Self-inclusion structure of 5,11,17,23-tetra­kis(azido­meth­yl)-25,26,27,28-tetra­hydroxy­calix[4]arene, and 5,11,17,23-tetra-tert-butyl-25,27-bis­(chloro­acet­oxy)-26,28-bis­(2-pyridylmeth­oxy)calix[4]arene

In the structures of the two title calix[4]arene derivatives, C₃₂H₂₈N₁₂O₄, (I), and C₆₀H₆₈Cl₂N₂O₆, (II), compound (I) adopts an open-cone conformation in which there are four intra­molecular O—H...O hydrogen bonds, while compound (II) adopts a distorted chalice conformation where the two pendant pyridyl rings, one of which is disordered, are almost mutually perpendicular, with an inter­planar angle of 79.2 (2) or 71.4 (2)°. The dihedral angles between the virtual plane defined by the four bridging methyl­ene C atoms and the phenol rings are 120.27 (7), 124.03 (6), 120.14 (8) and 128.25 (7)° for (I), and 95.99 (8), 135.93 (7), 97.21 (8) and 126.10 (8)° for (II). In the supra­molecular structure of (I), pairs of mol­ecules associate by self-inclusion, where one azide group of the mol­ecule is inserted into the cavity of the inversion-related mol­ecule, and the association is stabilized by weak inter­molecular C—H...N hydrogen bonds and π(N₃)–π(aromatic) inter­actions. The mol­ecular pairs are linked into a two-dimensional network by a combination of weak inter­molecular C—H...N contacts. Each network is further connected to its neighbor to produce a three-dimensional framework via inter­sheet C—H...N hydrogen bonds. In the crystal packing of (II), the mol­ecular components are linked into an infinite chain by inter­molecular C—H...O hydrogen bonds. This study demonstrates the ability of calix[4]arene derivatives to form self-inclusion structures.

S1. Comment

Calix[4]arenes, as the most fascinating macrocyclic receptors in supramolecular chemistry, have attracted much interest owing to their specific affinity and selectivity for ion recognition (Gutsche, 1998; Ungaro & Pochini, 1991; Böhmer, 1995). This can be attained by appropriate chemical modifications to the upper or/and lower rims of a calix[4]arene platform (Gutsche, 1998), especially by incorporating organic functional groups containing N, O, P, S, Cl etc. heteroatoms as donor centers. On the other hand, these molecules are useful building blocks for the construction of larger supramolecular assemblies. The crystal structures of self-inclusion aggregations based on some calix[4]arene derivatives have been described (Gallagher et al., 1994; Böhmer et al., 1996; Brouwer et al., 2001; Ben Othman et al., 2004). Recently, azide groups have been introduced successfully into the calix[4]arene platform in order to construct more sophisticated receptors via click chemistry (Rostovtsev et al., 2002; Bew et al., 2007; Colasson et al., 2007; Vecchi et al., 2008; Julia et al., 2008); however, to the best of our knowledge, no example of self-inclusion structures of such derivatives in the solid state has been described. We report here the self-inclusion structures of a calix[4]arene azide derivative, (I), and a p-tert-butylcalix[4]arene picolyl derivative, (II), namely 5,11,17,23-tetrakis(azidomethyl)-25,26,27,28-tetrahydroxycalix[4]arene and 5,11,17,23-tetra-tert-butyl-25,27-bis(chloroacetoxy)-26,28-bis(2-pyridylmethoxy)calix[4]arene, respectively.

The molecular structures of (I) and (II) are shown in Figs. 1 and 2, respectively. Structural analysis reveals that (I) bears four CH₂N₃ arms at the upper rim of the calix[4]arene platform, while about 9% of (I) has been converted into its analog in which one CH₂N₃ unit has been oxidized into a CHO group (Abbenante, et al., 2007), consistent with the results of MS analysis using the same crystals. We presume that the oxidation occurs during crystal growth or/and diffraction analysis based on the fact that pure (I) was used when the crystallization was set up. Evaluation of the real mechanism of this interesting event is currently in progress.

