3-Oxa-6,8-diaza-1,2:4,5-dibenzocycloocta-1,4-dien-7-one: a three-dimensional network assembled by hydrogen-bonding, π–π and edge-to-face interactions

The title compound, C₁₃H₁₀N₂O₂, is the first structure in which the urea moiety is incorporated into an eight-membered ring. Two mol­ecules are found in the asymmetric unit, which are almost identical in their conformation and their hydrogen-bond pattern. The carbonyl O atom acts as a double acceptor for the NH groups of two adjacent mol­ecules. In this way, infinite tapes are formed, which are connected via π–π and edge-to-face interactions in the second and third dimension. This hierarchical order of interactions is confirmed by molecular mechanics calculations. Force-field and semi-empirical calculations for a single mol­ecule did not find the envelope conformation present in the crystal, indicating instead a C_s conformation. Only with a model consisting of a hydrogen-bonded dimer or a larger hydrogen-bonded section was a conformation found that was similar to the one present in the crystal.

S1. Comment

Dialkyl/aryl ureas are self-complementary hydrogen-bond donors and acceptors. They form one-dimensional networks (or chains), (Ia), in which each urea molecule donates two H atoms to the next, thereby chelating the carbonyl O atom. Thus, they are suitable building blocks for supramolecular structures assembled via hydrogen bonding (Lortie et al., 2003). Perhaps the most intriguing examples are dimeric capsules (Rebek, 2000; Böhmer & Vysotsky, 2001) formed from calix[4]arenes bearing four urea –NH—C(O)—NH—R functions on their wide rim. In cyclic ureas, the amide functions are constrained in a cis arrangement so that both the hydrogen-bond donor and acceptor functions point in the same direction. Such cyclic ureas usually adopt tape-like structures, (Ib), in the crystal, provided that no other groups capable of forming hydrogen bonds are present (Macdonald & Whitesides, 1994; Schwiebert et al., 1996; Ebbing et al., 2002). Please clarify, as a scheme showing (Ia) and (Ib) was not provided in the original submission.

With the idea of synthesizing new cyclic and linear oligoureas as anion receptors (e.g. Scheerder et al., 1994; Boerrigter et al., 1998; Budka et al., 2001; Herges et al., 2002), we undertook the reaction of o,o-diaminodiphenylether, (I), with p-nitrophenylchloroformate. From one experiment, the title compound, (II), was obtained as the product. This compound was identified as a cyclic urea by its ¹H NMR spectrum. It readily formed single crystals, the structure of which was solved before the mass spectrum confirmed its `monomeric' nature. The results of the crystal structure determination of (II) are presented here. \sch

Compound (II) is the first example of a crystal structure containing this type of eight-membered heterocycle (Cambridge Structural Database, Version 5.24, March 2003; Allen, 2002). The asymmetric unit contains two almost identical molecules (Fig. 1). A least-squares fit of all non-H atoms yields an r.m.s. deviation of 0.061 Å. The conformation of the eight-membered heterocycle may be described as an envelope consisting of two nearly planar moieties: one contains the C11—C16 aromatic ring (C11A—C16A for the second molecule in the asymmetric unit) and the attached atoms N1 and O2 (or N1A and O2A) (r.m.s. deviations 0.012 and 0.021 Å, respectively), while the other contains the C21—C26 aromatic ring (C21A—C26A) and the atoms N2, C1 and O2 (N1A, C1A and O2A) (r.m.s. deviations 0.079 and 0.062 Å, respectively). The dihedral angles between these two planes are 72.19 (2) and 68.97 (2)°, respectively. The intra-ring angle at one of the two N atoms (N2, N2A) is considerably widened (Table 1), the other one (at N1, N1A) only slightly so. The two N—C_ar bonds are of equal length but the N—C_carbonyl bonds differ markedly.

