0.0563 (16)	0.0437 (14)	0.103 (2)	−0.0019 (12)	0.0104 (14)	−0.0104 (15)
C20	0.0451 (14)	0.0637 (16)	0.0699 (16)	−0.0027 (12)	0.0037 (11)	−0.0220 (13)
N1	0.0604 (12)	0.0393 (10)	0.0429 (10)	−0.0058 (8)	0.0053 (9)	−0.0045 (8)
N2	0.0516 (11)	0.0542 (11)	0.0386 (9)	−0.0002 (9)	0.0004 (8)	−0.0049 (8)
N3	0.0657 (12)	0.0402 (10)	0.0382 (10)	0.0041 (9)	−0.0019 (9)	−0.0024 (8)
N4	0.0541 (11)	0.0527 (11)	0.0409 (10)	−0.0018 (9)	0.0054 (8)	−0.0043 (8)
O1	0.0920 (12)	0.0513 (9)	0.0380 (8)	−0.0111 (8)	0.0048 (7)	−0.0027 (7)
O2	0.0781 (11)	0.0682 (11)	0.0487 (9)	−0.0066 (9)	−0.0016 (8)	−0.0227 (8)

Geometric parameters (Å, º)

C1—C2	1.383 (3)	C11—N2	1.451 (2)
C1—C6	1.397 (3)	C11—C12	1.536 (3)
C1—C8	1.509 (3)	C11—H11	0.9800
C2—C3	1.387 (3)	C12—N4	1.441 (2)
C2—H2	0.9300	C12—N3	1.445 (2)
C3—C4	1.365 (4)	C12—H12	0.9800
C3—H3	0.9300	C13—N3	1.450 (3)
C4—C5	1.369 (4)	C13—C16	1.507 (3)
C4—H4	0.9300	C13—H13A	0.9700
C5—C6	1.380 (3)	C13—H13B	0.9700
C5—H5	0.9300	C14—N4	1.450 (3)
C6—C7	1.506 (3)	C14—C15	1.508 (3)
C7—N1	1.457 (3)	C14—H14A	0.9700
C7—H7A	0.9700	C14—H14B	0.9700
C7—H7B	0.9700	C15—C20	1.388 (3)
C8—N2	1.444 (3)	C15—C16	1.394 (3)
C8—H8A	0.9700	C16—C17	1.388 (3)
C8—H8B	0.9700	C17—C18	1.382 (3)
C9—O1	1.220 (2)	C17—H17	0.9300
C9—N3	1.362 (3)	C18—C19	1.366 (3)
C9—N1	1.374 (3)	C18—H18	0.9300
C10—O2	1.223 (2)	C19—C20	1.371 (3)
C10—N2	1.355 (3)	C19—H19	0.9300
C10—N4	1.378 (3)	C20—H20	0.9300
C11—N1	1.441 (2)
C2—C1—C6	119.1 (2)	N4—C12—H12	112.0
C2—C1—C8	119.9 (2)	N3—C12—H12	112.0
C6—C1—C8	120.99 (19)	C11—C12—H12	112.0
C1—C2—C3	121.1 (2)	N3—C13—C16	114.12 (16)
C1—C2—H2	119.5	N3—C13—H13A	108.7
C3—C2—H2	119.5	C16—C13—H13A	108.7
C4—C3—C2	119.4 (2)	N3—C13—H13B	108.7
C4—C3—H3	120.3	C16—C13—H13B	108.7
C2—C3—H3	120.3	H13A—C13—H13B	107.6
C3—C4—C5	120.1 (3)	N4—C14—C15	116.47 (17)
C3—C4—H4	120.0	N4—C14—H14A	108.2
C5—C4—H4	120.0	C15—C14—H14A	108.2
C4—C5—C6	121.7 (2)	N4—C14—H14B	108.2
C4—C5—H5	119.1	C15—C14—H14B	108.2
C6—C5—H5	119.1	H14A—C14—H14B	107.3
C5—C6—C1	118.6 (2)	C20—C15—C16	118.60 (19)
C5—C6—C7	119.6 (2)	C20—C15—C14	119.77 (19)
C1—C6—C7	121.82 (19)	C16—C15—C14	121.56 (18)
N1—C7—C6	113.92 (17)	C17—C16—C15	118.66 (19)
N1—C7—H7A	108.8	C17—C16—C13	119.73 (19)
C6—C7—H7A	108.8	C15—C16—C13	121.55 (18)
N1—C7—H7B	108.8	C18—C17—C16	121.5 (2)
C6—C7—H7B	108.8	C18—C17—H17	119.3
H7A—C7—H7B	107.7	C16—C17—H17	119.3
N2—C8—C1	113.52 (16)	C19—C18—C17	119.7 (2)
N2—C8—H8A	108.9	C19—C18—H18	120.1
C1—C8—H8A	108.9	C17—C18—H18	120.1
N2—C8—H8B	108.9	C18—C19—C20	119.4 (2)
C1—C8—H8B	108.9	C18—C19—H19	120.3
H8A—C8—H8B	107.7	C20—C19—H19	120.3
O1—C9—N3	126.4 (2)	C19—C20—C15	122.1 (2)