Compound (I) adopts an open-cone conformation, where an eight-membered ring is formed by intramolecular O—H···O hydrogen bonds connecting all four phenol hydroxy groups, with an O···O distance range of 2.687 (3)–2.726 (3) Å (Table 1), and the four CH₂N₃ arms are pitched slightly away from the calix cavity. Similar O···O distances [2.673 (2)–2.708 (2) Å] are observed in the structure of 5,17-diethoxycarbonyl-25,26,27,28-tetrahydroxycalix[4]arene (Böhmer et al., 1996). The conformation in (I) leads to distances between diametrically opposed atoms O1 and O3, and O2 and O4, of 3.944 (3) and 3.683 (3) Å, respectively. The dihedral angles between the virtual plane (R) defined by the four bridging methylene C atoms and the C2–C7, C9–C14, C17–C22 and C25–C30 rings are 120.27 (7), 124.03 (6), 120.14 (8) and 128.25 (7)°, respectively.

Compound (II), which possesses two ClCH₂CO₂ groups and two 2-pyridylmethoxy units at the lower rim of the p-tert-butylcalix[4]arene scaffold, has a distorted chalice conformation. One tert-butyl group shows rotational disorder, and one pyridyl ring is disordered over two orientations. The two pendant pyridyl rings are nearly perpendicular to one another, with an interplanar angle of 79.2 (2), or 71.4 (2)° for the other disordered conformation, oriented in a fashion similar to that found in the structures of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(2-pyridylmethoxy)calix[4]arene (Pappalardo et al., 1992) and l,3-bis(2-pyridylmethoxy)-p-tert-butylcalix[4]crown-5 (Gattuso et al., 2006). The two opposing phenol rings bearing a ClCH₂CO₂ group are tilted away from one another at an interplanar angle of 82.04 (9)°, and make dihedral angles of 126.10 (8) and 135.93 (7)° with plane R, so that their tert-butyl groups are pitched away from the calix cavity. However, the other two phenol rings bearing a 2-pyridylmethoxy group are almost parallel to one another, with an interplanar angle of 13.21 (16)°, and create dihedral angles of 95.99 (8) and 97.21 (8)° with plane R. This conformation results in a separation between diametrically opposed atoms O1 and O4 of 3.996 (3) Å, which is much shorter than the 4.987 (3) Å between atoms O2 and O3. Other molecular dimensions of both compounds are normal.

In the supramolecular structure of (I), novel self-inclusion occurs when the molecules pack in pairs about inversion centers, creating a loosely interlocked dimer (Fig. 3), in which one CH₂N₃ arm of the molecule slots into the cavity of the inversion-related molecule. In each dimer, two weak intermolecular C—H···N hydrogen bonds (Table 1) locally form an R₂²(22) ring motif (Bernstein et al., 1995) from atoms C20/H20 in the molecules at (x, y, z) and (-x + 1, -y + 1, -z + 2), which act as hydrogen-bond donors, to atoms N12 at (-x + 1, -y + 1, -z + 2) and (x, y, z), respectively. Moreover, an intermolecular π–π interaction was observed with a Cg1···Cg2ⁱ distance of 3.5409 (4) Å [Cg1 and Cg2 are the centroids of the C2–C7 ring and the N7–N9 group, respectively; symmetry code: (i) -x + 1, -y + 1, -z + 2]; the perpendicular distance between Cg2ⁱ and the plane of the C2–C7 ring is 3.1308 (3) Å. In this interaction, the N7–N9 system lies approximately parallel to the plane of the C2–C7 ring and close to atoms C2, C3 and C7. There have been several previous reports on the self-inclusion of calixarenes in the solid state (Gallagher et al., 1994; Böhmer et al., 1996; Brouwer et al., 2001; Ben Othman et al., 2004); however, this self-inclusion usually involves weak intermolecular C—H···π contacts. The structure of (I) is the first example of calixarene self-inclusion stabilized by weak intermolecular C—H···N hydrogen bonds and π(N₃)···π(aromatic) interactions. In our case, one azide group (N7–N9) of the molecule of (I) is anchored into the bowl-shaped cavity of an adjacent inversion-related molecule, while the others lie outside the calix bowl of the inversion-related molecule. Each dimer is linked to its neighbours to produce a two-dimensional network parallel to the c axis (Fig. 4) by a combination of intermolecular C32—H32A···N4(-x, y + 1/2, -z + 3/2) hydrogen bonds, locally forming a C(9) chain motif (Bernstein et al., 1995) at each link in the network. Neighboring networks are further connected to a three-dimensional framework via intersheet C15—H15A···N7(x, -y + 3/2, z - 1/2) interactions, locally creating a C(13) chain motif (Bernstein et al., 1995).

