Two-dimensional hydrogen-bonded networks in two novel glycoluril derivatives

Two new glycoluril derivatives, namely diethyl 6-ethyl-1,4-dioxo-1,2,2a,3,4,6,7,7b-octa­hydro-5H-2,3,4a,6,7a-penta­aza­cyclo­penta­[cd]indene-2a,7b-dicarboxyl­ate, C₁₄H₂₁N₅O₆, (I), and 6-ethyl-2a,7b-diphenyl-1,2,2a,3,4,6,7,7b-octa­hydro-5H-2,3,4a,6,7a-penta­azacyclo­penta­[cd]indene-1,4-dione, C₂₀H₂₁N₅O₂, (II), both bearing two free syn-urea NH groups and two ureidyl C=O groups, assemble the same one-dimensional chains in the solid state running parallel to the [010] direction via N—H...O hydrogen bonds. Furthermore, the chains of (I) are linked together into two-dimensional networks via C—H...O hydrogen bonds.

S1. Comment

Glycoluril, a biurea compound known for about 130 years, has established an impressive career as a building block for molecular and supramolecular chemistry during the past two decades. For example, glycoluril derivatives have been used in a variety of applications, including polymer cross-linking (Jacobs et al., 1996), explosives (Yinon et al., 1994), the stabilization of organic compounds against photodegradation (Krause et al., 1997), textile waste stream purification (Karcher et al., 1999) and combinatorial chemistry, and furthermore in the fields of cucurbituril chemistry (Freeman et al., 1981; Kim et al., 2000; Pryor & Rebek, 1999; Lee et al., 2003; Burnett et al., 2003) and anion sensors (Kang et al., 2004; Kang & Kim, 2005). The intriguing structural feature in a number of glycoluril derivatives is the twisting observed about the bridgehead dihedral angle, and the rigid and non-planar glycoluril skeleton, with well defined geometry, is more favourable for constructing a three-dimensional structure, which suggests that glycoluril derivatives have significant potential as building blocks in crystal engineering studies. Rebek and co-workers have reported that achiral glycolurils form chiral hydrogen-bonded ribbons in the solid state, and subsequently observed four complementary hydrogen bonds between sulfamides and ureas linking adjacent hydrogen-bonded ribbons (Johnson et al., 2002, 2003). Isaacs and co-workers have reported similar hydrogen-bonded ribbons in a related syn-protected glycoluril derivative (Wu et al., 2002). One of our laboratory interests is to develop a robust supramolecular synthon based on glycoluril for crystal engineering (Wang et al., 2006; Chen et al., 2007). As part of our research programme aimed at the study of hydogen-bonding interactions involving glycoluril, the present work has been undertaken. We report here the two-dimensional hydrogen-bonded networks formed by two novel glycoluril derivatives, (I) and (II), that adopt an unusual twisted conformation in the solid state (Matta et al., 2000; Li et al., 1994; Duspara et al., 2001).

The molecular structures of (I) and (II) (Fig. 1) are built up from three fused rings, namely two nearly planar imidazole five-membered rings that adopt envelope conformations, with the C═O groups at the flap positions, and one six-membered triazacyclohexane ring that adopts a chair conformation. These rings bear two CO₂Et groups in (I) and two Ph groups in (II) on their `convex' faces, respectively. The bond lengths and angles in both compounds are similar to those reported previously (Johnson et al., 2002, 2003; Wu et al., 2002; Wang et al., 2006; Chen et al., 2007). Selected geometric parameters for (I) and (II) are listed in Tables 1 and 3, respectively. The ═O···O═distances are 5.657 (2) Å in (I) and 5.691 (2) Å in (II). All Csp<sup>2</sup>—N and Csp<sup>3</sup>—N distances lie in the ranges 1.349 (4)–1.381 (4) and 1.442 (3)–1.478 (4) Å, respectively. Obviously, the N—C(carbonyl) bond distances are much shorter than the other N—C bond distances in the three fused rings, indicating some electron delocalization within these rings. Again, the cis-fused five-membered rings bearing CO<sub>2</sub>Et or Ph groups enforce their cup-shaped geometry. The angles between the mean planes defined by the five-membered rings are 115.1 (1)° in (I) and 112.9 (1)° in (II). The glycoluril units are both almost coplanar, which is indicated by the key torsion angles [in (I), N1—C3—C7—N3 = 2.9 (3)° and C4—C3—C7—C8 = 9.6 (3)°; in (II), N1—C1—C8—N3 = -4.7 (2)° and C2—C1—C8—C9 = -5.1 (3)°]. These slight differences are thought to be due to the different substitutes on the `convex' faces.

In their supramolecular structures formed via N—H···O and C—H···O hydrogen bonds, the molecules of both (I) and (II) are linked into two-dimensional networks. In (I), the crystal packing can be easily analysed in terms of two simple substructures. In the first substructure, amide atoms N1 and N2 in the molecule at (x, y, z) act as hydrogen-bond donors, via atoms H1 and H2, respectively, to carboxyl atom O2 in the molecule at (-x + 1/2, y + 1/2, -z + 1/2) and atom O1 at (-x + 1/2, y - 1/2, -z + 1/2), both producing one-dimensional chains running parallel to the [010] direction generated by the 2₁ screw axis at (1/4, y, 1/4). These two types of [010] chains are interlinked by the approximately centrosymmetric R₂²(8) (Bernstein et al. 1995) hydrogen-bonding motif centred at (0.257, 0.295, 0.249), forming a one-dimensional chain structure along the [010] direction (Fig. 2, Table 2). Four chains of this type pass through each unit cell; two of these, running along the (1/4, y, 1/4) and (3/4, y, 3/4) directions, respectively, are antiparallel to the other two, which run along the (3/4, y, 1/4) and (1/4, y, 3/4) directions, respectively. As reported by Wu et al. (2002), if all the CO₂Et groups were located on one side of the molecule, this would lead to cyclic structures for these analogues. We do not observe these cyclic structures in the solid state of (I), which may be due to the unfavourable entropy associated with the formation of cyclic structures. In the second substructure, ethyl atom C13 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via atom H13B, to carboxyl atom O3 in the molecule at (x, -y, z + 1/2), forming the other one-dimensional chain along the [001] direction generated by a c-glide plane at y = 0, which suffices to link the [010] chains into a two-dimensional network (Fig. 3) running parallel to the (100) direction. No direction-specific interactions between adjacent two-dimensional networks are observed.