The molecules are arranged via hydrogen bonds to form infinite tapes, which include one benzene ring of each molecule. Due to the asymmetric conformation of the cyclic urea, these tapes are not planar, and the D···A distances differ. The second benzene ring is oriented perpendicular to the tape, pointing alternately to either side. The distance between parallel rings on one side is 7.00 Å. Their zip-like intercalation leads to the arrangement shown in Fig. 2, where we can distinguish (along the tape) π–π-stacked dimers with centroid separations of 3.91 Å (offset 1.52 Å, angle 0°), while the distance between these dimers is 4.07 Å (offset 2.08 Å, angle 0°). These values are commensurate with attractive interactions between aromatic rings (Hunter, 1994; Hunter et al., 2001). In addition, as depicted in Fig. 2, the π–π-stacked dimers are held together by two close edge-to-face contacts (centroid separations of 4.80 Å).

The two-dimensional arrangement described so far occurs between symmetry-related molecules of (II). The second molecule in the asymmetric unit displays the same arrangement and both are combined in the third direction, as illustrated in Fig. 3. Here, short contacts of the edge-to-face type (5.15 Å between the centroids of the aromatic rings) are found. These edge-to-face contacts (or π-facial hydrogen bonds) in the crystal are close to the optimum centroid-centroid distance of 5 Å calculated for the `tilted-T' structure of benzene (Jorgensen & Severance, 1990).

Molecular mechanics calculations with the MM3(96) force field (Allinger et al., 1989; Lii & Allinger, 1989a,b) showed that the envelope structure found in the crystal does not correspond to the global energy minimum. Instead, the C_s symmetrical conformer (r.m.s. deviation 0.31 Å from the crystal structure) was found to be the lowest in energy; minimization of the crystal structure both with this force field and with the semiempirical AM1 Hamiltonian (Dewar et al., 1985) in MOPAC6 also ended up in this conformer (Fig. 1). Our attempts to construct a two-dimensional network analogous to Fig. 2 from the C_s symmetrical conformer failed because, in this arrangement, the molecules of (II) cannot simultaneously undergo hydrogen bonding and π–π-stacking. To address the question of which molecular interaction induces the conformation in the crystal lattice, we have carried out molecular mechanics calculations on hexameric fragments of (i) tapes (A1–3/B1–3 in Fig. 2), (ii) π–π-stacked chains (B1–3/C1–3), (iii) edge-to-face bonded oligomers (Fig. 3) and (iv) a hybrid structure of tape and chain (B1/2, C1/2, D1/2). In these calculations, the corresponding sections of the crystal lattice served as the starting point.

As represented in Fig. 4, the distorted envelope conformations of the π–π-stacked and edge-to-face hexamers converge to the C_s symmetrical structure, while the packing remains similar to that in the crystal [distances between the centroids of the π–π-stacked rings of 3.70 and 4.15 Å, and edge-to-face contacts of 5.00 Å in fragment (ii) and 5.12 Å in fragment (iii)]. In contrast, in the optimized tape structure as well as the hybrid structure of fragment (iv), all hydrogen-bonded monomers retain their conformation, while in fragment (iv), the π–π-stacked dimers B1/2 adopt the C_s symmetrical structure. Although the calculations are for the gas phase rather than for a true crystal lattice, the interaction energies for the central units [A2/B2 in fragment (i), and B2/C2 and C2/B3 in fragment (ii)] allow a rough estimation of the order of magnitude of the non-bonded contacts (cf. Fig. 4). The dominating force is hydrogen bonding, followed by π–π-stacking and two edge-to-face interactions in the dimers, π–π-stacking between the dimers and, weakest, the edge-to-face contacts between the two-dimensional networks.

In summary, the cyclic urea, (II), forms a unique three-dimensional network in the crystal, which is built up by hydrogen bonding (calculated interaction energy E = −13.2 kcal mol⁻¹ per molecule; 1kcal mol⁻¹ = 4.184 kJ mol⁻¹) in one direction, by π–π-stacking and edge-to-face interactions (E = −5.5 kcal mol⁻¹) in the second dimension and by edge-to-face contacts (E = −2.2 kcal mol⁻¹) in the third dimension. Molecular mechanics calculations for hexameric sections of the crystal lattice indicate that the conformation found in the crystal is attributable to hydrogen bonding.