In the crystal structure of (II), there are several intra- and intermolecular C—H···O and C—H···N short contacts (Table 2), although no classical hydrogen bonds are found. The intramolecular C41—H41A···O2, C41—H41B···O3 and C42—H42A···O5 interactions result in atoms O1, C40, C41 and Cl2 of one ClCH₂CO₂ group approaching plane R more closely than the equivalent atoms of the other ClCH₂CO₂ group. A hydrogen-bonded infinite chain parallel to [010] (Fig. 5) is formed by a combination of intermolecular C56—H56···O5(-x + 3/2, y + 1/2, z) interactions, which locally creates a C(14) motif (Bernstein et al., 1995) at each link in the chain.

Related literature

For related literature, see: Abbenante et al. (2007); Böhmer (1995); Böhmer et al. (1996); Bernstein et al. (1995); Bew et al. (2007); Brouwer et al. (2001); Colasson et al. (2007); Gallagher et al. (1994); Gattuso et al. (2006); Gutsche (1998); Julia et al. (2008); Kotch et al. (2003); Pappalardo et al. (1992); Rostovtsev et al. (2002); Ungaro & Pochini (1991); Vecchi et al. (2008).

S2. Experimental

For the synthesis of (I), a solution of p-chloromethylcalix[4]arene (0.300 g, 0.49 mmol), prepared according to a published procedure (Kotch et al., 2003), and NaN₃ (0.319 g, 4.90 mmol) in dimethylformamide (10 ml) was stirred at 343 K for 8 h. After removal of the solvent under reduced pressure, the residue was extracted with CH₂Cl₂ and washed with brine. The organic layer was dried over anhydrous MgSO₄. Removal of the solvent gave (I) as a white solid (yield 85%; m.p. 423 K, decomposition) purified by recrystallization from CH₃OH/CH₂Cl₂. ¹H NMR (300 MHz, CDCl₃): δ 10.12 (s, 4H), 7.02 (s, 8H), 4.26 (d, 4H, J = 12.5 Hz), 4.15 (s, 8H), 5.58 (d, 4H, J = 12.6 Hz). MS (analyzed using the crystals) m/e: 667.5 ([M + Na]⁺), 645.6 ([M + 1]⁺); 640.7 ([M' + Na]⁺), 618.7 (M' + 1]⁺).

For the synthesis of (II), to a stirred suspension of 5,11,17,23-tetra-tert-butyl-25,27-bis(2-pyridylmethoxy)-26,28-dihydroxycalix[4]arene (0.200 g, 0.24 mmol), obtained according to a published procedure (Pappalardo et al., 1992), and NaH (0.029 g, 80%, 0.96 mmol) in dry tetrahydrofuran (15 ml) at 273 K was added chloroacetyl chloride (0.19 ml, 2.4 mmol) dropwise. The resulting mixture was stirred for 20 h at 343 K. After removal of the solvent under reduced pressure, the residue was poured into an ice–water mixture, extracted with CH₂Cl₂ and washed with brine. The organic layer was dried over anhydrous MgSO₄. Removal of the solvent gave (II) as a white solid (yield 74%; m.p. 492 K, decomposition) purified by flash column chromatography (EtOAc/hexane = 1:4, R_f = 0.4). ¹H NMR (300 MHz, CDCl₃): δ 8.80 (d, 2H, J = 4.0 Hz), 7.78 (t, 2H, J = 7.6 Hz), 7.36 (s, 2H), 7.33 (s, 2H), 7.24 (s, 4H), 6.71 (s, 4H), 4.76 (s, 4H), 4.71 (s, 4H), 4.14 (d, 4H, J = 12.9 Hz), 3.27 (d, 4H, J = 12.9 Hz), 1.36 (s, 18H), 0.89 (s, 18H).