Similar to compound (I), molecules in compound (II) also form one-dimensional hydrogen-bonded tapes in the solid state along the [010] direction (Fig. 4, Table 4). Structure (II) also can be easily analysed in terms of two one-dimensional substructures. In the first substructure, two amide atoms, N1 and N2, in the molecule at (x, y, z) act as hydrogen-bond donors, via atoms H1 and H2, respectively, to carboxyl atom O2 in the molecule at (-x + 3/2, y + 1/2, -z + 1/2) and atom O1 at (-x + 3/2, y - 1/2, -z + 1/2), both producing one-dimensional chains running parallel to the [010] direction generated by the 2₁ screw axis at (3/4, y, 3/4). These two type [010] chains are interlinked by the approximately centrosymmetric R₂²(8) (Bernstein et al. 1995) hydrogen-bonding motif centred at (0.966, 0.400, 0.279), forming a one-dimensional chain structure along the [010] direction. In comparison with the formation of the four chains in each unit cell in compound (I), only two one-dimensional chains pass through each unit cell in (II); these two chains run along the (3/4, y, 1/4) and (1/4, y, 3/4) directions, respectively. The second substructure is constructed by C—H···O hydrogen bonds. Methylene atoms C17 and C18 in the molecule at (x, y, z) act as hydrogen-bond donors, via atoms H17A and H18B, respectively, to carboxyl atom O2 in the molecule at (-x + 1/2, y + 1/2, -z + 1/2) and atom O1 at (-x + 1/2, y - 1/2, -z + 1/2), forming the other one-dimensional tape along the [100] direction, which suffices to link the [010] tapes into a two-dimensional network running parallel to the (001) direction (Fig. 5). There are no direction-specific interactions between adjacent two-dimensional frameworks in (II) either.

As noted above, the same one-dimensional hydrogen-bonded chains along the [010] direction are found here for (I) and (II). This may be ascribed to the same motifs of these two novel glycoluril derivatives, which both bear two free syn-urea N—H groups and two ureidyl C═O. The C—H···O hydrogen bonds {along the [001] direction in (I) and along the [100] direction in (II)} link these one-dimensional helical chains into two-dimensional networks.

Related literature

For related literature, see: Bernstein et al. (1995); Burnett et al. (2003); Chen et al. (2007); Duspara et al. (2001); Freeman et al. (1981); Jacobs et al. (1996); Johnson et al. (2002, 2003); Kang & Kim (2005); Kang et al. (2004); Karcher et al. (1999); Kim et al. (2000); Krause et al. (1997); Lee et al. (2003); Li et al. (1994, 2006); Matta et al. (2000); Pryor & Rebek (1999); Wang et al. (2006); Wu et al. (2002); Yin et al. (2006); Yinon et al. (1994).

S2. Experimental

The preparation of the glycoluril monomers (I) and (II) followed a well established methodology (Yin et al., 2006; Li et al., 2006), but ethanol was used as a solvent. When diethoxycarbonyl- or diphenylglycoluril are combined with equivalent ethyl amines in the presence of anhydrous formaldehyde in ethanol at reflux, the expected compounds, the new glycolurils, were obtained in good yields. EtOH and the ethyl amines were freshly distilled. A suspension of diethoxycarbonylglycoluril (1.43 g, 5 mmol) or diphenylglycoluril (1.47 g, 5 mmol) in anhydrous formaldehyde (0.3 g, 10 mmol) and EtOH (50 ml) was brought to reflux under magnetic stirring. A solution of ethylamine (5 mmol) in EtOH (10 ml) was added dropwise (over 1 h) to the mixture. Refluxing was continued for 10–12 h, monitored by thin-layer chromatography. The solvent was removed under reduced pressure and the products were separated by column chromatography (silica gel) in 80% and 50% isolated yields, respectively. Crystals of (I) and (II) suitable for X-ray data collection were obtained by slow evaporation of dichloroethane–methanol solutions (4:1 v/v) at 293 K.

S3. Refinement

For both (I) and (II), all H atoms bonded to C atoms were initially located in difference Fourier maps and then constrained to their ideal geometry positions, with C—H = 0.96 (methyl) or 0.97 Å (methylene), and with U_iso(H) = 1.5U_eq(methyl C) or 1.2U_eq(methylene C). H atoms bonded to amine N atoms were found in difference maps; the N—H distances were refined freely [Please give range of refined distances] and U_iso(H) = 1.2U_eq(N).

Computing details

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

Figures

	Fig. 1. The molecular structures of compounds (I) and (II), showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The packing of (I), showing the formation of a one-dimensional hydrogen-bonded R2^2(8) chain along the b axis involving syn-NH atoms and C═O. Hydrogen bonds are drawn as dashed lines. [Symmetry codes: (i) -x + 1/2, y - 1/2, -z + 1/2; (ii) -x + 1/2, y + 1/2, -z + 1/2.]
	Fig. 3. Part of the crystal structure of (I), showing the formation of the two-dimensional network linked by C—H···O hydrogen bonds along the [100] direction. Hydrogen bonds are shown as dashed lines. [Symmetry code: (iii) x, -y, z + 1/2.]
	Fig. 4. The packing of (II), showing the formation of a one-dimensional hydrogen-bonded R2^2(8) chain along the b axis involving syn-NH atoms and C═O. Hydrogen bonds are drawn as dashed lines. [Symmetry codes: (i) -x + 3/2, y - 1/2, -z + 1/2; (ii) -x + 3/2, y + 1/2, -z + 1/2.]
	Fig. 5. Part of the crystal structure of (II), showing the formation of the two-dimensional network linked by C—H···O hydrogen bonds along the [001] direction. Hydrogen bonds are shown as dashed lines. [Symmetry codes: (iii) -x + 1/2, y - 1/2, -z + 1/2; (iv) -x + 1/2, y + 1/2, -z + 1/2.]

