2,12-Dichloro-10,20-diphenyl-5,7,15,17-tetra­hydro-6H,16H-dibenzo[d,l][1,9,2,6,10,14]dioxo­tetraaza­cyclo­hexa­decine-6,16-dione dioxane solvate as a potential macrocyclic hexa­dentate ligand

The macrocyclic title compound crystallizes as a dioxane solvate, C₃₀H₂₂Cl₂N₄O₄·C₄H₈O₂, with two independent formula units in the unit cell. The observed syn conformation is controlled by both intra­molecular N—H...O hydrogen bonds and inter­molecular C—H...π inter­actions. The relative macrocyclic inner bore is estimated to be 4.19 Å. In the crystal structure, mol­ecules form dimers via inter­molecular C—H...π inter­actions, and these dimers are, in turn, linked to form columns along the a axis by inter­molecular C—H...O hydrogen bonds. Both X-ray diffraction analysis and density functional theory (DFT) calculations reveal that the macrocycle possesses very high flexibility. This property, as well as the presence of six donor atoms accessible for coordination, makes the title macrocycle a very promising ligand for complexation with the majority of transition metals.

S1. Comment

Azamacrocyclic compounds are interesting macrocyclic objects with regard to their spatial structures, their self-assembly, chemical and coordination properties, and their biological activity (Hiraoka, 1978; Gokel & Korzeniowski, 1982; Gokel, 1991; Cooper, 1992; Bradshaw et al., 1993; Lehn, 1995; Bradshaw & Izatt, 1997; Kulikov et al., 2005). Recently, we have reported on the synthesis, crystal structure (Dvorkin et al., 1985; Andronati et al.,2005) and chemical properties (Kulikov et al., 2003), in particular, complexation with lanthanides (Pavlovsky et al., 2004; Rusakova et al., 2005), of the 16- and 18-membered dibenzodioxatetraazamacrocycles shown in the scheme. Here, we present the investigation, by experimental and theoretical methods, of the structural features of the macrocycle of the title solvate, (I), which are relevant to its complexation capabilities.

Two independent macrocycles, together with two dioxane molecules, are found in the asymmetric unit of (I), i.e. the macrocyclic ligand crystallizes as a solvate with dioxane in a 1:1 ratio. The structure of the macrocycles of (I) is shown in Fig. 1. The main difference between the two macrocyclic molecules is only in the relative orientations of the phenyl groups (Fig. 2). Therefore, for the most part, only the geometry and conformation of one of the independent macrocycles is discussed.

The macrocycle of compound (I) has two O– and four N-donor atoms in the macrocyclic ring, two fused chloro-substituted benzene rings, and two carbonyl and two phenyl groups in the side chains. The bond lengths and angles fall within the expected ranges. The syn configuration at the C═N bond is unchanged compared with that in the starting material, 2-chloroacetamidobenzophenone syn-oxime. Both amide groups have E configurations, which are apparently determined by intramolecular N—H···O hydrogen bonds (Table 1). It is noteworthy that the formation of an intramolecular hydrogen bond between an H atom of the amide group and the oxime O atom in a sterically unfavoured seven-membered ring has also been found in the previously described molecular structure of 5-bromo-2-propenoylaminobenzophenone syn-oxime (Andronati et al., 2005). The angle between the planes formed by the two fused benzene rings is 79.0 (3)°. The phenyl substituents at atoms C10 and C20 are syn relative to the macrocyclic core. The interplanar angle between these phenyl rings is 37.2 (3)° [24.3 (3)° for the second independent macrocycle].

The conformational assignment for the macrocycle of (I) is close to t-c-g^--t-c-g^--c-t-t-c-g^--t-c-g^--c-t (t = 180°, c = 0° and g = ±60°). The overall idealized symmetry of the macrocyclic ligand is C₂, but the two bridged chains between the fused aromatic rings adopt different conformations. Although most of the corresponding dihedral angles of these chains are within 5° of each other, there are three dihedral angles which deviate considerably (Table 2). Moreover, except for the C6—C7—O8—N9 and C16—C17—O18—N19 torsion angles, the dihedral angles of the C4A–C10A [Please list all atoms involved, separated by /] chain around one side of the molecule are somewhat smaller in absolute value than the dihedral angles of the C14A–C20A [Please list all atoms involved, separated by /] chain along the other side of the molecule. The flexibility of the macrocycle allows it to adopt such an essentially puckered conformation, which is stabilized by both intramolecular N—H···O hydrogen bonds and intermolecular C—H···π interactions (see below).

The intramolecular distances O8···O18 [3.979 (3) Å], N5···N15 [4.120 (3) Å] and N9···N19 [3.853 (3) Å] can be used to estimate the inner hole size of the macrocyclic ring. The dimensions of the macrocyclic bore, estimated to be twice as large as the mean distance from the donor atoms to their centroid, is 4.19 Å, and is thus sufficiently large to accomodate many transition metal ions.

In the crystal structure, the two independent molecules of (I) form dimers via intermolecular C—H···π interactions [H14A···C35 = 2.68 Å, H14A···C36 = 3.02 Å, H46A···C3 = 2.74 Å and H46A···C2 = 3.05 Å; these distances are given for the C14—H14A and C46—H46A bond lengths normalized to 1.05 Å (Fig. 1)]. The dimers, in turn, are linked in to columns along the a axis by two intermolecular C—H···O hydrogen bonds (Table 1, Fig. 3). The dioxane molecules apparently occupy the cavities between these columns in the unit cell and are bound to them via weak intermolecular C—H···O hydrogen bonds.

We used the PRIRODA program (Laikov, 1997) to perfom quantum-chemical calculations for two different conformations of (I), namely syn, which is realised in the crystal, and anti. The geometry optimizations were carried out using the PBE generalized gradient function with C₁ symmetry and the TZ2P valence basis set. Vibration frequencies were used to characterize stationary points as minima. According to the calculations, both conformations correspond to minima of the potential energy surface, with a very small energy difference of 2.2 kcal mol^-1 (1 kcal mol^-1 = 4.184 kJ mol^-1). It is very important to note that both the calculated syn and anti conformations of the macrocycle of (I) (Figs. 4 and 5) have intrinsic C₂ and C_s symmetries, respectively. We attribute the observed distortions of the macrocycle of (I) from C₂ symmetry in the crystal to the aforementioned intra- and intermolecular interactions. The results obtained prove that the macrocycle of (I) is highly flexible.

Thus, the data presented above show that the studied macrocycle, (I), is a good potential hexadentate ligand for complexation with transition metals. The presence of six donor atoms accessible for coordination, as well as the high flexibility of the molecule, which allows it to adopt various conformations, make this compound a very promising ligand for complexation with the majority of transition metals. These investigations are currently in progress.

Related literature

For related literature, see: Andronati et al. (2005); Bradshaw & Izatt (1997); Bradshaw et al. (1993); Cooper (1992); Dvorkin et al. (1985); Gokel (1991); Gokel & Korzeniowski (1982); Hiraoka (1978); Kulikov et al. (2003, 2005); Laikov (1997); Lehn (1995); Pavlovsky et al. (2004); Rusakova et al. (2005).

S2. Experimental

A solution of NaOH (0.619 g, 15.48 mmol) in water (10 ml) was added dropwise with stirring to a solution of 2-chloroacetamidobenzophenone syn-oxime (5.0 g, 15.48 mmol) in dioxane (10 ml), and the mixture was then stirred at room temperature overnight. The white solid that formed was separated off by filtration. The crude product was purified by recrystallization from dioxane to give (I) as the dioxane solvate (yield 1.82 g, 41%; m.p. 589–590 K). ¹H NMR (DMSO-d₆, δ, p.p.m.): 4.44–4.73 (dd, J = 15.6 and 55.7 Hz, 4H), 7.10–7.58 (m, 16H), 9.83 (s, 2H); MS m/z: 572 (22) [M⁺], 270 (7), 257 (100), 228 (21), 192 (7); IR (CHCl₃, ν, cm^-1): 3400, 3000, 1680, 1600, 1500. Single crystals of the macrocycle (I) suitable for X-ray structural analysis were grown from a dioxane solution by slow evaporation at room temperature.