Single crystals of (I) and (II) suitable for X-ray diffraction analysis were obtained by slow evaporation of solutions in CH₃OH and CH₂Cl₂, respectively, at 273 K.

S3. Refinement

All H atoms were placed in geometrically idealized positions and refined using a riding model, with C—H distances of 0.93–0.99 Å, and with U_iso(H) values of 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for all other H atoms. In (I), one N₃ group is disordered with the O atom of an aldehyde decomposition product. The site occupation factors of the disordered atoms refined to 0.909 (5) for atoms N7–N9 and 0.091 (5) for atom O5. In (II), one tert-butyl group (C1–C4) shows rotational disorder; the site-occupation factor of the major orientation (C1, C2 and C3) is 0.5554 (13). The C—C bond lengths involving the disordered atoms were restrained to be similar, and the refined distances lie in the range 1.507 (3)–1.582 (3) Å. One pyridyl ring in (II) (C23–C27/N2) is also disordered over two positions; the site occupancy factor of the major conformation defined by atoms C23–C27/N2 refined to 0.5165 (13). The C—C and C—N bonds involving the disordered atoms were restrained to be similar, and the refined distances lie in the ranges 1.363 (4)–1.482 (4) and 1.335 (3)–1.407 (4) Å, respectively, while the atomic displacement parameters of adjacent atoms in both conformations of the disordered ring were restrained to be similar.

Computing details

For both compounds, data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Version 6.12; Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Version 6.12; Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level. The minor oxidized component is shown, but H atoms have been omitted for clarity.
	Fig. 2. The molecular structure of (II), with displacement ellipsoids drawn at the 30% probability level. The minor disordered conformation has been included, but H atoms have been omitted for clarity.
	Fig. 3. A view of two inversion-related molecules of (I), showing the mutual inclusion with an R2^2(22) motif. For the sake of clarity, the minor oxidized component and H atoms not involved in the hydrogen bonds have been omitted. [Symmetry code: (i) -x + 1, -y + 1, -z + 2.]
	Fig. 4. The two-dimensional network of (I), viewed along the c axis, showing the C(9) motifs. For the sake of clarity, the minor oxidized component and H atoms not involved in the hydrogen bonds have been omitted. [Symmetry codes: (i) -x + 1, -y + 1, -z + 2; (ii) -x, y + 1/2, -z + 3/2; (iii) x + 1, -y + 1/2, z + 1/2; (iv) -x, y - 1/2, -z + 3/2; (v) x + 1, -y + 3/2, z + 1/2.]
	Fig. 5. The hydrogen-bonded one-dimensional chain of (II), viewed along the a axis with C(14) motifs along [010]. For the sake of clarity, the minor disordered atoms and H atoms not involved in the motifs shown have been omitted. [Symmetry codes: (i) - x + 3/2, y + 1/2, z; (ii) -x + 3/2, y - 1/2, z; (iii) x, y + 1, z.]