(I) 6-ethyl-1,4-dioxo-2,2a,3,4,6,7-hexahydro-1H,5H-2,3,4a,6,7a- pentaazacyclopenta[cd]indene-2a,7 b-dicarboxylate

Crystal data

C14H21N5O6	F(000) = 1504
Mr = 355.36	Dx = 1.358 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2051 reflections
a = 23.898 (2) Å	θ = 2.2–22.3°
b = 10.4791 (9) Å	µ = 0.11 mm^−1
c = 15.9302 (13) Å	T = 296 K
β = 119.412 (1)°	Block, colourless
V = 3475.2 (5) Å^3	0.20 × 0.20 × 0.10 mm
Z = 8

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3061 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	2206 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
0.3° wide ω exposures scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→28
Tmin = 0.979, Tmax = 0.989	k = −12→12
10973 measured 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)] = 0.069	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) + (0.0728P)^2 + 4.4873P] where P = (Fo^2 + 2Fc^2)/3
3061 reflections	(Δ/σ)max < 0.001
236 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.41 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	0.17081 (14)	0.3335 (3)	0.2399 (2)	0.0357 (7)
C2	0.16144 (14)	−0.0151 (3)	0.2027 (2)	0.0417 (8)
C3	0.17397 (14)	0.1757 (3)	0.1383 (2)	0.0369 (7)
C4	0.17494 (15)	0.2013 (3)	0.0443 (2)	0.0450 (8)
C5	0.1455 (3)	0.3511 (6)	−0.0811 (4)	0.1038 (18)
H5A	0.1715	0.4275	−0.0673	0.125*
H5B	0.1643	0.2854	−0.1022	0.125*
C6	0.0812 (4)	0.3775 (7)	−0.1567 (5)	0.157 (3)
H6A	0.0558	0.3013	−0.1716	0.235*
H6B	0.0823	0.4061	−0.2131	0.235*
H6C	0.0626	0.4427	−0.1358	0.235*
C7	0.10693 (13)	0.1752 (2)	0.1334 (2)	0.0352 (7)
C8	0.05016 (15)	0.1789 (3)	0.0301 (2)	0.0432 (8)
C9	−0.04711 (19)	0.2766 (4)	−0.0793 (3)	0.0722 (12)
H9A	−0.0754	0.2055	−0.0879	0.087*
H9B	−0.0341	0.2708	−0.1281	0.087*
C10	−0.0806 (3)	0.3966 (5)	−0.0894 (4)	0.1050 (17)
H10A	−0.0877	0.4077	−0.0355	0.158*
H10B	−0.1212	0.3954	−0.1480	0.158*
H10C	−0.0551	0.4660	−0.0915	0.158*
C11	0.07313 (14)	0.2671 (3)	0.2454 (2)	0.0414 (8)
H11A	0.0853	0.3351	0.2925	0.050*
H11B	0.0278	0.2771	0.1994	0.050*
C12	0.06719 (16)	0.0436 (3)	0.2241 (3)	0.0485 (8)
H12A	0.0219	0.0485	0.1766	0.058*
H12B	0.0748	−0.0383	0.2564	0.058*
C13	0.14668 (17)	0.1292 (4)	0.3792 (3)	0.0594 (10)
H13A	0.1791	0.1533	0.3623	0.071*
H13B	0.1531	0.0399	0.3976	0.071*
C14	0.1555 (3)	0.2066 (6)	0.4628 (3)	0.1041 (17)
H14A	0.1538	0.2956	0.4474	0.156*
H14B	0.1964	0.1873	0.5176	0.156*
H14C	0.1219	0.1871	0.4774	0.156*
N1	0.20655 (13)	0.2775 (2)	0.2060 (2)	0.0437 (7)
H1	0.2470 (17)	0.302 (3)	0.222 (2)	0.052*
N2	0.19845 (13)	0.0500 (2)	0.1748 (2)	0.0454 (7)
H2	0.2345 (17)	0.017 (3)	0.175 (2)	0.054*
N3	0.11016 (11)	0.2801 (2)	0.19456 (17)	0.0345 (6)
N4	0.10575 (11)	0.0516 (2)	0.17482 (19)	0.0398 (6)
N5	0.08274 (12)	0.1450 (2)	0.2943 (2)	0.0446 (7)
O1	0.18833 (10)	0.41850 (19)	0.30059 (16)	0.0477 (6)
O2	0.17362 (10)	−0.1192 (2)	0.24359 (18)	0.0548 (6)
O3	0.20115 (14)	0.1339 (3)	0.0142 (2)	0.0730 (8)
O4	0.14544 (13)	0.3091 (2)	0.00594 (18)	0.0666 (7)
O5	0.04553 (12)	0.1026 (2)	−0.02871 (18)	0.0681 (8)
O6	0.00918 (10)	0.2715 (2)	0.01628 (16)	0.0523 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0301 (16)	0.0309 (15)	0.0442 (18)	−0.0038 (13)	0.0168 (15)	−0.0004 (14)
C2	0.0300 (17)	0.0315 (16)	0.064 (2)	0.0012 (13)	0.0234 (16)	−0.0026 (15)
C3	0.0285 (16)	0.0304 (15)	0.0528 (19)	−0.0008 (12)	0.0206 (15)	−0.0027 (13)
C4	0.0365 (18)	0.0437 (18)	0.057 (2)	−0.0048 (15)	0.0242 (17)	−0.0041 (16)
C5	0.104 (4)	0.127 (4)	0.106 (4)	0.029 (3)	0.070 (4)	0.052 (3)
C6	0.160 (7)	0.186 (7)	0.125 (6)	−0.021 (6)	0.070 (6)	0.033 (5)
C7	0.0288 (16)	0.0274 (14)	0.0503 (18)	−0.0020 (12)	0.0203 (15)	−0.0023 (13)
C8	0.0307 (17)	0.0372 (16)	0.059 (2)	−0.0055 (14)	0.0205 (16)	−0.0058 (16)
C9	0.053 (2)	0.081 (3)	0.056 (2)	0.012 (2)	0.007 (2)	0.006 (2)
C10	0.084 (4)	0.086 (3)	0.101 (4)	0.022 (3)	0.012 (3)	0.016 (3)
C11	0.0341 (17)	0.0364 (16)	0.058 (2)	0.0042 (13)	0.0258 (16)	−0.0016 (14)
C12	0.0385 (19)	0.0353 (16)	0.075 (2)	−0.0040 (14)	0.0301 (18)	0.0045 (16)
C13	0.052 (2)	0.066 (2)	0.057 (2)	0.0028 (18)	0.0242 (19)	0.0156 (19)
C14	0.101 (4)	0.135 (5)	0.067 (3)	0.015 (3)	0.033 (3)	0.003 (3)
N1	0.0299 (14)	0.0444 (15)	0.0611 (18)	−0.0109 (12)	0.0257 (14)	−0.0146 (13)
N2	0.0342 (15)	0.0330 (13)	0.077 (2)	0.0057 (12)	0.0337 (15)	0.0059 (13)
N3	0.0300 (13)	0.0263 (11)	0.0485 (14)	−0.0007 (10)	0.0203 (12)	−0.0014 (11)
N4	0.0275 (13)	0.0275 (12)	0.0678 (17)	0.0005 (10)	0.0259 (13)	−0.0003 (12)
N5	0.0358 (15)	0.0433 (15)	0.0600 (18)	0.0016 (12)	0.0276 (14)	0.0059 (13)
O1	0.0444 (13)	0.0397 (12)	0.0600 (14)	−0.0118 (10)	0.0264 (11)	−0.0160 (11)
O2	0.0442 (14)	0.0327 (11)	0.0909 (18)	0.0078 (10)	0.0358 (13)	0.0141 (12)
O3	0.085 (2)	0.0712 (17)	0.086 (2)	0.0085 (15)	0.0604 (18)	−0.0081 (15)
O4	0.0718 (18)	0.0664 (16)	0.0748 (18)	0.0185 (14)	0.0463 (15)	0.0265 (14)
O5	0.0523 (16)	0.0684 (16)	0.0658 (16)	−0.0008 (13)	0.0152 (13)	−0.0293 (14)
O6	0.0377 (13)	0.0538 (13)	0.0491 (14)	0.0078 (11)	0.0088 (11)	0.0011 (11)