S3. Refinement

H atoms were placed in calculated positions and refined using a riding model, with C—H = 0.95 or 0.99 Å and N—H = 0.88 Å [Please check added text], and with fixed displacement parameters [U_iso(H) = 1.2U_eq(C,N)]. The asymmetric unit contains two solvate dioxane molecules, one of which is disordered over two sites with occupancies of 0.6 and 0.4. 28 distance restraints were used to fit the ideal chair conformations for both orientations of the disordered dioxane molecule. 73 reflections, with experimentally observed F² deviating significantly from the theoretically calculated F², were omitted from the refinement.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The two independent macrocycles of (I), forming the dimer via intermolecular C—H···π interactions and intramolecular N—H···O hydrogen bonds (shown as dotted and dashed lines, respectively). The atom-numbering scheme is shown, and displacement ellipsoids are drawn at the 40% probability level. The two solvate dioxane molecules and most of the H atoms have been omitted for clarity.
	Fig. 2. An overlay diagram, demonstrating the structural differences between the two symmetry-independent macrocyclic molecules of (I).
	Fig. 3. A packing diagram for (I)·C4H8O2, along the a axis, showing the columns of dimers of (I) and the arrangement of the solvate dioxane molecules. The orientation of the lower-occupancy disordered dioxane molecule is not presented. Only H atoms participating in the formation of hydrogen bonds are shown. Hydrogen bonds are drawn as dashed lines
	Fig. 4. The calculated syn conformation for the macrocycle of (I).
	Fig. 5. The calculated anti conformation for the macrocycle of (I).

2,12-Dichloro-10,20-diphenyl-5,7,15,17-tetrahydro-6H,16H- dibenzo[d,l][1,9,2,6,10,14]dioxotetraazacyclohexadecine-6,16-dione dioxane solvate

Crystal data

C30H22Cl2N4O4·C4H8O2	Z = 4
Mr = 661.52	F(000) = 1376
Triclinic, P1	Dx = 1.448 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.6834 (6) Å	Cell parameters from 8835 reflections
b = 14.2960 (8) Å	θ = 2.2–28.0°
c = 22.2970 (13) Å	µ = 0.27 mm^−1
α = 92.389 (2)°	T = 120 K
β = 99.896 (3)°	Orthogonal prism, colourless
γ = 92.476 (2)°	0.30 × 0.25 × 0.20 mm
V = 3034.1 (3) Å^3

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	14551 independent reflections
Radiation source: normal-focus sealed tube	10236 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ϕ and ω scans	θmax = 28.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −12→12
Tmin = 0.928, Tmax = 0.944	k = −18→18
31338 measured reflections	l = −29→29

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.05P)^2 + 2P] where P = (Fo^2 + 2Fc^2)/3
14551 reflections	(Δ/σ)max = 0.001
874 parameters	Δρmax = 0.56 e Å^−3
28 restraints	Δρmin = −0.37 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.