S2. Experimental

Solutions of the bis-trifluoroacetate of bis-(2-aminophenyl)ether (150 mg, 0.75 mmol) and of 4-nitrophenyl chloroformate (152 mg, 0.75 mmol) in CH₂Cl₂ (50 ml each) were mixed. A solution of N-ethyldiisopropylamine (388 mg, 3 mmol) in CH₂Cl₂ (50 ml) was added dropwise over 2 h. Stirring was continued for the next 4 h. The solvent was removed under reduced pressure and the crude product was triturated with ethylacetate (30 ml). A slightly grey solid was filtered off and identified as the cyclic dimer (25 mg, 15%). The filtrate was washed with 5% sodium carbonate solution and water until the yellow colour of p-nitrophenol disappeared. The organic layer was then filtered through silica gel (30 g), which was subsequently washed three times with ethyl acetate (75 ml). The final product was precipitated from ethyl acetate (5 ml) with hexane (25 ml), as a brown powder (39 mg, 23%). Colourless crystals of (II), suitable for X-ray analysis, separated from a solution of the product in a mixture of tetrahydrofuran-methanol (1:1) upon slow evaporation. ¹H NMR (400 MHz, DMSO-d₆, δ, p.p.m.): 8.89 (s, NH, 2H), 7.396 (dd, ArH, 2H, ³J = 7.8 Hz, ⁴J = 1.0 Hz) coupled with ³J to 7.065 (td, ArH, 2H, ³J = 7.2 Hz, ⁴J = 1.4 Hz), 7.028 (dd, ArH, 2H, ³J = 8.2 Hz, ⁴J = 2.4 Hz) coupled with ³J to 6.98 (ddd, ArH, 2H, ³J₁ = 6.8 Hz, ³J₂ = 7.8 Hz, ⁴J = 2.4 Hz); ¹³C NMR (100 MHz, DMSO-d₆, δ, p.p.m.): 154.86, 150.45, 132.89, 126.32, 124.83, 123.30, 123.06; MS (FD) M/Z calculated: 226.24; found: 226.5; m.p. > 489 K (decomposition).

S3. Refinement

H atoms bonded to C atoms were refined with fixed individual displacement parameters [U_iso(H) = 1.2 U_eq(C)], using a riding model with C—H = 0.95 Å. H atoms bonded to N atoms were found in a difference map and refined freely. The conformational search for (II) was performed with the stochastic search routine of the standard MM3(96) force field included in the SYBYL program package (TRIPOS Associates, Inc., 1996) using the default parameters, except for the number of pushes which was set to 10000. The conformers obtained from the search were further refined using the full-matrix Newton-Raphson minimization algorithm and characterized as minima or transition states by means of the eigenvalues of the Hessian matrix. Oligomers of (II) were constructed from the crystal structure and submitted to a minimization with the block-diagonal Newton-Raphson method followed, when possible, by the full-matrix Newton-Raphson algorithm.

Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 1990).

Figures

	Fig. 1. Perspective views of the two independent molecules of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The infinite tapes of hydrogen-bonded molecules of (II) (dashed thin lines), and the connection of these tapes via π–π-stacking (dashed thick lines) and π–facial hydrogen bonds (squares); the view is along the a axis.
	Fig. 3. The molecular arrangement of (II) seen along the c axis, perpendicular to the π–π-stacks. The two molecules in the asymmetric unit are represented as light and dark grey, respectively. Edge-to-face contacts are represented by dashed thick lines.
	Fig. 4. The optimized structures for the central units of the hexameric fragments of the crystal lattice. E is the interaction energy per molecule.

12-Oxa-5,7-diazadibenzo[a,f]cyclonona-1,6-dien-6-one

Crystal data

C13H10N2O2	F(000) = 944
Mr = 226.23	Dx = 1.397 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 33907 reflections
a = 17.5679 (10) Å	θ = 2.2–27.7°
b = 7.1586 (3) Å	µ = 0.10 mm^−1
c = 17.730 (1) Å	T = 100 K
β = 105.203 (4)°	Block, colourless
V = 2151.72 (19) Å^3	0.42 × 0.32 × 0.28 mm
Z = 8

Data collection

Stoe IPDS-II two-circle diffractometer	4291 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.054
Graphite monochromator	θmax = 27.8°, θmin = 2.4°
ω scans	h = −23→22
35184 measured reflections	k = −9→9
5093 independent reflections	l = −23→23

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0518P)^2 + 0.397P] where P = (Fo^2 + 2Fc^2)/3
5093 reflections	(Δ/σ)max = 0.001
323 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

Experimental.