Geometric parameters (Å, º)

C1—O1	1.226 (3)	C9—O6	1.456 (4)
C1—N1	1.349 (4)	C9—C10	1.457 (6)
C1—N3	1.381 (4)	C9—H9A	0.9700
C2—O2	1.230 (3)	C9—H9B	0.9700
C2—N2	1.353 (4)	C10—H10A	0.9600
C2—N4	1.370 (4)	C10—H10B	0.9600
C3—N2	1.443 (4)	C10—H10C	0.9600
C3—N1	1.443 (4)	C11—N5	1.456 (4)
C3—C4	1.532 (5)	C11—N3	1.470 (4)
C3—C7	1.565 (4)	C11—H11A	0.9700
C4—O3	1.190 (4)	C11—H11B	0.9700
C4—O4	1.313 (4)	C12—N5	1.452 (4)
C5—C6	1.439 (8)	C12—N4	1.478 (4)
C5—O4	1.455 (5)	C12—H12A	0.9700
C5—H5A	0.9700	C12—H12B	0.9700
C5—H5B	0.9700	C13—N5	1.470 (4)
C6—H6A	0.9600	C13—C14	1.483 (6)
C6—H6B	0.9600	C13—H13A	0.9700
C6—H6C	0.9600	C13—H13B	0.9700
C7—N3	1.446 (3)	C14—H14A	0.9600
C7—N4	1.460 (3)	C14—H14B	0.9600
C7—C8	1.536 (4)	C14—H14C	0.9600
C8—O5	1.194 (4)	N1—H1	0.91 (3)
C8—O6	1.318 (4)	N2—H2	0.93 (3)
O1—C1—N1	126.4 (3)	N5—C11—N3	113.4 (2)
O1—C1—N3	124.8 (3)	N5—C11—H11A	108.9
N1—C1—N3	108.8 (2)	N3—C11—H11A	108.9
O2—C2—N2	126.7 (3)	N5—C11—H11B	108.9
O2—C2—N4	124.3 (3)	N3—C11—H11B	108.9
N2—C2—N4	108.9 (3)	H11A—C11—H11B	107.7
N2—C3—N1	114.2 (3)	N5—C12—N4	112.1 (2)
N2—C3—C4	110.9 (2)	N5—C12—H12A	109.2
N1—C3—C4	109.9 (2)	N4—C12—H12A	109.2
N2—C3—C7	102.7 (2)	N5—C12—H12B	109.2
N1—C3—C7	101.7 (2)	N4—C12—H12B	109.2
C4—C3—C7	117.3 (2)	H12A—C12—H12B	107.9
O3—C4—O4	126.2 (3)	N5—C13—C14	112.9 (3)
O3—C4—C3	123.6 (3)	N5—C13—H13A	109.0
O4—C4—C3	110.1 (3)	C14—C13—H13A	109.0
C6—C5—O4	110.8 (4)	N5—C13—H13B	109.0
C6—C5—H5A	109.5	C14—C13—H13B	109.0
O4—C5—H5A	109.5	H13A—C13—H13B	107.8
C6—C5—H5B	109.5	C13—C14—H14A	109.5
O4—C5—H5B	109.5	C13—C14—H14B	109.5
H5A—C5—H5B	108.1	H14A—C14—H14B	109.5
N3—C7—N4	112.1 (2)	C13—C14—H14C	109.5
N3—C7—C8	115.5 (2)	H14A—C14—H14C	109.5
N4—C7—C8	107.7 (2)	H14B—C14—H14C	109.5
N3—C7—C3	104.5 (2)	C1—N1—C3	114.0 (2)
N4—C7—C3	103.1 (2)	C1—N1—H1	124 (2)
C8—C7—C3	113.4 (2)	C3—N1—H1	122 (2)
O5—C8—O6	125.9 (3)	C2—N2—C3	113.0 (2)
O5—C8—C7	121.1 (3)	C2—N2—H2	125 (2)
O6—C8—C7	113.0 (3)	C3—N2—H2	122 (2)
O6—C9—C10	108.8 (4)	C1—N3—C7	110.8 (2)
O6—C9—H9A	109.9	C1—N3—C11	120.7 (2)
C10—C9—H9A	109.9	C7—N3—C11	117.0 (2)
O6—C9—H9B	109.9	C2—N4—C7	111.6 (2)
C10—C9—H9B	109.9	C2—N4—C12	123.9 (3)
H9A—C9—H9B	108.3	C7—N4—C12	116.5 (2)
C9—C10—H10A	109.5	C12—N5—C11	108.5 (2)
C9—C10—H10B	109.5	C12—N5—C13	112.5 (3)
H10A—C10—H10B	109.5	C11—N5—C13	114.2 (2)
C9—C10—H10C	109.5	C4—O4—C5	116.9 (3)
H10A—C10—H10C	109.5	C8—O6—C9	115.5 (3)
H10B—C10—H10C	109.5
N2—C3—C4—O3	−10.3 (4)	N1—C1—N3—C11	147.5 (3)