28 distance restraints were used to fit the ideal chair-conformations for both orientations of the disordered dioxane molecule. The O—C distances are fixed at 1.425 Å (8 restraints), the C—C distances are fixed at 1.500 Å (4 restraints), 1–3 C···C distances are fixed at 2.330 Å (4 restraints), 1–3 C···O distances are fixed at 2.400 Å (8 restraints), and 1–4 C···C distances are fixed at 2.770 Å (4 restraints).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.87342 (5)	−0.20339 (3)	0.34469 (2)	0.02792 (11)
Cl2	0.76542 (6)	0.56333 (3)	−0.04519 (2)	0.03612 (13)
Cl3	0.60505 (5)	0.69774 (3)	0.16428 (2)	0.03111 (11)
Cl4	0.70951 (6)	−0.06562 (3)	0.55434 (2)	0.03439 (12)
C1	0.82351 (18)	−0.09369 (12)	0.24804 (8)	0.0217 (4)
H1A	0.7368	−0.1290	0.2369	0.026*
C2	0.91736 (19)	−0.11434 (12)	0.29946 (8)	0.0213 (3)
C3	1.04568 (19)	−0.06456 (13)	0.31588 (8)	0.0229 (4)
H3A	1.1109	−0.0811	0.3502	0.028*
C4	1.07727 (19)	0.00924 (13)	0.28165 (8)	0.0232 (4)
H4A	1.1639	0.0445	0.2933	0.028*
C4A	0.98411 (18)	0.03257 (12)	0.23047 (8)	0.0196 (3)
N5	1.00871 (15)	0.11102 (10)	0.19674 (7)	0.0209 (3)
H5A	0.9345	0.1322	0.1739	0.025*
C6	1.13264 (18)	0.15768 (12)	0.19530 (8)	0.0196 (3)
O6	1.24692 (13)	0.13455 (9)	0.22040 (6)	0.0248 (3)
C7	1.12312 (18)	0.24742 (13)	0.16089 (8)	0.0229 (4)
H7A	1.1595	0.3005	0.1901	0.027*
H7B	1.1857	0.2438	0.1302	0.027*
O8	0.98598 (13)	0.26797 (9)	0.13042 (5)	0.0216 (3)
N9	0.95052 (15)	0.20441 (10)	0.07816 (6)	0.0204 (3)
C10	0.85277 (17)	0.23481 (12)	0.03828 (8)	0.0189 (3)
C10A	0.78365 (18)	0.32556 (12)	0.04383 (8)	0.0194 (3)
C11	0.80260 (19)	0.39350 (12)	0.00225 (8)	0.0226 (4)
H11A	0.8590	0.3818	−0.0279	0.027*
C12	0.7387 (2)	0.47780 (13)	0.00530 (8)	0.0252 (4)
C13	0.6537 (2)	0.49574 (13)	0.04803 (9)	0.0266 (4)
H13A	0.6093	0.5536	0.0491	0.032*
C14	0.6341 (2)	0.42875 (13)	0.08899 (9)	0.0261 (4)
H14A	0.5757	0.4406	0.1183	0.031*
C14A	0.69941 (18)	0.34375 (12)	0.08775 (8)	0.0220 (4)
N15	0.68395 (16)	0.27653 (11)	0.13118 (7)	0.0238 (3)
H15A	0.7575	0.2439	0.1438	0.029*
C16	0.56715 (19)	0.25733 (12)	0.15528 (8)	0.0224 (4)
O16	0.45737 (14)	0.29602 (10)	0.14237 (7)	0.0334 (3)
C17	0.58171 (19)	0.18420 (13)	0.20336 (9)	0.0242 (4)
H17A	0.5868	0.2167	0.2438	0.029*
H17B	0.4958	0.1423	0.1960	0.029*
O18	0.70046 (13)	0.12796 (9)	0.20540 (6)	0.0224 (3)
N19	0.67593 (15)	0.06789 (10)	0.15126 (7)	0.0216 (3)
C20	0.75662 (17)	−0.00140 (12)	0.15585 (8)	0.0194 (3)
C20A	0.85729 (17)	−0.02079 (12)	0.21287 (8)	0.0195 (3)
C21	0.81026 (18)	0.17301 (12)	−0.01787 (8)	0.0201 (3)
C22	0.9018 (2)	0.10760 (13)	−0.03451 (8)	0.0260 (4)
H22A	0.9923	0.1036	−0.0106	0.031*
C23	0.8607 (2)	0.04859 (14)	−0.08590 (9)	0.0310 (4)
H23A	0.9234	0.0045	−0.0972	0.037*
C24	0.7277 (2)	0.05347 (14)	−0.12117 (9)	0.0296 (4)
H24A	0.6996	0.0128	−0.1564	0.036*
C25	0.6371 (2)	0.11796 (14)	−0.10450 (9)	0.0274 (4)
H25A	0.5462	0.1212	−0.1283	0.033*
C26	0.67780 (19)	0.17811 (13)	−0.05321 (8)	0.0240 (4)
H26A	0.6152	0.2226	−0.0423	0.029*
C27	0.74233 (18)	−0.06596 (12)	0.10066 (8)	0.0207 (3)
C28	0.7977 (2)	−0.15393 (13)	0.10405 (8)	0.0262 (4)
H28A	0.8513	−0.1714	0.1413	0.031*
C29	0.7758 (2)	−0.21698 (14)	0.05357 (9)	0.0313 (4)
H29A	0.8131	−0.2773	0.0567	0.038*
C30	0.6999 (2)	−0.19171 (14)	−0.00109 (9)	0.0295 (4)
H30A	0.6825	−0.2351	−0.0353	0.035*
C31	0.6491 (2)	−0.10258 (15)	−0.00566 (9)	0.0322 (4)
H31A	0.5995	−0.0843	−0.0436	0.039*
C32	0.6702 (2)	−0.03995 (14)	0.04446 (9)	0.0279 (4)
H32A	0.6354	0.0210	0.0407	0.034*
C33	0.66005 (19)	0.58814 (13)	0.26031 (8)	0.0229 (4)
H33A	0.7439	0.6264	0.2721	0.028*
C34	0.56563 (19)	0.60699 (12)	0.20917 (8)	0.0222 (4)
C35	0.44127 (19)	0.55373 (13)	0.19155 (8)	0.0237 (4)
H35A	0.3762	0.5687	0.1568	0.028*
C36	0.41316 (19)	0.47852 (13)	0.22523 (8)	0.0244 (4)
H36A	0.3284	0.4413	0.2133	0.029*
C36A	0.50773 (18)	0.45670 (12)	0.27650 (8)	0.0206 (3)
N37	0.48416 (15)	0.37764 (11)	0.31004 (7)	0.0229 (3)
H37A	0.5592	0.3548	0.3313	0.028*
C38	0.36014 (18)	0.33287 (12)	0.31342 (8)	0.0190 (3)
O38	0.24562 (12)	0.35689 (9)	0.28868 (6)	0.0236 (3)