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	0.68504 (6)	0.58832 (15)	0.22010 (6)	0.0192 (2)
N1	0.65406 (6)	0.74194 (13)	0.17931 (6)	0.02263 (19)
H1	0.6837 (9)	0.842 (2)	0.1879 (9)	0.029 (4)*
N2	0.64294 (6)	0.42339 (13)	0.21535 (6)	0.02136 (19)
H2	0.6753 (9)	0.326 (2)	0.2277 (9)	0.028 (4)*
O2	0.50476 (5)	0.68099 (11)	0.19510 (5)	0.02354 (17)
O1	0.75504 (5)	0.58848 (11)	0.25964 (4)	0.02148 (17)
C11	0.51315 (7)	0.71301 (15)	0.12007 (7)	0.0222 (2)
C12	0.58851 (6)	0.74518 (14)	0.11209 (6)	0.0213 (2)
C13	0.59913 (7)	0.78287 (15)	0.03843 (7)	0.0239 (2)
H13	0.6504	0.8079	0.0326	0.029*
C14	0.53442 (7)	0.78367 (16)	−0.02638 (7)	0.0263 (2)
H14	0.5414	0.8091	−0.0767	0.032*
C15	0.45934 (7)	0.74728 (16)	−0.01776 (7)	0.0277 (2)
H15	0.4154	0.7463	−0.0624	0.033*
C16	0.44819 (7)	0.71246 (16)	0.05568 (7)	0.0258 (2)
H16	0.3969	0.6887	0.0617	0.031*
C21	0.50060 (7)	0.49134 (15)	0.21079 (6)	0.0217 (2)
C22	0.56584 (6)	0.37358 (15)	0.21966 (6)	0.0200 (2)
C23	0.55589 (7)	0.18440 (15)	0.23560 (6)	0.0227 (2)
H23	0.5992	0.1012	0.2417	0.027*
C24	0.48399 (7)	0.11615 (17)	0.24257 (7)	0.0261 (2)
H24	0.4785	−0.0126	0.2530	0.031*
C25	0.42002 (7)	0.23593 (17)	0.23426 (7)	0.0283 (2)
H25	0.3709	0.1902	0.2395	0.034*
C26	0.42890 (7)	0.42311 (17)	0.21825 (7)	0.0260 (2)
H26	0.3854	0.5057	0.2123	0.031*
C1A	0.72179 (6)	0.50711 (15)	0.68616 (6)	0.0196 (2)
O1A	0.76166 (5)	0.51520 (11)	0.75585 (4)	0.02161 (17)
N1A	0.68402 (6)	0.34756 (13)	0.65954 (5)	0.02167 (19)
H1A	0.6963 (10)	0.255 (2)	0.6905 (10)	0.034 (4)*
N2A	0.71445 (6)	0.66740 (13)	0.64166 (5)	0.02161 (19)
H2A	0.7263 (9)	0.768 (2)	0.6732 (9)	0.033 (4)*
O2A	0.70505 (5)	0.39183 (11)	0.51279 (5)	0.02323 (17)
C11A	0.62988 (7)	0.34253 (15)	0.51868 (6)	0.0218 (2)
C12A	0.61949 (7)	0.32112 (14)	0.59288 (6)	0.0209 (2)
C13A	0.54679 (7)	0.26117 (15)	0.60179 (7)	0.0240 (2)
H13A	0.5394	0.2449	0.6526	0.029*
C14A	0.48532 (7)	0.22538 (16)	0.53617 (7)	0.0268 (2)
H14A	0.4359	0.1833	0.5419	0.032*
C15A	0.49621 (7)	0.25124 (16)	0.46193 (7)	0.0284 (2)
H15A	0.4537	0.2286	0.4171	0.034*
C16A	0.56860 (7)	0.30992 (15)	0.45266 (7)	0.0259 (2)
H16A	0.5760	0.3274	0.4019	0.031*
C21A	0.71266 (6)	0.58349 (15)	0.50295 (6)	0.0214 (2)
C22A	0.71642 (6)	0.70977 (15)	0.56402 (6)	0.0197 (2)
C23A	0.72499 (6)	0.89957 (15)	0.54816 (6)	0.0216 (2)
H23A	0.7281	0.9888	0.5885	0.026*
C24A	0.72904 (7)	0.96005 (16)	0.47492 (7)	0.0249 (2)
H24A	0.7344	1.0895	0.4656	0.030*
C25A	0.72524 (7)	0.83187 (17)	0.41514 (7)	0.0269 (2)
H25A	0.7281	0.8725	0.3649	0.032*
C26A	0.71724 (7)	0.64383 (16)	0.43000 (7)	0.0257 (2)