N1—C3—C4—O3	116.9 (3)	N4—C7—N3—C1	105.9 (3)
C7—C3—C4—O3	−127.7 (3)	C8—C7—N3—C1	−130.3 (3)
N2—C3—C4—O4	172.3 (3)	C3—C7—N3—C1	−5.0 (3)
N1—C3—C4—O4	−60.5 (3)	N4—C7—N3—C11	−37.8 (3)
C7—C3—C4—O4	54.9 (3)	C8—C7—N3—C11	86.0 (3)
N2—C3—C7—N3	121.3 (2)	C3—C7—N3—C11	−148.8 (2)
N1—C3—C7—N3	2.9 (3)	N5—C11—N3—C1	−91.8 (3)
C4—C3—C7—N3	−116.9 (3)	N5—C11—N3—C7	48.2 (3)
N2—C3—C7—N4	4.0 (3)	O2—C2—N4—C7	176.6 (3)
N1—C3—C7—N4	−114.4 (2)	N2—C2—N4—C7	−5.7 (4)
C4—C3—C7—N4	125.8 (3)	O2—C2—N4—C12	28.9 (5)
N2—C3—C7—C8	−112.2 (3)	N2—C2—N4—C12	−153.3 (3)
N1—C3—C7—C8	129.4 (2)	N3—C7—N4—C2	−111.0 (3)
C4—C3—C7—C8	9.6 (3)	C8—C7—N4—C2	120.9 (3)
N3—C7—C8—O5	174.2 (3)	C3—C7—N4—C2	0.8 (3)
N4—C7—C8—O5	−59.8 (4)	N3—C7—N4—C12	39.2 (3)
C3—C7—C8—O5	53.7 (4)	C8—C7—N4—C12	−88.8 (3)
N3—C7—C8—O6	−6.6 (4)	C3—C7—N4—C12	151.0 (3)
N4—C7—C8—O6	119.5 (3)	N5—C12—N4—C2	95.4 (3)
C3—C7—C8—O6	−127.1 (3)	N5—C12—N4—C7	−50.8 (4)
O1—C1—N1—C3	177.1 (3)	N4—C12—N5—C11	57.0 (3)
N3—C1—N1—C3	−3.3 (3)	N4—C12—N5—C13	−70.4 (3)
N2—C3—N1—C1	−109.7 (3)	N3—C11—N5—C12	−56.0 (3)
C4—C3—N1—C1	125.0 (3)	N3—C11—N5—C13	70.4 (3)
C7—C3—N1—C1	0.1 (3)	C14—C13—N5—C12	−162.6 (3)
O2—C2—N2—C3	−173.6 (3)	C14—C13—N5—C11	73.0 (4)
N4—C2—N2—C3	8.7 (4)	O3—C4—O4—C5	−0.8 (6)
N1—C3—N2—C2	101.4 (3)	C3—C4—O4—C5	176.5 (4)
C4—C3—N2—C2	−133.9 (3)	C6—C5—O4—C4	127.1 (5)
C7—C3—N2—C2	−7.8 (3)	O5—C8—O6—C9	1.6 (5)
O1—C1—N3—C7	−175.1 (3)	C7—C8—O6—C9	−177.6 (3)
N1—C1—N3—C7	5.3 (3)	C10—C9—O6—C8	−168.8 (4)
O1—C1—N3—C11	−32.9 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^i	0.93 (3)	1.98 (4)	2.886 (3)	166 (3)
N1—H1···O2^ii	0.91 (3)	1.89 (4)	2.786 (3)	170 (3)
C13—H13B···O3^iii	0.97	2.45	3.342 (4)	153

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

(II) 6-ethyl-2a,7 b-diphenyl-2,2a,3,4,6,7-hexahydro-1H,5H-2,3,4a,6,7a- pentaazacyclopenta[cd]azulene-1,4-dione

Crystal data

C20H21N5O2	F(000) = 768
Mr = 363.42	Dx = 1.358 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2090 reflections
a = 8.0724 (5) Å	θ = 2.6–21.4°
b = 11.6462 (7) Å	µ = 0.09 mm^−1
c = 19.2338 (12) Å	T = 295 K
β = 100.462 (1)°	Block, colourless
V = 1778.16 (19) Å^3	0.20 × 0.20 × 0.10 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3860 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	2581 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
0.3° wide ω exposures scans	θmax = 27.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→9
Tmin = 0.982, Tmax = 0.991	k = −14→14
16184 measured reflections	l = −24→24