C39	0.36808 (18)	0.24516 (13)	0.34957 (8)	0.0224 (4)
H39A	0.3062	0.2513	0.3804	0.027*
H39B	0.3302	0.1911	0.3215	0.027*
O40	0.50511 (12)	0.22457 (8)	0.38016 (5)	0.0208 (3)
N41	0.54371 (15)	0.29143 (10)	0.43027 (6)	0.0193 (3)
C42	0.64560 (17)	0.26425 (12)	0.46936 (7)	0.0182 (3)
C42A	0.70932 (18)	0.17123 (12)	0.46522 (8)	0.0197 (3)
C43	0.68430 (19)	0.10397 (12)	0.50613 (8)	0.0222 (4)
H43A	0.6253	0.1168	0.5351	0.027*
C44	0.74551 (19)	0.01853 (12)	0.50454 (8)	0.0232 (4)
C45	0.83406 (19)	−0.00098 (13)	0.46334 (9)	0.0262 (4)
H45A	0.8772	−0.0594	0.4632	0.031*
C46	0.8591 (2)	0.06543 (13)	0.42238 (9)	0.0265 (4)
H46A	0.9197	0.0525	0.3941	0.032*
C46A	0.79570 (18)	0.15098 (13)	0.42256 (8)	0.0221 (4)
N47	0.81223 (16)	0.21764 (11)	0.37894 (7)	0.0248 (3)
H47A	0.7412	0.2535	0.3686	0.030*
C48	0.92468 (19)	0.23294 (13)	0.35113 (8)	0.0233 (4)
O48	1.03179 (14)	0.19106 (10)	0.36066 (7)	0.0363 (3)
C49	0.90843 (19)	0.30707 (13)	0.30373 (9)	0.0244 (4)
H49A	0.9940	0.3493	0.3111	0.029*
H49B	0.9028	0.2755	0.2630	0.029*
O50	0.78909 (13)	0.36289 (9)	0.30264 (6)	0.0223 (3)
N51	0.81619 (15)	0.42523 (10)	0.35577 (7)	0.0208 (3)
C52	0.73729 (17)	0.49545 (12)	0.35019 (8)	0.0194 (3)
C52A	0.63177 (18)	0.51242 (12)	0.29479 (8)	0.0198 (3)
C53	0.69752 (18)	0.33064 (12)	0.52244 (8)	0.0201 (3)
C54	0.6470 (2)	0.42097 (14)	0.52388 (9)	0.0297 (4)
H54A	0.5815	0.4402	0.4905	0.036*
C55	0.6923 (2)	0.48228 (15)	0.57375 (10)	0.0337 (5)
H55A	0.6567	0.5431	0.5747	0.040*
C56	0.7893 (2)	0.45535 (14)	0.62232 (9)	0.0303 (4)
H56A	0.8188	0.4971	0.6569	0.036*
C57	0.8427 (2)	0.36787 (14)	0.62022 (9)	0.0303 (4)
H57A	0.9108	0.3499	0.6531	0.036*
C58	0.7981 (2)	0.30557 (13)	0.57059 (8)	0.0267 (4)
H58A	0.8365	0.2456	0.5695	0.032*
C59	0.75937 (18)	0.56626 (12)	0.40223 (8)	0.0217 (4)
C60	0.6582 (2)	0.63084 (13)	0.40804 (8)	0.0257 (4)
H60A	0.5730	0.6282	0.3795	0.031*
C61	0.6815 (2)	0.69942 (14)	0.45564 (9)	0.0305 (4)
H61A	0.6126	0.7437	0.4592	0.037*
C62	0.8044 (2)	0.70277 (14)	0.49745 (9)	0.0309 (4)
H62A	0.8204	0.7496	0.5297	0.037*
C63	0.9044 (2)	0.63806 (15)	0.49260 (9)	0.0337 (5)
H63A	0.9885	0.6403	0.5219	0.040*
C64	0.8831 (2)	0.56992 (14)	0.44534 (9)	0.0283 (4)
H64A	0.9524	0.5258	0.4423	0.034*
O65	0.49423 (14)	0.91082 (11)	0.25012 (6)	0.0329 (3)
C66	0.3889 (2)	0.84160 (16)	0.25717 (9)	0.0334 (5)
H66A	0.3836	0.7910	0.2251	0.040*
H66B	0.2965	0.8701	0.2526	0.040*
C67	0.4219 (3)	0.80132 (17)	0.31868 (11)	0.0419 (5)
H67A	0.3482	0.7531	0.3230	0.050*
H67B	0.5126	0.7707	0.3226	0.050*
O68	0.42968 (18)	0.87262 (13)	0.36552 (7)	0.0470 (4)
C69	0.5350 (2)	0.94244 (17)	0.35902 (9)	0.0373 (5)
H69A	0.6278	0.9145	0.3648	0.045*
H69B	0.5380	0.9933	0.3908	0.045*
C70	0.5060 (2)	0.98249 (15)	0.29732 (10)	0.0351 (5)
H70A	0.4176	1.0159	0.2931	0.042*
H70B	0.5829	1.0284	0.2933	0.042*
O71	−0.0202 (4)	0.6165 (2)	0.23660 (13)	0.0522 (16)	0.60
C72	0.0953 (3)	0.67603 (19)	0.22703 (8)	0.0404 (9)	0.60
H72A	0.1843	0.6504	0.2467	0.048*	0.60
H72B	0.0886	0.7392	0.2459	0.048*	0.60
C73	0.0954 (2)	0.68323 (9)	0.16025 (7)	0.0399 (5)
H73A	0.0088	0.7123	0.1411	0.048*	0.60
H73B	0.1768	0.7239	0.1542	0.048*	0.60
H73C	0.1935	0.6686	0.1764	0.048*	0.40
H73D	0.0973	0.7439	0.1404	0.048*	0.40
O74	0.1028 (3)	0.59313 (12)	0.13183 (9)	0.0309 (6)	0.60
C75	−0.0123 (4)	0.53352 (16)	0.14157 (14)	0.0354 (12)	0.60
H75A	−0.0057	0.4704	0.1225	0.042*	0.60
H75B	−0.1015	0.5591	0.1221	0.042*	0.60
C76	−0.0116 (4)	0.52606 (18)	0.20853 (16)	0.0388 (13)	0.60
H76A	−0.0923	0.4849	0.2147	0.047*	0.60
H76B	0.0756	0.4977	0.2276	0.047*	0.60
O71'	0.0072 (5)	0.6038 (3)	0.23986 (15)	0.0429 (18)	0.40
C72'	0.0149 (4)	0.6910 (2)	0.21175 (13)	0.0418 (14)	0.40
H72C	0.0615	0.7397	0.2423	0.050*	0.40
H72D	−0.0811	0.7102	0.1962	0.050*	0.40
O74'	0.0330 (4)	0.61166 (19)	0.11652 (11)	0.0479 (13)	0.40
C75'	0.0256 (6)	0.52461 (13)	0.1448 (2)	0.040 (2)	0.40
H75C	0.1215	0.5059	0.1610	0.048*	0.40
H75D	−0.0199	0.4755	0.1143	0.048*	0.40
C76'	−0.0569 (6)	0.5330 (3)	0.1957 (2)	0.042 (2)	0.40
H76C	−0.1541	0.5490	0.1793	0.050*	0.40
H76D	−0.0611	0.4722	0.2153	0.050*	0.40