H26A	0.7149	0.5551	0.3896	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0196 (5)	0.0206 (5)	0.0182 (5)	−0.0001 (4)	0.0064 (4)	−0.0019 (4)
N1	0.0208 (5)	0.0201 (4)	0.0247 (5)	−0.0028 (4)	0.0020 (4)	0.0011 (3)
N2	0.0185 (4)	0.0179 (4)	0.0273 (5)	0.0009 (3)	0.0055 (4)	0.0003 (3)
O2	0.0266 (4)	0.0192 (4)	0.0263 (4)	0.0011 (3)	0.0094 (3)	−0.0012 (3)
O1	0.0191 (4)	0.0225 (4)	0.0217 (4)	−0.0002 (3)	0.0034 (3)	−0.0007 (3)
C11	0.0241 (5)	0.0174 (5)	0.0247 (5)	0.0011 (4)	0.0059 (4)	−0.0009 (4)
C12	0.0215 (5)	0.0167 (5)	0.0237 (5)	0.0010 (4)	0.0022 (4)	−0.0001 (4)
C13	0.0242 (5)	0.0204 (5)	0.0268 (5)	0.0007 (4)	0.0062 (4)	0.0013 (4)
C14	0.0326 (6)	0.0217 (5)	0.0233 (5)	0.0027 (4)	0.0047 (5)	0.0003 (4)
C15	0.0284 (6)	0.0224 (5)	0.0265 (6)	0.0021 (4)	−0.0031 (5)	−0.0020 (4)
C16	0.0209 (5)	0.0213 (5)	0.0330 (6)	0.0007 (4)	0.0030 (5)	−0.0007 (4)
C21	0.0240 (5)	0.0198 (5)	0.0219 (5)	−0.0007 (4)	0.0073 (4)	−0.0023 (4)
C22	0.0205 (5)	0.0210 (5)	0.0184 (5)	−0.0013 (4)	0.0051 (4)	−0.0020 (4)
C23	0.0253 (6)	0.0209 (5)	0.0226 (5)	0.0002 (4)	0.0074 (4)	−0.0006 (4)
C24	0.0312 (6)	0.0230 (5)	0.0265 (5)	−0.0044 (4)	0.0118 (5)	−0.0014 (4)
C25	0.0264 (6)	0.0305 (6)	0.0317 (6)	−0.0064 (5)	0.0142 (5)	−0.0048 (5)
C26	0.0221 (5)	0.0286 (6)	0.0292 (6)	0.0006 (4)	0.0102 (4)	−0.0037 (4)
C1A	0.0187 (5)	0.0215 (5)	0.0190 (5)	0.0030 (4)	0.0060 (4)	−0.0005 (4)
O1A	0.0229 (4)	0.0221 (4)	0.0182 (3)	0.0011 (3)	0.0024 (3)	−0.0008 (3)
N1A	0.0243 (5)	0.0193 (4)	0.0190 (4)	−0.0001 (4)	0.0013 (4)	0.0029 (3)
N2A	0.0272 (5)	0.0191 (4)	0.0179 (4)	−0.0006 (4)	0.0048 (4)	−0.0018 (3)
O2A	0.0274 (4)	0.0182 (4)	0.0254 (4)	0.0009 (3)	0.0093 (3)	−0.0008 (3)
C11A	0.0246 (5)	0.0167 (5)	0.0231 (5)	0.0013 (4)	0.0045 (4)	−0.0005 (4)
C12A	0.0227 (5)	0.0165 (5)	0.0210 (5)	0.0009 (4)	0.0014 (4)	−0.0002 (4)
C13A	0.0260 (6)	0.0204 (5)	0.0251 (5)	0.0000 (4)	0.0058 (4)	0.0017 (4)
C14A	0.0238 (6)	0.0197 (5)	0.0340 (6)	−0.0011 (4)	0.0023 (5)	−0.0008 (4)
C15A	0.0294 (6)	0.0206 (5)	0.0280 (6)	0.0010 (4)	−0.0048 (5)	−0.0020 (4)
C16A	0.0346 (6)	0.0200 (5)	0.0205 (5)	0.0014 (4)	0.0022 (5)	−0.0009 (4)
C21A	0.0224 (5)	0.0194 (5)	0.0231 (5)	0.0016 (4)	0.0070 (4)	0.0003 (4)
C22A	0.0184 (5)	0.0211 (5)	0.0194 (5)	0.0006 (4)	0.0047 (4)	0.0009 (4)
C23A	0.0214 (5)	0.0204 (5)	0.0233 (5)	0.0000 (4)	0.0064 (4)	−0.0018 (4)
C24A	0.0273 (6)	0.0207 (5)	0.0289 (6)	0.0003 (4)	0.0116 (5)	0.0023 (4)
C25A	0.0337 (6)	0.0266 (6)	0.0242 (5)	0.0005 (5)	0.0142 (5)	0.0024 (4)
C26A	0.0307 (6)	0.0254 (5)	0.0233 (5)	0.0005 (4)	0.0109 (5)	−0.0028 (4)