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.159	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0709P)^2 + 0.4735P] where P = (Fo^2 + 2Fc^2)/3
3860 reflections	(Δ/σ)max < 0.001
251 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.21 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	0.6718 (3)	0.68744 (19)	0.17062 (11)	0.0291 (5)
C2	0.7753 (3)	0.7129 (2)	0.11401 (12)	0.0364 (6)
C3	0.8332 (3)	0.8224 (3)	0.10483 (15)	0.0554 (8)
H3	0.8148	0.8808	0.1355	0.066*
C4	0.9187 (4)	0.8459 (4)	0.0501 (2)	0.0841 (12)
H4	0.9598	0.9194	0.0450	0.101*
C5	0.9428 (4)	0.7610 (5)	0.0035 (2)	0.0976 (16)
H5	0.9982	0.7772	−0.0337	0.117*
C6	0.8854 (4)	0.6531 (4)	0.01190 (17)	0.0835 (12)
H6	0.9018	0.5957	−0.0198	0.100*
C7	0.8028 (3)	0.6279 (3)	0.06721 (13)	0.0560 (8)
H7	0.7657	0.5535	0.0729	0.067*
C8	0.4729 (3)	0.69466 (18)	0.14481 (10)	0.0263 (5)
C9	0.4133 (3)	0.73594 (19)	0.06922 (10)	0.0279 (5)
C10	0.3957 (3)	0.8517 (2)	0.05468 (12)	0.0427 (6)
H10	0.4153	0.9046	0.0915	0.051*
C11	0.3490 (3)	0.8901 (3)	−0.01449 (15)	0.0565 (8)
H11	0.3381	0.9684	−0.0237	0.068*
C12	0.3189 (3)	0.8137 (3)	−0.06903 (14)	0.0591 (8)
H12	0.2868	0.8395	−0.1153	0.071*
C13	0.3364 (4)	0.6988 (3)	−0.05513 (13)	0.0594 (8)
H13	0.3166	0.6464	−0.0922	0.071*
C14	0.3832 (3)	0.6596 (2)	0.01343 (11)	0.0425 (6)
H14	0.3945	0.5812	0.0221	0.051*
C15	0.5532 (3)	0.8141 (2)	0.24338 (11)	0.0341 (5)
C16	0.5426 (3)	0.5117 (2)	0.19058 (10)	0.0311 (5)
C17	0.2468 (3)	0.7614 (2)	0.20744 (12)	0.0369 (6)
H17A	0.2318	0.8093	0.2471	0.044*
H17B	0.1707	0.7891	0.1659	0.044*
C18	0.2402 (3)	0.5693 (2)	0.16625 (11)	0.0344 (5)
H18A	0.1651	0.5878	0.1223	0.041*
H18B	0.2186	0.4905	0.1782	0.041*
C19	0.2732 (4)	0.6034 (3)	0.29320 (12)	0.0527 (7)
H19A	0.2798	0.5202	0.2931	0.063*
H19B	0.3865	0.6332	0.3073	0.063*
C20	0.1691 (5)	0.6403 (4)	0.34440 (16)	0.0899 (12)
H20A	0.1698	0.7226	0.3473	0.135*
H20B	0.2140	0.6086	0.3900	0.135*
H20C	0.0557	0.6138	0.3293	0.135*
N1	0.6980 (3)	0.76980 (19)	0.22757 (10)	0.0407 (5)
H1	0.797 (3)	0.809 (2)	0.2453 (13)	0.049*
N2	0.6905 (2)	0.56991 (18)	0.19555 (10)	0.0367 (5)
H2	0.787 (3)	0.531 (2)	0.2024 (12)	0.044*
N3	0.4207 (2)	0.77285 (16)	0.19596 (9)	0.0295 (4)
N4	0.4148 (2)	0.57886 (15)	0.15536 (9)	0.0286 (4)
N5	0.2025 (2)	0.64405 (18)	0.22146 (9)	0.0369 (5)
O1	0.5438 (2)	0.88198 (15)	0.29134 (8)	0.0477 (5)
O2	0.5242 (2)	0.41385 (15)	0.21175 (9)	0.0454 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0238 (12)	0.0291 (12)	0.0338 (10)	0.0020 (9)	0.0034 (9)	0.0014 (9)
C2	0.0196 (11)	0.0481 (16)	0.0409 (12)	0.0031 (11)	0.0035 (9)	0.0087 (11)
C3	0.0370 (15)	0.0591 (19)	0.0693 (17)	−0.0017 (14)	0.0080 (13)	0.0240 (15)
C4	0.0405 (19)	0.113 (3)	0.100 (3)	0.001 (2)	0.0178 (18)	0.063 (3)
C5	0.041 (2)	0.187 (5)	0.071 (2)	0.029 (3)	0.0283 (17)	0.063 (3)
C6	0.061 (2)	0.141 (4)	0.0544 (18)	0.033 (2)	0.0267 (16)	0.008 (2)
C7	0.0442 (17)	0.080 (2)	0.0469 (15)	0.0114 (15)	0.0159 (12)	−0.0048 (14)
C8	0.0246 (11)	0.0240 (12)	0.0300 (10)	0.0004 (9)	0.0041 (8)	−0.0003 (8)
C9	0.0180 (11)	0.0334 (13)	0.0312 (10)	0.0007 (9)	0.0018 (8)	0.0048 (9)
C10	0.0431 (15)	0.0370 (15)	0.0452 (13)	−0.0041 (12)	0.0007 (11)	0.0103 (11)
C11	0.0476 (17)	0.0552 (19)	0.0640 (18)	−0.0046 (14)	0.0029 (14)	0.0333 (15)
C12	0.0452 (17)	0.094 (3)	0.0379 (14)	−0.0017 (17)	0.0060 (12)	0.0263 (16)
C13	0.065 (2)	0.084 (3)	0.0302 (13)	0.0060 (17)	0.0109 (12)	−0.0034 (13)
C14	0.0494 (16)	0.0444 (16)	0.0336 (12)	0.0058 (13)	0.0073 (10)	−0.0028 (11)
C15	0.0343 (13)	0.0328 (13)	0.0342 (11)	−0.0013 (11)	0.0030 (10)	−0.0034 (10)
C16	0.0322 (13)	0.0300 (13)	0.0318 (10)	0.0029 (10)	0.0076 (9)	0.0054 (9)
C17	0.0295 (13)	0.0428 (15)	0.0389 (12)	0.0060 (11)	0.0075 (10)	−0.0016 (10)
C18	0.0269 (12)	0.0353 (14)	0.0402 (12)	−0.0024 (10)	0.0037 (10)	0.0060 (10)
C19	0.0546 (18)	0.064 (2)	0.0408 (13)	0.0025 (15)	0.0123 (12)	0.0127 (12)
C20	0.112 (3)	0.112 (3)	0.0503 (17)	0.010 (3)	0.0277 (18)	0.0061 (19)
N1	0.0271 (11)	0.0489 (14)	0.0448 (11)	−0.0057 (10)	0.0030 (9)	−0.0178 (10)
N2	0.0231 (11)	0.0353 (12)	0.0503 (11)	0.0057 (9)	0.0033 (9)	0.0109 (9)
N3	0.0251 (10)	0.0308 (11)	0.0319 (9)	0.0022 (8)	0.0039 (8)	−0.0056 (8)
N4	0.0239 (10)	0.0271 (11)	0.0338 (9)	0.0007 (8)	0.0026 (7)	0.0051 (8)
N5	0.0296 (11)	0.0445 (13)	0.0376 (10)	0.0007 (9)	0.0092 (8)	0.0058 (9)
O1	0.0473 (11)	0.0506 (12)	0.0442 (9)	−0.0006 (9)	0.0056 (8)	−0.0220 (8)
O2	0.0406 (10)	0.0374 (11)	0.0585 (10)	0.0057 (8)	0.0101 (8)	0.0193 (8)