(I) 5,11,17,23-tetrakis(azidomethyl)-25,26,27,28-tetrahydroxycalix[4]arene

Crystal data

C32H27.91N11.73O4.09	F(000) = 1339.1
Mr = 642.20	Dx = 1.434 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.377 (2) Å	Cell parameters from 3158 reflections
b = 12.446 (2) Å	θ = 2.4–26.1°
c = 19.979 (3) Å	µ = 0.10 mm^−1
β = 104.812 (3)°	T = 298 K
V = 2975.3 (9) Å^3	Block, colourless
Z = 4	0.38 × 0.28 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3717 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
Graphite monochromator	θmax = 25.0°, θmin = 2.0°
phi and ω scans	h = −14→10
14693 measured reflections	k = −14→14
5228 independent reflections	l = −19→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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.168	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0819P)^2 + 1.3905P] whereP = (Fo^2 + 2Fc^2)/3
5228 reflections	(Δ/σ)max = 0.001
447 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.23 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	Occ. (<1)
C1	0.1875 (3)	0.5130 (3)	0.63322 (15)	0.0559 (8)
H1A	0.1924	0.5505	0.5915	0.067*
H1B	0.2608	0.4834	0.6543	0.067*
C2	0.1596 (2)	0.5942 (2)	0.68268 (13)	0.0412 (6)
C3	0.0814 (2)	0.5764 (2)	0.71977 (13)	0.0425 (7)
H3	0.0394	0.5136	0.7120	0.051*
C4	0.0635 (2)	0.6495 (2)	0.76838 (13)	0.0404 (7)
C5	0.1265 (2)	0.7437 (2)	0.77840 (13)	0.0405 (7)
C6	0.2065 (2)	0.7644 (2)	0.74207 (13)	0.0409 (6)
C7	0.2210 (2)	0.6885 (2)	0.69442 (13)	0.0428 (7)
H7	0.2737	0.7012	0.6695	0.051*
C8	0.2802 (2)	0.8629 (2)	0.75653 (14)	0.0460 (7)
H8A	0.2400	0.9207	0.7721	0.055*
H8B	0.2974	0.8859	0.7140	0.055*
C9	0.3886 (2)	0.8418 (2)	0.81111 (14)	0.0425 (7)
C10	0.3982 (2)	0.8555 (2)	0.88161 (14)	0.0395 (6)
C11	0.4975 (2)	0.8330 (2)	0.93143 (14)	0.0418 (7)
C12	0.5874 (2)	0.7951 (2)	0.90846 (16)	0.0506 (7)
H12	0.6539	0.7793	0.9409	0.061*
C13	0.5814 (3)	0.7802 (2)	0.83944 (17)	0.0523 (8)
C14	0.4816 (3)	0.8054 (2)	0.79147 (15)	0.0497 (7)
H14	0.4773	0.7976	0.7446	0.060*
C15	0.6779 (3)	0.7352 (3)	0.8164 (2)	0.0782 (11)
H15A	0.6886	0.7773	0.7778	0.094*
H15B	0.7450	0.7417	0.8539	0.094*
C16	0.5056 (2)	0.8431 (2)	1.00852 (14)	0.0442 (7)
H16A	0.5819	0.8604	1.0330	0.053*
H16B	0.4579	0.9013	1.0160	0.053*
C17	0.4706 (2)	0.7394 (2)	1.03720 (13)	0.0386 (6)
C18	0.3613 (2)	0.7210 (2)	1.03999 (12)	0.0354 (6)
C19	0.3283 (2)	0.6232 (2)	1.06271 (12)	0.0353 (6)
C20	0.4092 (2)	0.5448 (2)	1.08352 (13)	0.0429 (7)
H20	0.3889	0.4796	1.0994	0.051*
C21	0.5187 (2)	0.5596 (2)	1.08160 (14)	0.0473 (7)
C22	0.5479 (2)	0.6577 (2)	1.05814 (14)	0.0466 (7)
H22	0.6214	0.6688	1.0564	0.056*
C23	0.6045 (3)	0.4726 (3)	1.10523 (19)	0.0688 (10)
H23A	0.5672	0.4035	1.1010	0.083*	0.909 (5)
H23B	0.6551	0.4719	1.0753	0.083*	0.909 (5)