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0307 (2)	0.0264 (2)	0.0270 (2)	0.00062 (18)	0.00468 (18)	0.00688 (18)
Cl2	0.0574 (3)	0.0227 (2)	0.0295 (2)	0.0071 (2)	0.0089 (2)	0.00522 (19)
Cl3	0.0379 (3)	0.0269 (2)	0.0281 (2)	−0.00267 (19)	0.0036 (2)	0.00877 (18)
Cl4	0.0479 (3)	0.0215 (2)	0.0336 (3)	0.0047 (2)	0.0047 (2)	0.00663 (19)
C1	0.0184 (8)	0.0223 (9)	0.0240 (9)	0.0002 (7)	0.0033 (7)	−0.0011 (7)
C2	0.0238 (9)	0.0201 (8)	0.0207 (8)	0.0025 (7)	0.0058 (7)	0.0001 (7)
C3	0.0207 (9)	0.0274 (9)	0.0198 (8)	0.0040 (7)	0.0008 (7)	−0.0002 (7)
C4	0.0187 (8)	0.0279 (9)	0.0215 (9)	−0.0009 (7)	0.0008 (7)	−0.0009 (7)
C4A	0.0179 (8)	0.0205 (8)	0.0205 (8)	0.0009 (6)	0.0044 (7)	−0.0010 (7)
N5	0.0151 (7)	0.0241 (8)	0.0215 (7)	−0.0001 (6)	−0.0024 (6)	0.0025 (6)
C6	0.0176 (8)	0.0232 (9)	0.0170 (8)	0.0000 (7)	0.0020 (6)	−0.0045 (7)
O6	0.0165 (6)	0.0298 (7)	0.0271 (7)	0.0014 (5)	0.0009 (5)	0.0025 (5)
C7	0.0176 (8)	0.0263 (9)	0.0228 (9)	−0.0024 (7)	−0.0011 (7)	0.0024 (7)
O8	0.0213 (6)	0.0233 (6)	0.0179 (6)	0.0005 (5)	−0.0015 (5)	−0.0037 (5)
N9	0.0208 (7)	0.0213 (7)	0.0183 (7)	0.0004 (6)	0.0022 (6)	−0.0030 (6)
C10	0.0169 (8)	0.0207 (8)	0.0192 (8)	0.0006 (6)	0.0039 (6)	−0.0001 (6)
C10A	0.0181 (8)	0.0200 (8)	0.0183 (8)	0.0012 (6)	−0.0014 (6)	−0.0027 (6)
C11	0.0249 (9)	0.0226 (9)	0.0189 (8)	0.0021 (7)	0.0004 (7)	−0.0017 (7)
C12	0.0309 (10)	0.0200 (9)	0.0224 (9)	0.0004 (7)	−0.0015 (7)	0.0003 (7)
C13	0.0277 (10)	0.0213 (9)	0.0292 (10)	0.0049 (7)	0.0000 (8)	−0.0014 (7)
C14	0.0246 (9)	0.0251 (9)	0.0283 (9)	0.0042 (7)	0.0042 (8)	−0.0038 (7)
C14A	0.0184 (8)	0.0235 (9)	0.0226 (9)	0.0006 (7)	0.0001 (7)	−0.0013 (7)
N15	0.0212 (7)	0.0247 (8)	0.0266 (8)	0.0065 (6)	0.0059 (6)	0.0022 (6)
C16	0.0212 (9)	0.0215 (9)	0.0236 (9)	0.0005 (7)	0.0029 (7)	−0.0043 (7)
O16	0.0217 (7)	0.0338 (8)	0.0461 (9)	0.0065 (6)	0.0071 (6)	0.0090 (6)
C17	0.0206 (9)	0.0254 (9)	0.0274 (9)	0.0047 (7)	0.0058 (7)	−0.0006 (7)
O18	0.0191 (6)	0.0235 (6)	0.0234 (6)	0.0025 (5)	0.0008 (5)	−0.0035 (5)
N19	0.0192 (7)	0.0216 (7)	0.0223 (7)	−0.0012 (6)	0.0001 (6)	−0.0027 (6)
C20	0.0156 (8)	0.0203 (8)	0.0217 (8)	−0.0024 (6)	0.0020 (6)	0.0011 (7)
C20A	0.0167 (8)	0.0213 (8)	0.0193 (8)	0.0024 (6)	0.0003 (6)	−0.0014 (7)
C21	0.0221 (8)	0.0182 (8)	0.0199 (8)	0.0001 (7)	0.0042 (7)	0.0003 (6)
C22	0.0250 (9)	0.0285 (10)	0.0239 (9)	0.0052 (8)	0.0022 (7)	−0.0027 (7)
C23	0.0354 (11)	0.0300 (10)	0.0274 (10)	0.0070 (8)	0.0058 (8)	−0.0064 (8)
C24	0.0356 (11)	0.0272 (10)	0.0236 (9)	−0.0018 (8)	0.0007 (8)	−0.0053 (8)
C25	0.0266 (9)	0.0299 (10)	0.0228 (9)	−0.0008 (8)	−0.0031 (7)	−0.0005 (8)
C26	0.0240 (9)	0.0255 (9)	0.0223 (9)	0.0041 (7)	0.0026 (7)	0.0008 (7)
C27	0.0174 (8)	0.0215 (9)	0.0224 (8)	−0.0029 (7)	0.0029 (7)	−0.0004 (7)
C28	0.0307 (10)	0.0262 (9)	0.0213 (9)	0.0042 (8)	0.0029 (8)	0.0019 (7)
C29	0.0417 (12)	0.0255 (10)	0.0279 (10)	0.0055 (8)	0.0086 (9)	−0.0002 (8)
C30	0.0346 (11)	0.0291 (10)	0.0246 (9)	−0.0040 (8)	0.0073 (8)	−0.0052 (8)
C31	0.0324 (11)	0.0414 (12)	0.0210 (9)	0.0028 (9)	−0.0004 (8)	0.0010 (8)
C32	0.0291 (10)	0.0298 (10)	0.0244 (9)	0.0041 (8)	0.0018 (8)	0.0034 (8)
C33	0.0211 (8)	0.0221 (9)	0.0248 (9)	−0.0020 (7)	0.0026 (7)	−0.0003 (7)
C34	0.0256 (9)	0.0197 (8)	0.0221 (9)	0.0022 (7)	0.0059 (7)	0.0013 (7)
C35	0.0224 (9)	0.0285 (9)	0.0197 (8)	0.0036 (7)	0.0014 (7)	0.0016 (7)
C36	0.0192 (8)	0.0282 (10)	0.0240 (9)	−0.0012 (7)	−0.0009 (7)	0.0014 (7)
C36A	0.0183 (8)	0.0218 (9)	0.0216 (8)	−0.0002 (7)	0.0037 (7)	0.0011 (7)
N37	0.0171 (7)	0.0250 (8)	0.0245 (8)	−0.0008 (6)	−0.0033 (6)	0.0060 (6)
C38	0.0195 (8)	0.0197 (8)	0.0170 (8)	−0.0010 (6)	0.0025 (6)	−0.0022 (6)
O38	0.0166 (6)	0.0282 (7)	0.0254 (6)	0.0015 (5)	0.0013 (5)	0.0022 (5)
C39	0.0184 (8)	0.0247 (9)	0.0222 (9)	−0.0028 (7)	−0.0013 (7)	0.0022 (7)
O40	0.0199 (6)	0.0208 (6)	0.0194 (6)	0.0011 (5)	−0.0020 (5)	−0.0026 (5)
N41	0.0198 (7)	0.0205 (7)	0.0169 (7)	0.0015 (6)	0.0021 (6)	−0.0019 (6)
C42	0.0182 (8)	0.0191 (8)	0.0179 (8)	0.0018 (6)	0.0047 (6)	0.0004 (6)
C42A	0.0188 (8)	0.0202 (8)	0.0182 (8)	0.0021 (7)	−0.0016 (6)	−0.0017 (6)
C43	0.0233 (9)	0.0223 (9)	0.0193 (8)	0.0019 (7)	−0.0010 (7)	−0.0011 (7)
C44	0.0236 (9)	0.0198 (9)	0.0239 (9)	0.0002 (7)	−0.0027 (7)	0.0019 (7)
C45	0.0220 (9)	0.0212 (9)	0.0325 (10)	0.0058 (7)	−0.0034 (8)	−0.0038 (7)
C46	0.0253 (9)	0.0240 (9)	0.0297 (10)	0.0039 (7)	0.0044 (8)	−0.0045 (8)
C46A	0.0193 (8)	0.0236 (9)	0.0223 (9)	0.0022 (7)	0.0009 (7)	−0.0016 (7)
N47	0.0227 (8)	0.0267 (8)	0.0270 (8)	0.0094 (6)	0.0075 (6)	0.0041 (6)
C48	0.0207 (9)	0.0224 (9)	0.0255 (9)	−0.0001 (7)	0.0031 (7)	−0.0067 (7)
O48	0.0219 (7)	0.0336 (8)	0.0556 (10)	0.0081 (6)	0.0092 (7)	0.0114 (7)
C49	0.0206 (9)	0.0262 (9)	0.0273 (9)	0.0040 (7)	0.0070 (7)	−0.0017 (7)
O50	0.0193 (6)	0.0242 (6)	0.0222 (6)	0.0023 (5)	0.0010 (5)	−0.0040 (5)
N51	0.0193 (7)	0.0221 (7)	0.0199 (7)	−0.0010 (6)	0.0013 (6)	−0.0019 (6)
C52	0.0161 (8)	0.0217 (8)	0.0202 (8)	−0.0027 (6)	0.0033 (6)	0.0010 (7)
C52A	0.0169 (8)	0.0220 (8)	0.0200 (8)	0.0019 (7)	0.0016 (6)	−0.0009 (7)
C53	0.0192 (8)	0.0230 (9)	0.0181 (8)	0.0014 (7)	0.0040 (7)	−0.0011 (7)
C54	0.0314 (10)	0.0272 (10)	0.0281 (10)	0.0070 (8)	−0.0014 (8)	−0.0039 (8)
C55	0.0345 (11)	0.0285 (10)	0.0361 (11)	0.0085 (8)	0.0013 (9)	−0.0071 (8)
C56	0.0323 (10)	0.0306 (10)	0.0261 (10)	−0.0012 (8)	0.0026 (8)	−0.0085 (8)
C57	0.0328 (10)	0.0310 (10)	0.0238 (9)	0.0020 (8)	−0.0033 (8)	−0.0026 (8)
C58	0.0294 (10)	0.0240 (9)	0.0244 (9)	0.0037 (8)	−0.0019 (8)	−0.0009 (7)
C59	0.0218 (9)	0.0225 (9)	0.0200 (8)	−0.0038 (7)	0.0031 (7)	0.0000 (7)
C60	0.0259 (9)	0.0261 (9)	0.0247 (9)	0.0018 (7)	0.0034 (7)	0.0015 (7)
C61	0.0359 (11)	0.0279 (10)	0.0298 (10)	0.0068 (8)	0.0104 (9)	0.0007 (8)
C62	0.0390 (11)	0.0297 (10)	0.0233 (9)	−0.0035 (9)	0.0070 (8)	−0.0062 (8)
C63	0.0317 (11)	0.0395 (12)	0.0267 (10)	−0.0020 (9)	−0.0011 (8)	−0.0049 (9)
C64	0.0247 (9)	0.0307 (10)	0.0278 (10)	0.0019 (8)	0.0010 (8)	−0.0026 (8)
O65	0.0284 (7)	0.0462 (9)	0.0238 (7)	−0.0066 (6)	0.0060 (6)	−0.0008 (6)
C66	0.0264 (10)	0.0423 (12)	0.0305 (10)	−0.0048 (9)	0.0057 (8)	−0.0040 (9)
C67	0.0441 (13)	0.0399 (13)	0.0414 (13)	−0.0052 (10)	0.0077 (10)	0.0061 (10)
O68	0.0507 (10)	0.0657 (11)	0.0252 (8)	−0.0142 (8)	0.0135 (7)	−0.0010 (7)
C69	0.0334 (11)	0.0498 (13)	0.0272 (10)	−0.0043 (10)	0.0040 (9)	−0.0058 (9)
C70	0.0307 (11)	0.0352 (11)	0.0389 (12)	0.0018 (9)	0.0049 (9)	0.0014 (9)
O71	0.0223 (15)	0.089 (4)	0.043 (3)	−0.0122 (18)	0.0137 (15)	−0.036 (2)
C72	0.039 (2)	0.042 (2)	0.039 (2)	−0.0064 (18)	0.0106 (18)	−0.0153 (18)
C73	0.0372 (12)	0.0354 (12)	0.0472 (13)	0.0000 (9)	0.0093 (10)	−0.0011 (10)
O74	0.0431 (16)	0.0286 (14)	0.0214 (12)	0.0003 (11)	0.0072 (11)	0.0001 (10)
C75	0.027 (2)	0.044 (3)	0.032 (2)	−0.0160 (17)	0.0029 (16)	−0.009 (2)
C76	0.043 (3)	0.040 (3)	0.036 (3)	0.001 (2)	0.013 (2)	0.0075 (19)
O71'	0.049 (4)	0.055 (4)	0.023 (3)	−0.014 (3)	0.003 (2)	0.004 (3)
C72'	0.059 (4)	0.030 (3)	0.034 (3)	0.016 (3)	−0.002 (3)	0.002 (2)
O74'	0.082 (4)	0.037 (2)	0.030 (2)	0.015 (2)	0.021 (2)	0.0060 (18)
C75'	0.019 (3)	0.064 (5)	0.033 (4)	−0.010 (3)	0.003 (2)	−0.012 (3)
C76'	0.066 (6)	0.030 (3)	0.033 (4)	0.017 (3)	0.012 (4)	0.007 (3)