Geometric parameters (Å, º)

C1—N1	1.442 (3)	C13—C14	1.382 (3)
C1—N2	1.449 (3)	C13—H13	0.9300
C1—C2	1.517 (3)	C14—H14	0.9300
C1—C8	1.594 (3)	C15—O1	1.227 (3)
C2—C3	1.381 (4)	C15—N3	1.361 (3)
C2—C7	1.383 (4)	C15—N1	1.361 (3)
C3—C4	1.386 (4)	C16—O2	1.229 (3)
C3—H3	0.9300	C16—N2	1.361 (3)
C4—C5	1.372 (6)	C16—N4	1.371 (3)
C4—H4	0.9300	C17—N5	1.451 (3)
C5—C6	1.358 (6)	C17—N3	1.467 (3)
C5—H5	0.9300	C17—H17A	0.9700
C6—C7	1.386 (4)	C17—H17B	0.9700
C6—H6	0.9300	C18—N5	1.447 (3)
C7—H7	0.9300	C18—N4	1.466 (3)
C8—N4	1.454 (3)	C18—H18A	0.9700
C8—N3	1.458 (3)	C18—H18B	0.9700
C8—C9	1.524 (3)	C19—C20	1.470 (4)
C9—C10	1.379 (3)	C19—N5	1.472 (3)
C9—C14	1.380 (3)	C19—H19A	0.9700
C10—C11	1.389 (3)	C19—H19B	0.9700
C10—H10	0.9300	C20—H20A	0.9600
C11—C12	1.363 (4)	C20—H20B	0.9600
C11—H11	0.9300	C20—H20C	0.9600
C12—C13	1.367 (4)	N1—H1	0.93 (3)
C12—H12	0.9300	N2—H2	0.89 (3)
N1—C1—N2	112.64 (18)	C13—C14—H14	119.7
N1—C1—C2	113.02 (19)	O1—C15—N3	125.6 (2)
N2—C1—C2	112.63 (18)	O1—C15—N1	125.8 (2)
N1—C1—C8	101.63 (16)	N3—C15—N1	108.55 (19)
N2—C1—C8	101.02 (17)	O2—C16—N2	126.6 (2)
C2—C1—C8	114.87 (16)	O2—C16—N4	124.6 (2)
C3—C2—C7	118.7 (2)	N2—C16—N4	108.81 (19)
C3—C2—C1	121.1 (2)	N5—C17—N3	112.84 (19)
C7—C2—C1	120.1 (2)	N5—C17—H17A	109.0
C2—C3—C4	120.4 (3)	N3—C17—H17A	109.0
C2—C3—H3	119.8	N5—C17—H17B	109.0
C4—C3—H3	119.8	N3—C17—H17B	109.0
C5—C4—C3	120.2 (4)	H17A—C17—H17B	107.8
C5—C4—H4	119.9	N5—C18—N4	113.27 (18)
C3—C4—H4	119.9	N5—C18—H18A	108.9
C6—C5—C4	119.8 (3)	N4—C18—H18A	108.9
C6—C5—H5	120.1	N5—C18—H18B	108.9
C4—C5—H5	120.1	N4—C18—H18B	108.9
C5—C6—C7	120.6 (4)	H18A—C18—H18B	107.7
C5—C6—H6	119.7	C20—C19—N5	111.2 (2)
C7—C6—H6	119.7	C20—C19—H19A	109.4
C2—C7—C6	120.3 (3)	N5—C19—H19A	109.4
C2—C7—H7	119.8	C20—C19—H19B	109.4
C6—C7—H7	119.8	N5—C19—H19B	109.4
N4—C8—N3	110.19 (16)	H19A—C19—H19B	108.0
N4—C8—C9	111.82 (16)	C19—C20—H20A	109.5
N3—C8—C9	111.53 (17)	C19—C20—H20B	109.5
N4—C8—C1	103.87 (16)	H20A—C20—H20B	109.5
N3—C8—C1	102.77 (15)	C19—C20—H20C	109.5
C9—C8—C1	116.06 (16)	H20A—C20—H20C	109.5
C10—C9—C14	118.3 (2)	H20B—C20—H20C	109.5
C10—C9—C8	120.33 (19)	C15—N1—C1	114.12 (19)
C14—C9—C8	121.3 (2)	C15—N1—H1	116.8 (16)
C9—C10—C11	120.6 (2)	C1—N1—H1	126.8 (15)
C9—C10—H10	119.7	C16—N2—C1	114.20 (18)
C11—C10—H10	119.7	C16—N2—H2	119.4 (17)
C12—C11—C10	120.4 (3)	C1—N2—H2	124.4 (16)
C12—C11—H11	119.8	C15—N3—C8	112.62 (18)
C10—C11—H11	119.8	C15—N3—C17	126.04 (18)