H23C	0.5812	0.4014	1.1041	0.083*	0.091 (5)
C24	0.2077 (2)	0.5993 (2)	1.06159 (13)	0.0394 (6)
H24A	0.2062	0.5523	1.1001	0.047*
H24B	0.1708	0.6658	1.0680	0.047*
C25	0.1434 (2)	0.5467 (2)	0.99489 (13)	0.0370 (6)
C26	0.0913 (2)	0.6062 (2)	0.93678 (13)	0.0392 (6)
C27	0.0337 (2)	0.5580 (2)	0.87478 (13)	0.0414 (7)
C28	0.0285 (2)	0.4470 (2)	0.87343 (14)	0.0461 (7)
H28	−0.0096	0.4130	0.8328	0.055*
C29	0.0778 (2)	0.3848 (2)	0.93020 (15)	0.0450 (7)
C30	0.1350 (2)	0.4357 (2)	0.99048 (14)	0.0422 (6)
H30	0.1686	0.3945	1.0290	0.051*
C31	0.0686 (3)	0.2643 (3)	0.92787 (18)	0.0605 (9)
H31A	0.0368	0.2398	0.9648	0.073*
H31B	0.0189	0.2425	0.8841	0.073*
C32	−0.0185 (2)	0.6242 (3)	0.81098 (14)	0.0477 (7)
H32A	−0.0815	0.5852	0.7825	0.057*
H32B	−0.0466	0.6909	0.8252	0.057*
N1	−0.0784 (3)	0.4633 (3)	0.55025 (17)	0.0861 (10)
N2	0.0131 (3)	0.4503 (2)	0.58022 (14)	0.0637 (8)
N3	0.1085 (3)	0.4237 (2)	0.61315 (15)	0.0663 (8)
N4	0.2128 (4)	0.1146 (4)	0.8429 (2)	0.1098 (14)
N5	0.1914 (2)	0.1649 (3)	0.88542 (17)	0.0679 (8)
N6	0.1790 (2)	0.2138 (2)	0.93553 (15)	0.0710 (8)
N7	0.7906 (4)	0.6355 (4)	1.20391 (19)	0.0883 (13)	0.909 (5)
N8	0.7318 (3)	0.5662 (4)	1.18505 (18)	0.0729 (11)	0.909 (5)
N9	0.6686 (4)	0.4875 (4)	1.1765 (2)	0.0967 (16)	0.909 (5)
N10	0.5192 (6)	0.5844 (4)	0.6944 (4)	0.183 (3)
N11	0.5875 (5)	0.6071 (3)	0.7417 (3)	0.1134 (15)
N12	0.6624 (4)	0.6221 (3)	0.7954 (2)	0.0915 (12)
O1	0.11049 (18)	0.82045 (16)	0.82495 (10)	0.0522 (5)
H1	0.0944	0.7908	0.8578	0.078*
O2	0.30977 (16)	0.89352 (16)	0.90442 (10)	0.0501 (5)
H2	0.2510	0.8774	0.8765	0.075*
O3	0.28120 (15)	0.80002 (15)	1.02037 (9)	0.0450 (5)
H3A	0.2923	0.8334	0.9874	0.067*
O4	0.09191 (16)	0.71711 (15)	0.93971 (10)	0.0491 (5)
H4	0.1487	0.7375	0.9679	0.074*
O5	0.7081 (16)	0.4940 (18)	1.1267 (10)	0.040 (6)	0.091 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.064 (2)	0.0599 (19)	0.0448 (17)	−0.0083 (16)	0.0166 (15)	−0.0054 (15)
C2	0.0457 (16)	0.0476 (16)	0.0271 (13)	0.0032 (13)	0.0032 (11)	0.0046 (12)
C3	0.0423 (15)	0.0507 (17)	0.0296 (14)	−0.0021 (13)	0.0005 (11)	0.0025 (12)
C4	0.0339 (14)	0.0545 (17)	0.0272 (13)	0.0051 (12)	−0.0022 (11)	0.0047 (12)
C5	0.0407 (15)	0.0471 (16)	0.0291 (14)	0.0095 (13)	0.0003 (11)	0.0038 (12)
C6	0.0467 (16)	0.0414 (15)	0.0305 (14)	0.0085 (12)	0.0023 (12)	0.0076 (12)
C7	0.0452 (16)	0.0512 (17)	0.0310 (14)	0.0044 (13)	0.0079 (11)	0.0107 (13)
C8	0.0605 (18)	0.0412 (16)	0.0343 (15)	0.0025 (13)	0.0086 (13)	0.0080 (12)
C9	0.0519 (17)	0.0312 (14)	0.0435 (16)	−0.0031 (12)	0.0108 (13)	0.0066 (12)
C10	0.0437 (16)	0.0303 (14)	0.0443 (16)	0.0000 (12)	0.0107 (12)	0.0061 (12)
C11	0.0436 (16)	0.0345 (14)	0.0461 (16)	−0.0089 (12)	0.0097 (12)	0.0068 (12)
C12	0.0406 (16)	0.0513 (18)	0.0581 (19)	−0.0048 (13)	0.0091 (14)	0.0126 (15)