Geometric parameters (Å, º)

C1—O1	1.2456 (13)	C1A—O1A	1.2518 (13)
C1—N1	1.3498 (14)	C1A—N1A	1.3429 (14)
C1—N2	1.3841 (14)	C1A—N2A	1.3792 (14)
N1—C12	1.4239 (14)	N1A—C12A	1.4196 (14)
N1—H1	0.877 (16)	N1A—H1A	0.850 (17)
N2—C22	1.4218 (14)	N2A—C22A	1.4189 (14)
N2—H2	0.888 (16)	N2A—H2A	0.899 (17)
O2—C21	1.3916 (13)	O2A—C21A	1.3938 (13)
O2—C11	1.3954 (14)	O2A—C11A	1.3972 (14)
C11—C16	1.3865 (16)	C11A—C12A	1.3832 (15)
C11—C12	1.3871 (16)	C11A—C16A	1.3866 (16)
C12—C13	1.3931 (16)	C12A—C13A	1.3949 (16)
C13—C14	1.3884 (16)	C13A—C14A	1.3880 (16)
C13—H13	0.9500	C13A—H13A	0.9500
C14—C15	1.3918 (18)	C14A—C15A	1.3912 (18)
C14—H14	0.9500	C14A—H14A	0.9500
C15—C16	1.3891 (18)	C15A—C16A	1.3895 (18)
C15—H15	0.9500	C15A—H15A	0.9500
C16—H16	0.9500	C16A—H16A	0.9500
C21—C26	1.3894 (16)	C21A—C26A	1.3859 (15)
C21—C22	1.3980 (15)	C21A—C22A	1.3988 (15)
C22—C23	1.4037 (15)	C22A—C23A	1.4035 (15)
C23—C24	1.3898 (16)	C23A—C24A	1.3883 (15)
C23—H23	0.9500	C23A—H23A	0.9500
C24—C25	1.3904 (18)	C24A—C25A	1.3902 (16)
C24—H24	0.9500	C24A—H24A	0.9500
C25—C26	1.3869 (17)	C25A—C26A	1.3859 (16)
C25—H25	0.9500	C25A—H25A	0.9500
C26—H26	0.9500	C26A—H26A	0.9500
O1—C1—N1	120.04 (10)	O1A—C1A—N1A	118.90 (10)
O1—C1—N2	117.91 (10)	O1A—C1A—N2A	118.05 (10)
N1—C1—N2	121.90 (10)	N1A—C1A—N2A	122.89 (10)
C1—N1—C12	125.85 (9)	C1A—N1A—C12A	128.26 (9)
C1—N1—H1	115.9 (10)	C1A—N1A—H1A	114.5 (11)
C12—N1—H1	116.5 (10)	C12A—N1A—H1A	116.6 (11)
C1—N2—C22	135.41 (9)	C1A—N2A—C22A	135.27 (9)
C1—N2—H2	110.7 (10)	C1A—N2A—H2A	109.7 (10)
C22—N2—H2	110.4 (10)	C22A—N2A—H2A	111.8 (10)
C21—O2—C11	112.03 (8)	C21A—O2A—C11A	112.43 (8)
C16—C11—C12	121.20 (11)	C12A—C11A—C16A	121.16 (11)
C16—C11—O2	120.97 (10)	C12A—C11A—O2A	117.53 (10)
C12—C11—O2	117.83 (10)	C16A—C11A—O2A	121.27 (10)
C11—C12—C13	119.59 (10)	C11A—C12A—C13A	119.66 (10)
C11—C12—N1	119.73 (10)	C11A—C12A—N1A	120.08 (10)