C11—C12—C13	119.4 (2)	C8—N3—C17	116.55 (17)
C11—C12—H12	120.3	C16—N4—C8	111.40 (17)
C13—C12—H12	120.3	C16—N4—C18	122.86 (18)
C12—C13—C14	120.7 (3)	C8—N4—C18	115.65 (17)
C12—C13—H13	119.6	C18—N5—C17	109.79 (17)
C14—C13—H13	119.6	C18—N5—C19	113.4 (2)
C9—C14—C13	120.6 (3)	C17—N5—C19	114.3 (2)
C9—C14—H14	119.7
N1—C1—C2—C3	−23.1 (3)	N2—C1—N1—C15	−101.6 (2)
N2—C1—C2—C3	−152.1 (2)	C2—C1—N1—C15	129.4 (2)
C8—C1—C2—C3	92.9 (3)	C8—C1—N1—C15	5.7 (2)
N1—C1—C2—C7	161.6 (2)	O2—C16—N2—C1	−175.6 (2)
N2—C1—C2—C7	32.5 (3)	N4—C16—N2—C1	6.5 (2)
C8—C1—C2—C7	−82.4 (3)	N1—C1—N2—C16	106.0 (2)
C7—C2—C3—C4	−0.6 (4)	C2—C1—N2—C16	−124.7 (2)
C1—C2—C3—C4	−176.0 (2)	C8—C1—N2—C16	−1.7 (2)
C2—C3—C4—C5	1.6 (4)	O1—C15—N3—C8	179.3 (2)
C3—C4—C5—C6	−1.2 (5)	N1—C15—N3—C8	0.8 (3)
C4—C5—C6—C7	−0.1 (5)	O1—C15—N3—C17	−26.3 (4)
C3—C2—C7—C6	−0.7 (4)	N1—C15—N3—C17	155.3 (2)
C1—C2—C7—C6	174.7 (2)	N4—C8—N3—C15	112.8 (2)
C5—C6—C7—C2	1.0 (5)	C9—C8—N3—C15	−122.4 (2)
N1—C1—C8—N4	−119.56 (17)	C1—C8—N3—C15	2.6 (2)
N2—C1—C8—N4	−3.42 (19)	N4—C8—N3—C17	−44.3 (2)
C2—C1—C8—N4	118.06 (19)	C9—C8—N3—C17	80.5 (2)
N1—C1—C8—N3	−4.7 (2)	C1—C8—N3—C17	−154.46 (17)
N2—C1—C8—N3	111.44 (17)	N5—C17—N3—C15	−103.2 (2)
C2—C1—C8—N3	−127.07 (19)	N5—C17—N3—C8	50.4 (2)
N1—C1—C8—C9	117.3 (2)	O2—C16—N4—C8	173.2 (2)
N2—C1—C8—C9	−126.58 (19)	N2—C16—N4—C8	−8.9 (2)
C2—C1—C8—C9	−5.1 (3)	O2—C16—N4—C18	29.4 (3)
N4—C8—C9—C10	154.5 (2)	N2—C16—N4—C18	−152.67 (19)
N3—C8—C9—C10	30.6 (3)	N3—C8—N4—C16	−101.92 (19)
C1—C8—C9—C10	−86.6 (3)	C9—C8—N4—C16	133.45 (18)
N4—C8—C9—C14	−28.5 (3)	C1—C8—N4—C16	7.6 (2)
N3—C8—C9—C14	−152.4 (2)	N3—C8—N4—C18	44.7 (2)
C1—C8—C9—C14	90.4 (3)	C9—C8—N4—C18	−80.0 (2)
C14—C9—C10—C11	−0.1 (4)	C1—C8—N4—C18	154.14 (16)
C8—C9—C10—C11	177.0 (2)	N5—C18—N4—C16	90.4 (2)
C9—C10—C11—C12	0.3 (4)	N5—C18—N4—C8	−52.0 (2)
C10—C11—C12—C13	−0.5 (4)	N4—C18—N5—C17	54.1 (2)
C11—C12—C13—C14	0.3 (4)	N4—C18—N5—C19	−75.1 (2)
C10—C9—C14—C13	−0.1 (4)	N3—C17—N5—C18	−53.0 (2)
C8—C9—C14—C13	−177.1 (2)	N3—C17—N5—C19	75.7 (2)
C12—C13—C14—C9	0.0 (4)	C20—C19—N5—C18	−150.6 (3)
O1—C15—N1—C1	177.0 (2)	C20—C19—N5—C17	82.5 (3)
N3—C15—N1—C1	−4.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^i	0.89 (3)	2.20 (3)	3.043 (3)	158 (2)
N1—H1···O2^ii	0.93 (3)	1.96 (3)	2.873 (3)	168 (2)
C18—H18B···O1^iii	0.97	2.62	3.370 (3)	134 (1)
C17—H17A···O2^iv	0.97	2.64	3.404 (3)	135 (1)

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x+1/2, y+1/2, −z+1/2.