C13	0.0488 (18)	0.0494 (18)	0.063 (2)	−0.0025 (14)	0.0216 (15)	0.0113 (15)
C14	0.065 (2)	0.0433 (16)	0.0451 (16)	−0.0058 (14)	0.0216 (15)	0.0046 (13)
C15	0.069 (2)	0.085 (3)	0.091 (3)	0.007 (2)	0.041 (2)	0.015 (2)
C16	0.0409 (15)	0.0407 (15)	0.0445 (16)	−0.0085 (12)	−0.0008 (12)	0.0034 (13)
C17	0.0392 (15)	0.0386 (15)	0.0335 (14)	−0.0045 (12)	0.0013 (11)	0.0003 (11)
C18	0.0383 (14)	0.0359 (14)	0.0292 (13)	0.0016 (11)	0.0036 (11)	−0.0033 (11)
C19	0.0390 (14)	0.0416 (15)	0.0232 (12)	−0.0043 (12)	0.0040 (10)	−0.0046 (11)
C20	0.0490 (17)	0.0378 (15)	0.0390 (15)	−0.0048 (13)	0.0060 (12)	0.0073 (12)
C21	0.0433 (16)	0.0463 (17)	0.0483 (17)	0.0032 (13)	0.0047 (13)	0.0095 (14)
C22	0.0336 (15)	0.0524 (18)	0.0492 (17)	−0.0017 (13)	0.0021 (12)	0.0067 (14)
C23	0.053 (2)	0.062 (2)	0.085 (3)	0.0120 (16)	0.0069 (18)	0.0187 (19)
C24	0.0416 (15)	0.0482 (16)	0.0294 (13)	−0.0035 (12)	0.0108 (11)	−0.0024 (12)
C25	0.0296 (13)	0.0497 (16)	0.0344 (14)	−0.0047 (12)	0.0133 (11)	−0.0052 (12)
C26	0.0313 (14)	0.0502 (17)	0.0382 (15)	−0.0029 (12)	0.0127 (11)	−0.0060 (13)
C27	0.0268 (13)	0.0642 (19)	0.0342 (14)	−0.0069 (12)	0.0096 (11)	−0.0073 (13)
C28	0.0373 (15)	0.066 (2)	0.0366 (15)	−0.0140 (14)	0.0123 (12)	−0.0170 (14)
C29	0.0357 (15)	0.0530 (17)	0.0498 (17)	−0.0107 (13)	0.0174 (13)	−0.0122 (14)
C30	0.0350 (14)	0.0528 (17)	0.0400 (15)	−0.0043 (13)	0.0118 (11)	−0.0028 (13)
C31	0.0550 (19)	0.058 (2)	0.073 (2)	−0.0150 (16)	0.0247 (16)	−0.0201 (17)
C32	0.0337 (15)	0.070 (2)	0.0360 (15)	−0.0031 (13)	0.0022 (11)	−0.0051 (14)
N1	0.083 (2)	0.098 (3)	0.071 (2)	−0.025 (2)	0.0082 (18)	0.0044 (19)
N2	0.085 (2)	0.0592 (18)	0.0485 (16)	−0.0184 (17)	0.0192 (16)	−0.0052 (14)
N3	0.076 (2)	0.0587 (18)	0.0622 (18)	−0.0062 (15)	0.0141 (16)	−0.0011 (14)
N4	0.116 (3)	0.118 (3)	0.088 (3)	0.039 (3)	0.012 (2)	−0.024 (2)
N5	0.0591 (18)	0.0686 (19)	0.066 (2)	0.0041 (15)	−0.0020 (15)	−0.0111 (17)
N6	0.0641 (19)	0.074 (2)	0.0634 (18)	0.0019 (15)	−0.0043 (14)	−0.0248 (16)
N7	0.114 (4)	0.087 (3)	0.062 (2)	0.020 (3)	0.020 (2)	−0.011 (2)
N8	0.077 (3)	0.075 (3)	0.062 (2)	0.032 (2)	0.0080 (19)	0.013 (2)
N9	0.081 (3)	0.095 (3)	0.095 (3)	0.006 (2)	−0.014 (3)	0.050 (2)
N10	0.208 (7)	0.096 (4)	0.210 (7)	0.044 (4)	−0.010 (5)	−0.062 (4)
N11	0.144 (5)	0.070 (3)	0.132 (4)	0.033 (3)	0.046 (4)	−0.013 (3)
N12	0.115 (3)	0.081 (3)	0.098 (3)	0.033 (2)	0.062 (2)	0.024 (2)
O1	0.0555 (13)	0.0559 (12)	0.0453 (12)	0.0099 (10)	0.0131 (10)	−0.0043 (10)
O2	0.0477 (12)	0.0526 (12)	0.0471 (12)	0.0106 (10)	0.0066 (9)	0.0021 (10)
O3	0.0483 (11)	0.0414 (11)	0.0442 (11)	0.0079 (9)	0.0102 (9)	0.0018 (9)
O4	0.0481 (12)	0.0513 (12)	0.0440 (12)	−0.0001 (9)	0.0047 (9)	−0.0069 (9)
O5	0.031 (11)	0.066 (14)	0.023 (11)	0.013 (9)	0.009 (8)	0.000 (10)