Geometric parameters (Å, º)

Cl1—C2	1.7397 (18)	C42—C53	1.488 (2)
Cl2—C12	1.7369 (19)	C42—C42A	1.496 (2)
Cl3—C34	1.7400 (18)	C42A—C43	1.394 (2)
Cl4—C44	1.7349 (19)	C42A—C46A	1.400 (2)
C1—C2	1.386 (2)	C43—C44	1.382 (2)
C1—C20A	1.391 (2)	C43—H43A	0.9500
C1—H1A	0.9500	C44—C45	1.388 (3)
C2—C3	1.389 (2)	C45—C46	1.387 (3)
C3—C4	1.382 (3)	C45—H45A	0.9500
C3—H3A	0.9500	C46—C46A	1.392 (2)
C4—C4A	1.390 (2)	C46—H46A	0.9500
C4—H4A	0.9500	C46A—N47	1.413 (2)
C4A—C20A	1.405 (2)	N47—C48	1.357 (2)
C4A—N5	1.410 (2)	N47—H47A	0.8800
N5—C6	1.354 (2)	C48—O48	1.212 (2)
N5—H5A	0.8800	C48—C49	1.522 (3)
C6—O6	1.217 (2)	C49—O50	1.430 (2)
C6—C7	1.520 (2)	C49—H49A	0.9900
C7—O8	1.432 (2)	C49—H49B	0.9900
C7—H7A	0.9900	O50—N51	1.4323 (18)
C7—H7B	0.9900	N51—C52	1.285 (2)
O8—N9	1.4313 (18)	C52—C59	1.488 (2)
N9—C10	1.286 (2)	C52—C52A	1.497 (2)
C10—C21	1.489 (2)	C53—C58	1.390 (2)
C10—C10A	1.496 (2)	C53—C54	1.401 (3)
C10A—C11	1.398 (2)	C54—C55	1.384 (3)
C10A—C14A	1.401 (2)	C54—H54A	0.9500
C11—C12	1.383 (3)	C55—C56	1.386 (3)
C11—H11A	0.9500	C55—H55A	0.9500
C12—C13	1.385 (3)	C56—C57	1.376 (3)
C13—C14	1.380 (3)	C56—H56A	0.9500
C13—H13A	0.9500	C57—C58	1.387 (3)
C14—C14A	1.395 (3)	C57—H57A	0.9500
C14—H14A	0.9500	C58—H58A	0.9500
C14A—N15	1.414 (2)	C59—C60	1.393 (3)
N15—C16	1.356 (2)	C59—C64	1.399 (3)
N15—H15A	0.8800	C60—C61	1.397 (3)
C16—O16	1.216 (2)	C60—H60A	0.9500
C16—C17	1.522 (3)	C61—C62	1.377 (3)
C17—O18	1.427 (2)	C61—H61A	0.9500
C17—H17A	0.9900	C62—C63	1.383 (3)
C17—H17B	0.9900	C62—H62A	0.9500
O18—N19	1.4313 (18)	C63—C64	1.387 (3)
N19—C20	1.285 (2)	C63—H63A	0.9500
C20—C27	1.490 (2)	C64—H64A	0.9500
C20—C20A	1.507 (2)	O65—C66	1.423 (2)
C21—C26	1.392 (2)	O65—C70	1.425 (3)
C21—C22	1.398 (2)	C66—C67	1.499 (3)
C22—C23	1.384 (3)	C66—H66A	0.9900
C22—H22A	0.9500	C66—H66B	0.9900
C23—C24	1.395 (3)	C67—O68	1.419 (3)
C23—H23A	0.9500	C67—H67A	0.9900
C24—C25	1.383 (3)	C67—H67B	0.9900
C24—H24A	0.9500	O68—C69	1.426 (3)
C25—C26	1.391 (3)	C69—C70	1.499 (3)
C25—H25A	0.9500	C69—H69A	0.9900
C26—H26A	0.9500	C69—H69B	0.9900
C27—C28	1.388 (3)	C70—H70A	0.9900
C27—C32	1.399 (3)	C70—H70B	0.9900
C28—C29	1.393 (3)	O71—C76	1.425 (4)
C28—H28A	0.9500	O71—C72	1.427 (4)
C29—C30	1.381 (3)	C72—C73	1.497 (4)
C29—H29A	0.9500	C72—H72A	0.9900
C30—C31	1.387 (3)	C72—H72B	0.9900
C30—H30A	0.9500	C73—O74	1.422 (4)
C31—C32	1.384 (3)	C73—O74'	1.422 (4)
C31—H31A	0.9500	C73—C72'	1.498 (4)
C32—H32A	0.9500	C73—H73A	0.9900
C33—C34	1.377 (3)	C73—H73B	0.9900
C33—C52A	1.398 (2)	C73—H73C	0.9900
C33—H33A	0.9500	C73—H73D	0.9900
C34—C35	1.385 (3)	O74—C75	1.426 (4)
C35—C36	1.381 (3)	C75—C76	1.500 (4)
C35—H35A	0.9500	C75—H75A	0.9900
C36—C36A	1.392 (2)	C75—H75B	0.9900
C36—H36A	0.9500	C76—H76A	0.9900
C36A—C52A	1.402 (2)	C76—H76B	0.9900
C36A—N37	1.413 (2)	O71'—C72'	1.423 (4)
N37—C38	1.351 (2)	O71'—C76'	1.425 (4)
N37—H37A	0.8800	C72'—H72C	0.9900
C38—O38	1.221 (2)	C72'—H72D	0.9900
C38—C39	1.516 (2)	O74'—C75'	1.423 (4)
C39—O40	1.432 (2)	C75'—C76'	1.500 (4)
C39—H39A	0.9900	C75'—H75C	0.9900
C39—H39B	0.9900	C75'—H75D	0.9900
O40—N41	1.4278 (18)	C76'—H76C	0.9900
N41—C42	1.285 (2)	C76'—H76D	0.9900
C2—C1—C20A	119.45 (16)	C43—C44—Cl4	119.35 (15)
C2—C1—H1A	120.3	C45—C44—Cl4	119.74 (14)
C20A—C1—H1A	120.3	C46—C45—C44	119.52 (17)
C1—C2—C3	121.13 (16)	C46—C45—H45A	120.2
C1—C2—Cl1	119.56 (14)	C44—C45—H45A	120.2
C3—C2—Cl1	119.31 (14)	C45—C46—C46A	120.19 (17)
C4—C3—C2	119.17 (16)	C45—C46—H46A	119.9
C4—C3—H3A	120.4	C46A—C46—H46A	119.9
C2—C3—H3A	120.4	C46—C46A—C42A	120.05 (17)
C3—C4—C4A	120.91 (16)	C46—C46A—N47	121.45 (16)
C3—C4—H4A	119.5	C42A—C46A—N47	118.46 (16)
C4A—C4—H4A	119.5	C48—N47—C46A	127.69 (16)
C4—C4A—C20A	119.36 (16)	C48—N47—H47A	116.2
C4—C4A—N5	122.46 (15)	C46A—N47—H47A	116.2
C20A—C4A—N5	118.12 (15)	O48—C48—N47	124.81 (18)
C6—N5—C4A	127.87 (15)	O48—C48—C49	119.77 (16)
C6—N5—H5A	116.1	N47—C48—C49	115.40 (15)
C4A—N5—H5A	116.1	O50—C49—C48	115.52 (14)
O6—C6—N5	125.19 (17)	O50—C49—H49A	108.4
O6—C6—C7	119.25 (15)	C48—C49—H49A	108.4
N5—C6—C7	115.53 (15)	O50—C49—H49B	108.4
O8—C7—C6	116.02 (14)	C48—C49—H49B	108.4
O8—C7—H7A	108.3	H49A—C49—H49B	107.5
C6—C7—H7A	108.3	C49—O50—N51	107.40 (12)
O8—C7—H7B	108.3	C52—N51—O50	111.72 (14)
C6—C7—H7B	108.3	N51—C52—C59	116.27 (15)
H7A—C7—H7B	107.4	N51—C52—C52A	124.85 (16)
N9—O8—C7	107.47 (12)	C59—C52—C52A	118.82 (15)
C10—N9—O8	111.71 (13)	C33—C52A—C36A	119.29 (16)
N9—C10—C21	115.16 (15)	C33—C52A—C52	117.43 (15)
N9—C10—C10A	125.49 (15)	C36A—C52A—C52	123.28 (15)
C21—C10—C10A	119.34 (15)	C58—C53—C54	118.82 (17)
C11—C10A—C14A	119.45 (16)	C58—C53—C42	121.21 (16)
C11—C10A—C10	117.79 (15)	C54—C53—C42	119.95 (16)
C14A—C10A—C10	122.74 (15)	C55—C54—C53	120.26 (18)
C12—C11—C10A	119.55 (17)	C55—C54—H54A	119.9
C12—C11—H11A	120.2	C53—C54—H54A	119.9
C10A—C11—H11A	120.2	C54—C55—C56	120.31 (19)
C11—C12—C13	121.31 (17)	C54—C55—H55A	119.8
C11—C12—Cl2	119.62 (15)	C56—C55—H55A	119.8
C13—C12—Cl2	119.07 (14)	C57—C56—C55	119.63 (18)
C14—C13—C12	119.36 (17)	C57—C56—H56A	120.2
C14—C13—H13A	120.3	C55—C56—H56A	120.2
C12—C13—H13A	120.3	C56—C57—C58	120.71 (18)
C13—C14—C14A	120.59 (18)	C56—C57—H57A	119.6