C13—C12—N1	120.67 (10)	C13A—C12A—N1A	120.11 (10)
C14—C13—C12	119.65 (11)	C14A—C13A—C12A	119.73 (11)
C14—C13—H13	120.2	C14A—C13A—H13A	120.1
C12—C13—H13	120.2	C12A—C13A—H13A	120.1
C13—C14—C15	120.15 (11)	C13A—C14A—C15A	119.92 (11)
C13—C14—H14	119.9	C13A—C14A—H14A	120.0
C15—C14—H14	119.9	C15A—C14A—H14A	120.0
C16—C15—C14	120.47 (11)	C16A—C15A—C14A	120.61 (11)
C16—C15—H15	119.8	C16A—C15A—H15A	119.7
C14—C15—H15	119.8	C14A—C15A—H15A	119.7
C11—C16—C15	118.91 (11)	C11A—C16A—C15A	118.89 (11)
C11—C16—H16	120.5	C11A—C16A—H16A	120.6
C15—C16—H16	120.5	C15A—C16A—H16A	120.6
C26—C21—O2	117.29 (10)	C26A—C21A—O2A	117.03 (10)
C26—C21—C22	120.95 (10)	C26A—C21A—C22A	121.23 (10)
O2—C21—C22	121.76 (10)	O2A—C21A—C22A	121.73 (9)
C21—C22—C23	117.56 (10)	C21A—C22A—C23A	117.15 (10)
C21—C22—N2	127.38 (10)	C21A—C22A—N2A	127.20 (10)
C23—C22—N2	115.05 (10)	C23A—C22A—N2A	115.63 (9)
C24—C23—C22	121.41 (11)	C24A—C23A—C22A	121.59 (10)
C24—C23—H23	119.3	C24A—C23A—H23A	119.2
C22—C23—H23	119.3	C22A—C23A—H23A	119.2
C23—C24—C25	120.14 (11)	C23A—C24A—C25A	120.22 (10)
C23—C24—H24	119.9	C23A—C24A—H24A	119.9
C25—C24—H24	119.9	C25A—C24A—H24A	119.9
C26—C25—C24	119.10 (11)	C26A—C25A—C24A	118.89 (10)
C26—C25—H25	120.4	C26A—C25A—H25A	120.6
C24—C25—H25	120.4	C24A—C25A—H25A	120.6
C25—C26—C21	120.84 (11)	C25A—C26A—C21A	120.92 (10)
C25—C26—H26	119.6	C25A—C26A—H26A	119.5
C21—C26—H26	119.6	C21A—C26A—H26A	119.5
O1—C1—N1—C12	155.86 (10)	O1A—C1A—N1A—C12A	160.18 (10)
N2—C1—N1—C12	−19.54 (16)	N2A—C1A—N1A—C12A	−15.30 (17)
O1—C1—N2—C22	136.54 (12)	O1A—C1A—N2A—C22A	138.34 (12)
N1—C1—N2—C22	−47.96 (18)	N1A—C1A—N2A—C22A	−46.14 (18)
C21—O2—C11—C16	82.32 (12)	C21A—O2A—C11A—C12A	−96.49 (11)
C21—O2—C11—C12	−97.63 (11)	C21A—O2A—C11A—C16A	85.70 (12)
C16—C11—C12—C13	1.83 (16)	C16A—C11A—C12A—C13A	1.63 (16)
O2—C11—C12—C13	−178.23 (9)	O2A—C11A—C12A—C13A	−176.19 (9)