O1—C9—N1	125.9 (2)	C19—C20—H20	119.0
N3—C9—N1	107.65 (17)	C15—C20—H20	119.0
O2—C10—N2	126.4 (2)	C9—N1—C11	111.65 (17)
O2—C10—N4	125.5 (2)	C9—N1—C7	122.01 (18)
N2—C10—N4	107.99 (18)	C11—N1—C7	121.00 (17)
N1—C11—N2	114.20 (16)	C10—N2—C8	125.16 (18)
N1—C11—C12	103.60 (16)	C10—N2—C11	112.71 (17)
N2—C11—C12	102.33 (16)	C8—N2—C11	121.65 (17)
N1—C11—H11	112.0	C9—N3—C12	112.86 (17)
N2—C11—H11	112.0	C9—N3—C13	124.92 (17)
C12—C11—H11	112.0	C12—N3—C13	122.21 (17)
N4—C12—N3	113.71 (16)	C10—N4—C12	110.57 (17)
N4—C12—C11	103.96 (16)	C10—N4—C14	122.12 (18)
N3—C12—C11	102.62 (16)	C12—N4—C14	120.47 (16)
C6—C1—C2—C3	−0.7 (3)	N3—C9—N1—C7	162.83 (16)
C8—C1—C2—C3	178.5 (2)	N2—C11—N1—C9	97.8 (2)
C1—C2—C3—C4	1.2 (4)	C12—C11—N1—C9	−12.7 (2)
C2—C3—C4—C5	−0.3 (4)	N2—C11—N1—C7	−56.9 (2)
C3—C4—C5—C6	−1.2 (4)	C12—C11—N1—C7	−167.34 (16)
C4—C5—C6—C1	1.7 (3)	C6—C7—N1—C9	−76.3 (2)
C4—C5—C6—C7	−178.3 (2)	C6—C7—N1—C11	75.7 (2)
C2—C1—C6—C5	−0.8 (3)	O2—C10—N2—C8	4.5 (3)
C8—C1—C6—C5	−179.91 (19)	N4—C10—N2—C8	−178.65 (17)
C2—C1—C6—C7	179.28 (19)	O2—C10—N2—C11	176.66 (19)
C8—C1—C6—C7	0.1 (3)	N4—C10—N2—C11	−6.5 (2)
C5—C6—C7—N1	120.4 (2)	C1—C8—N2—C10	94.7 (2)
C1—C6—C7—N1	−59.6 (3)	C1—C8—N2—C11	−76.8 (2)
C2—C1—C8—N2	−119.7 (2)	N1—C11—N2—C10	−114.59 (19)
C6—C1—C8—N2	59.5 (3)	C12—C11—N2—C10	−3.4 (2)
N1—C11—C12—N4	130.26 (15)	N1—C11—N2—C8	57.9 (2)
N2—C11—C12—N4	11.27 (19)	C12—C11—N2—C8	169.12 (17)
N1—C11—C12—N3	11.55 (18)	O1—C9—N3—C12	−177.63 (18)
N2—C11—C12—N3	−107.43 (16)	N1—C9—N3—C12	−0.1 (2)
N4—C14—C15—C20	124.7 (2)	O1—C9—N3—C13	3.2 (3)
N4—C14—C15—C16	−58.4 (3)	N1—C9—N3—C13	−179.29 (16)
C20—C15—C16—C17	0.4 (3)	N4—C12—N3—C9	−119.08 (19)
C14—C15—C16—C17	−176.54 (19)	C11—C12—N3—C9	−7.5 (2)
C20—C15—C16—C13	177.8 (2)	N4—C12—N3—C13	60.2 (2)
C14—C15—C16—C13	0.8 (3)	C11—C12—N3—C13	171.78 (16)
N3—C13—C16—C17	−126.3 (2)	C16—C13—N3—C9	102.5 (2)
N3—C13—C16—C15	56.4 (3)	C16—C13—N3—C12	−76.7 (2)
C15—C16—C17—C18	0.4 (3)	O2—C10—N4—C12	−168.60 (19)
C13—C16—C17—C18	−177.0 (2)	N2—C10—N4—C12	14.5 (2)
C16—C17—C18—C19	−0.6 (3)	O2—C10—N4—C14	−17.6 (3)
C17—C18—C19—C20	0.1 (3)	N2—C10—N4—C14	165.55 (17)
C18—C19—C20—C15	0.7 (3)	N3—C12—N4—C10	94.7 (2)
C16—C15—C20—C19	−1.0 (3)	C11—C12—N4—C10	−16.1 (2)
C14—C15—C20—C19	176.1 (2)	N3—C12—N4—C14	−56.9 (2)
O1—C9—N1—C11	−173.95 (18)	C11—C12—N4—C14	−167.67 (17)
N3—C9—N1—C11	8.5 (2)	C15—C14—N4—C10	−74.2 (2)
O1—C9—N1—C7	−19.6 (3)	C15—C14—N4—C12	74.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···O1^i	0.93	2.55	3.252 (3)	132
C13—H13A···O1	0.97	2.58	2.924 (3)	101
C7—H7A···O2^ii	0.97	2.45	3.343 (3)	153

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y+1/2, −z+1/2.