C13—C14—H14A	119.7	C58—C57—H57A	119.6
C14A—C14—H14A	119.7	C57—C58—C53	120.20 (18)
C14—C14A—C10A	119.71 (17)	C57—C58—H58A	119.9
C14—C14A—N15	120.69 (16)	C53—C58—H58A	119.9
C10A—C14A—N15	119.58 (16)	C60—C59—C64	119.12 (17)
C16—N15—C14A	126.47 (15)	C60—C59—C52	120.44 (16)
C16—N15—H15A	116.8	C64—C59—C52	120.43 (16)
C14A—N15—H15A	116.8	C59—C60—C61	120.32 (18)
O16—C16—N15	124.64 (17)	C59—C60—H60A	119.8
O16—C16—C17	119.91 (16)	C61—C60—H60A	119.8
N15—C16—C17	115.41 (15)	C62—C61—C60	119.94 (18)
O18—C17—C16	115.45 (14)	C62—C61—H61A	120.0
O18—C17—H17A	108.4	C60—C61—H61A	120.0
C16—C17—H17A	108.4	C61—C62—C63	120.15 (18)
O18—C17—H17B	108.4	C61—C62—H62A	119.9
C16—C17—H17B	108.4	C63—C62—H62A	119.9
H17A—C17—H17B	107.5	C62—C63—C64	120.51 (19)
C17—O18—N19	107.04 (12)	C62—C63—H63A	119.7
C20—N19—O18	111.72 (14)	C64—C63—H63A	119.7
N19—C20—C27	115.57 (15)	C63—C64—C59	119.94 (18)
N19—C20—C20A	124.03 (16)	C63—C64—H64A	120.0
C27—C20—C20A	120.37 (15)	C59—C64—H64A	120.0
C1—C20A—C4A	119.90 (16)	C66—O65—C70	110.09 (15)
C1—C20A—C20	118.85 (15)	O65—C66—C67	110.30 (17)
C4A—C20A—C20	121.24 (15)	O65—C66—H66A	109.6
C26—C21—C22	119.53 (16)	C67—C66—H66A	109.6
C26—C21—C10	120.31 (15)	O65—C66—H66B	109.6
C22—C21—C10	120.14 (16)	C67—C66—H66B	109.6
C23—C22—C21	120.03 (18)	H66A—C66—H66B	108.1
C23—C22—H22A	120.0	O68—C67—C66	110.62 (19)
C21—C22—H22A	120.0	O68—C67—H67A	109.5
C22—C23—C24	120.42 (18)	C66—C67—H67A	109.5
C22—C23—H23A	119.8	O68—C67—H67B	109.5
C24—C23—H23A	119.8	C66—C67—H67B	109.5
C25—C24—C23	119.46 (18)	H67A—C67—H67B	108.1
C25—C24—H24A	120.3	C67—O68—C69	109.52 (16)
C23—C24—H24A	120.3	O68—C69—C70	111.00 (17)
C24—C25—C26	120.58 (18)	O68—C69—H69A	109.4
C24—C25—H25A	119.7	C70—C69—H69A	109.4
C26—C25—H25A	119.7	O68—C69—H69B	109.4
C25—C26—C21	119.98 (17)	C70—C69—H69B	109.4
C25—C26—H26A	120.0	H69A—C69—H69B	108.0
C21—C26—H26A	120.0	O65—C70—C69	111.21 (18)
C28—C27—C32	118.48 (17)	O65—C70—H70A	109.4
C28—C27—C20	120.86 (16)	C69—C70—H70A	109.4
C32—C27—C20	120.65 (16)	O65—C70—H70B	109.4
C27—C28—C29	120.95 (18)	C69—C70—H70B	109.4
C27—C28—H28A	119.5	H70A—C70—H70B	108.0
C29—C28—H28A	119.5	C76—O71—C72	109.5 (2)
C30—C29—C28	119.95 (18)	O71—C72—C73	110.3 (2)
C30—C29—H29A	120.0	O71—C72—H72A	109.6
C28—C29—H29A	120.0	C73—C72—H72A	109.6
C29—C30—C31	119.55 (18)	O71—C72—H72B	109.6
C29—C30—H30A	120.2	C73—C72—H72B	109.6
C31—C30—H30A	120.2	H72A—C72—H72B	108.1
C32—C31—C30	120.60 (18)	O74—C73—C72	110.7 (2)
C32—C31—H31A	119.7	O74'—C73—C72'	110.6 (2)
C30—C31—H31A	119.7	O74—C73—H73A	109.5
C31—C32—C27	120.36 (18)	C72—C73—H73A	109.5
C31—C32—H32A	119.8	O74—C73—H73B	109.5
C27—C32—H32A	119.8	C72—C73—H73B	109.5
C34—C33—C52A	119.58 (16)	H73A—C73—H73B	108.1
C34—C33—H33A	120.2	O74'—C73—H73C	109.5
C52A—C33—H33A	120.2	C72'—C73—H73C	109.4
C33—C34—C35	121.56 (17)	O74'—C73—H73D	109.5
C33—C34—Cl3	119.47 (14)	C72'—C73—H73D	109.7
C35—C34—Cl3	118.95 (14)	H73C—C73—H73D	108.1
C36—C35—C34	119.10 (17)	C73—O74—C75	109.8 (2)
C36—C35—H35A	120.4	O74—C75—C76	110.3 (2)
C34—C35—H35A	120.4	O74—C75—H75A	109.6
C35—C36—C36A	120.65 (17)	C76—C75—H75A	109.6
C35—C36—H36A	119.7	O74—C75—H75B	109.6
C36A—C36—H36A	119.7	C76—C75—H75B	109.6
C36—C36A—C52A	119.80 (16)	H75A—C75—H75B	108.1
C36—C36A—N37	121.61 (16)	O71—C76—C75	110.2 (2)
C52A—C36A—N37	118.56 (15)	O71—C76—H76A	109.6
C38—N37—C36A	127.79 (15)	C75—C76—H76A	109.6
C38—N37—H37A	116.1	O71—C76—H76B	109.6
C36A—N37—H37A	116.1	C75—C76—H76B	109.6
O38—C38—N37	124.82 (16)	H76A—C76—H76B	108.1
O38—C38—C39	119.14 (15)	C72'—O71'—C76'	109.7 (2)
N37—C38—C39	116.02 (15)	O71'—C72'—C73	110.7 (2)
O40—C39—C38	115.83 (14)	O71'—C72'—H72C	109.5
O40—C39—H39A	108.3	C73—C72'—H72C	109.5
C38—C39—H39A	108.3	O71'—C72'—H72D	109.5
O40—C39—H39B	108.3	C73—C72'—H72D	109.5
C38—C39—H39B	108.3	H72C—C72'—H72D	108.1
H39A—C39—H39B	107.4	C73—O74'—C75'	110.1 (2)
N41—O40—C39	107.49 (12)	O74'—C75'—C76'	110.3 (2)
C42—N41—O40	111.59 (13)	O74'—C75'—H75C	109.6
N41—C42—C53	115.92 (15)	C76'—C75'—H75C	109.6
N41—C42—C42A	124.27 (15)	O74'—C75'—H75D	109.6
C53—C42—C42A	119.78 (14)	C76'—C75'—H75D	109.6
C43—C42A—C46A	119.39 (16)	H75C—C75'—H75D	108.1
C43—C42A—C42	118.74 (15)	O71'—C76'—C75'	110.1 (2)
C46A—C42A—C42	121.85 (15)	O71'—C76'—H76C	109.6
C44—C43—C42A	119.90 (17)	C75'—C76'—H76C	109.6
C44—C43—H43A	120.0	O71'—C76'—H76D	109.6
C42A—C43—H43A	120.0	C75'—C76'—H76D	109.6
C43—C44—C45	120.91 (17)	H76C—C76'—H76D	108.1
C20A—C1—C2—C3	−1.1 (3)	C38—C39—O40—N41	71.96 (17)
C20A—C1—C2—Cl1	178.28 (13)	C39—O40—N41—C42	162.55 (14)
C1—C2—C3—C4	2.7 (3)	O40—N41—C42—C53	177.87 (13)
Cl1—C2—C3—C4	−176.72 (14)	O40—N41—C42—C42A	−4.0 (2)
C2—C3—C4—C4A	−1.6 (3)	N41—C42—C42A—C43	−108.6 (2)
C3—C4—C4A—C20A	−1.1 (3)	C53—C42—C42A—C43	69.5 (2)
C3—C4—C4A—N5	175.83 (16)	N41—C42—C42A—C46A	73.0 (2)
C4—C4A—N5—C6	20.7 (3)	C53—C42—C42A—C46A	−108.91 (19)
C20A—C4A—N5—C6	−162.32 (17)	C46A—C42A—C43—C44	0.5 (3)
C4A—N5—C6—O6	5.5 (3)	C42—C42A—C43—C44	−177.97 (16)
C4A—N5—C6—C7	−172.34 (16)	C42A—C43—C44—C45	1.2 (3)
O6—C6—C7—O8	177.49 (15)	C42A—C43—C44—Cl4	−178.24 (13)
N5—C6—C7—O8	−4.5 (2)	C43—C44—C45—C46	−1.4 (3)
C6—C7—O8—N9	−73.11 (17)	Cl4—C44—C45—C46	178.02 (14)