C16—C11—C12—N1	−179.04 (10)	C16A—C11A—C12A—N1A	177.30 (10)
O2—C11—C12—N1	0.90 (15)	O2A—C11A—C12A—N1A	−0.52 (15)
C1—N1—C12—C11	71.89 (15)	C1A—N1A—C12A—C11A	68.72 (15)
C1—N1—C12—C13	−108.99 (13)	C1A—N1A—C12A—C13A	−115.63 (13)
C11—C12—C13—C14	−1.44 (16)	C11A—C12A—C13A—C14A	−0.65 (16)
N1—C12—C13—C14	179.44 (10)	N1A—C12A—C13A—C14A	−176.32 (10)
C12—C13—C14—C15	0.10 (16)	C12A—C13A—C14A—C15A	−0.66 (16)
C13—C14—C15—C16	0.90 (17)	C13A—C14A—C15A—C16A	1.03 (17)
C12—C11—C16—C15	−0.83 (16)	C12A—C11A—C16A—C15A	−1.26 (16)
O2—C11—C16—C15	179.22 (10)	O2A—C11A—C16A—C15A	176.47 (10)
C14—C15—C16—C11	−0.54 (17)	C14A—C15A—C16A—C11A	−0.07 (17)
C11—O2—C21—C26	−111.49 (11)	C11A—O2A—C21A—C26A	−108.60 (11)
C11—O2—C21—C22	69.23 (13)	C11A—O2A—C21A—C22A	72.10 (13)
C26—C21—C22—C23	0.58 (16)	C26A—C21A—C22A—C23A	0.02 (16)
O2—C21—C22—C23	179.83 (10)	O2A—C21A—C22A—C23A	179.29 (10)
C26—C21—C22—N2	−178.60 (10)	C26A—C21A—C22A—N2A	−178.33 (11)
O2—C21—C22—N2	0.66 (17)	O2A—C21A—C22A—N2A	0.94 (18)
C1—N2—C22—C21	18.01 (19)	C1A—N2A—C22A—C21A	13.1 (2)
C1—N2—C22—C23	−161.18 (11)	C1A—N2A—C22A—C23A	−165.32 (12)
C21—C22—C23—C24	−0.18 (16)	C21A—C22A—C23A—C24A	0.42 (16)
N2—C22—C23—C24	179.09 (10)	N2A—C22A—C23A—C24A	178.96 (10)
C22—C23—C24—C25	−0.41 (17)	C22A—C23A—C24A—C25A	−0.49 (18)
C23—C24—C25—C26	0.60 (18)	C23A—C24A—C25A—C26A	0.11 (18)
C24—C25—C26—C21	−0.21 (18)	C24A—C25A—C26A—C21A	0.32 (19)
O2—C21—C26—C25	−179.68 (10)	O2A—C21A—C26A—C25A	−179.70 (11)
C22—C21—C26—C25	−0.39 (17)	C22A—C21A—C26A—C25A	−0.39 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.877 (16)	2.145 (16)	2.9949 (12)	162.9 (14)
N1A—H1A···O1A^ii	0.850 (17)	2.009 (18)	2.8409 (12)	166.0 (15)
N2—H2···O1^iii	0.888 (16)	2.075 (16)	2.9564 (12)	172.0 (14)
N2A—H2A···O1A^iv	0.899 (17)	2.152 (17)	3.0458 (12)	172.5 (14)

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