C7—O8—N9—C10	−159.68 (14)	C44—C45—C46—C46A	−0.1 (3)
O8—N9—C10—C21	179.56 (13)	C45—C46—C46A—C42A	1.7 (3)
O8—N9—C10—C10A	0.8 (2)	C45—C46—C46A—N47	−176.02 (17)
N9—C10—C10A—C11	115.2 (2)	C43—C42A—C46A—C46	−1.9 (3)
C21—C10—C10A—C11	−63.4 (2)	C42—C42A—C46A—C46	176.51 (16)
N9—C10—C10A—C14A	−66.2 (2)	C43—C42A—C46A—N47	175.88 (16)
C21—C10—C10A—C14A	115.16 (18)	C42—C42A—C46A—N47	−5.7 (2)
C14A—C10A—C11—C12	0.4 (3)	C46—C46A—N47—C48	−31.1 (3)
C10—C10A—C11—C12	179.06 (16)	C42A—C46A—N47—C48	151.21 (18)
C10A—C11—C12—C13	−1.3 (3)	C46A—N47—C48—O48	−1.2 (3)
C10A—C11—C12—Cl2	178.52 (13)	C46A—N47—C48—C49	177.25 (17)
C11—C12—C13—C14	1.0 (3)	O48—C48—C49—O50	−170.34 (17)
Cl2—C12—C13—C14	−178.83 (14)	N47—C48—C49—O50	11.2 (2)
C12—C13—C14—C14A	0.2 (3)	C48—C49—O50—N51	72.36 (18)
C13—C14—C14A—C10A	−1.1 (3)	C49—O50—N51—C52	160.72 (14)
C13—C14—C14A—N15	177.50 (17)	O50—N51—C52—C59	−178.38 (13)
C11—C10A—C14A—C14	0.8 (3)	O50—N51—C52—C52A	−1.3 (2)
C10—C10A—C14A—C14	−177.77 (16)	C34—C33—C52A—C36A	0.2 (3)
C11—C10A—C14A—N15	−177.83 (16)	C34—C33—C52A—C52	−179.55 (16)
C10—C10A—C14A—N15	3.6 (3)	C36—C36A—C52A—C33	−1.4 (3)
C14—C14A—N15—C16	35.9 (3)	N37—C36A—C52A—C33	176.81 (16)
C10A—C14A—N15—C16	−145.44 (18)	C36—C36A—C52A—C52	178.38 (16)
C14A—N15—C16—O16	0.2 (3)	N37—C36A—C52A—C52	−3.4 (3)
C14A—N15—C16—C17	−177.46 (16)	N51—C52—C52A—C33	−110.9 (2)
O16—C16—C17—O18	166.21 (16)	C59—C52—C52A—C33	66.1 (2)
N15—C16—C17—O18	−16.0 (2)	N51—C52—C52A—C36A	69.3 (2)
C16—C17—O18—N19	−69.74 (18)	C59—C52—C52A—C36A	−113.71 (19)
C17—O18—N19—C20	−162.92 (14)	N41—C42—C53—C58	173.86 (17)
O18—N19—C20—C27	−177.81 (13)	C42A—C42—C53—C58	−4.3 (2)
O18—N19—C20—C20A	4.1 (2)	N41—C42—C53—C54	−7.5 (2)
C2—C1—C20A—C4A	−1.6 (3)	C42A—C42—C53—C54	174.32 (17)
C2—C1—C20A—C20	177.80 (15)	C58—C53—C54—C55	−2.9 (3)
C4—C4A—C20A—C1	2.7 (3)	C42—C53—C54—C55	178.44 (18)
N5—C4A—C20A—C1	−174.40 (15)	C53—C54—C55—C56	0.9 (3)
C4—C4A—C20A—C20	−176.68 (16)	C54—C55—C56—C57	1.3 (3)
N5—C4A—C20A—C20	6.3 (2)	C55—C56—C57—C58	−1.4 (3)
N19—C20—C20A—C1	104.9 (2)	C56—C57—C58—C53	−0.6 (3)
C27—C20—C20A—C1	−73.1 (2)	C54—C53—C58—C57	2.8 (3)
N19—C20—C20A—C4A	−75.8 (2)	C42—C53—C58—C57	−178.57 (17)
C27—C20—C20A—C4A	106.22 (19)	N51—C52—C59—C60	−163.40 (16)
N9—C10—C21—C26	156.47 (16)	C52A—C52—C59—C60	19.4 (2)
C10A—C10—C21—C26	−24.7 (2)	N51—C52—C59—C64	17.7 (2)
N9—C10—C21—C22	−21.7 (2)	C52A—C52—C59—C64	−159.50 (17)
C10A—C10—C21—C22	157.08 (16)	C64—C59—C60—C61	1.3 (3)
C26—C21—C22—C23	0.1 (3)	C52—C59—C60—C61	−177.62 (17)
C10—C21—C22—C23	178.36 (17)	C59—C60—C61—C62	−0.7 (3)
C21—C22—C23—C24	−0.4 (3)	C60—C61—C62—C63	−0.4 (3)
C22—C23—C24—C25	0.1 (3)	C61—C62—C63—C64	0.8 (3)
C23—C24—C25—C26	0.4 (3)	C62—C63—C64—C59	−0.1 (3)
C24—C25—C26—C21	−0.6 (3)	C60—C59—C64—C63	−0.9 (3)
C22—C21—C26—C25	0.4 (3)	C52—C59—C64—C63	178.01 (18)
C10—C21—C26—C25	−177.84 (16)	C70—O65—C66—C67	−57.3 (2)
N19—C20—C27—C28	−164.72 (17)	O65—C66—C67—O68	59.4 (2)
C20A—C20—C27—C28	13.4 (2)	C66—C67—O68—C69	−58.7 (2)
N19—C20—C27—C32	13.9 (2)	C67—O68—C69—C70	57.1 (2)
C20A—C20—C27—C32	−167.89 (16)	C66—O65—C70—C69	56.1 (2)
C32—C27—C28—C29	−3.4 (3)	O68—C69—C70—O65	−56.3 (2)
C20—C27—C28—C29	175.34 (17)	C76—O71—C72—C73	58.3 (2)
C27—C28—C29—C30	1.0 (3)	O71—C72—C73—O74	−58.3 (2)
C28—C29—C30—C31	1.7 (3)	O71—C72—C73—O74'	−25.7 (3)
C29—C30—C31—C32	−2.0 (3)	O71—C72—C73—C72'	51.9 (4)
C30—C31—C32—C27	−0.4 (3)	O74'—C73—O74—C75	−60.6 (4)
C28—C27—C32—C31	3.0 (3)	C72—C73—O74—C75	57.77 (19)
C20—C27—C32—C31	−175.65 (17)	C72'—C73—O74—C75	23.0 (3)
C52A—C33—C34—C35	1.3 (3)	C73—O74—C75—C76	−57.9 (2)
C52A—C33—C34—Cl3	−176.90 (14)	C72—O71—C76—C75	−58.7 (2)
C33—C34—C35—C36	−1.7 (3)	O74—C75—C76—O71	58.9 (2)
Cl3—C34—C35—C36	176.54 (14)	C76'—O71'—C72'—C73	−57.8 (2)
C34—C35—C36—C36A	0.5 (3)	O74—C73—C72'—O71'	24.0 (3)
C35—C36—C36A—C52A	1.0 (3)	O74'—C73—C72'—O71'	57.4 (2)
C35—C36—C36A—N37	−177.12 (17)	C72—C73—C72'—O71'	−60.6 (4)
C36—C36A—N37—C38	−24.3 (3)	O74—C73—O74'—C75'	53.3 (4)
C52A—C36A—N37—C38	157.50 (17)	C72—C73—O74'—C75'	−23.2 (3)
C36A—N37—C38—O38	−2.6 (3)	C72'—C73—O74'—C75'	−57.2 (2)
C36A—N37—C38—C39	175.66 (16)	C73—O74'—C75'—C76'	58.0 (2)
O38—C38—C39—O40	−176.50 (15)	C72'—O71'—C76'—C75'	58.6 (2)
N37—C38—C39—O40	5.1 (2)	O74'—C75'—C76'—O71'	−59.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O8	0.88	2.28	2.734 (2)	112
N5—H5A···O18	0.88	2.48	3.043 (2)	122
N5—H5A···N9	0.88	2.44	2.990 (2)	121
N5—H5A···N19	0.88	2.59	3.232 (2)	131
N15—H15A···O8	0.88	2.30	2.935 (2)	129
N15—H15A···O18	0.88	2.30	2.740 (2)	111
N37—H37A···O40	0.88	2.28	2.737 (2)	112
N37—H37A···O50	0.88	2.42	3.001 (2)	124
N37—H37A···N41	0.88	2.45	2.974 (2)	119
N37—H37A···N51	0.88	2.60	3.235 (2)	130
N47—H47A···O40	0.88	2.37	2.985 (2)	128
N47—H47A···O50	0.88	2.28	2.731 (2)	112
C1—H1A···O65^i	0.95	2.50	3.200 (2)	130
C7—H7A···O38^ii	0.99	2.31	3.206 (2)	150
C11—H11A···O74^iii	0.95	2.45	3.284 (3)	147
C33—H33A···O71^ii	0.95	2.55	3.241 (4)	130
C39—H39B···O6^iv	0.99	2.36	3.236 (2)	148
C43—H43A···O68^v	0.95	2.37	3.249 (2)	154
C57—H57A···O71^v	0.95	2.52	3.349 (4)	146

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