Geometric parameters (Å, º)

C1—N3	1.467 (4)	C20—C21	1.378 (4)
C1—C2	1.514 (4)	C20—H20	0.9300
C1—H1A	0.9700	C21—C22	1.388 (4)
C1—H1B	0.9700	C21—C23	1.505 (4)
C2—C3	1.379 (4)	C22—H22	0.9300
C2—C7	1.385 (4)	C23—O5	1.27 (2)
C3—C4	1.389 (4)	C23—N9	1.453 (6)
C3—H3	0.9300	C23—H23A	0.9700
C4—C5	1.393 (4)	C23—H23B	0.9700
C4—C32	1.516 (4)	C23—H23C	0.9300
C5—O1	1.382 (3)	C24—C25	1.515 (3)
C5—C6	1.394 (4)	C24—H24A	0.9700
C6—C7	1.385 (4)	C24—H24B	0.9700
C6—C8	1.511 (4)	C25—C30	1.386 (4)
C7—H7	0.9300	C25—C26	1.389 (4)
C8—C9	1.519 (4)	C26—O4	1.382 (3)
C8—H8A	0.9700	C26—C27	1.397 (4)
C8—H8B	0.9700	C27—C28	1.383 (4)
C9—C14	1.384 (4)	C27—C32	1.517 (4)
C9—C10	1.393 (4)	C28—C29	1.380 (4)
C10—O2	1.374 (3)	C28—H28	0.9300
C10—C11	1.397 (4)	C29—C30	1.385 (4)
C11—C12	1.390 (4)	C29—C31	1.504 (4)
C11—C16	1.523 (4)	C30—H30	0.9300
C12—C13	1.374 (4)	C31—N6	1.476 (4)
C12—H12	0.9300	C31—H31A	0.9700
C13—C14	1.392 (4)	C31—H31B	0.9700
C13—C15	1.495 (5)	C32—H32A	0.9700
C14—H14	0.9300	C32—H32B	0.9700
C15—N12	1.467 (6)	N1—N2	1.150 (4)
C15—H15A	0.9700	N2—N3	1.241 (4)
C15—H15B	0.9700	N4—N5	1.139 (4)
C16—C17	1.519 (4)	N5—N6	1.214 (4)
C16—H16A	0.9700	N7—N8	1.130 (5)
C16—H16B	0.9700	N8—N9	1.238 (5)
C17—C22	1.386 (4)	N10—N11	1.131 (7)
C17—C18	1.387 (4)	N11—N12	1.239 (6)
C18—O3	1.381 (3)	O1—H1	0.8200
C18—C19	1.396 (4)	O2—H2	0.8200
C19—C20	1.384 (4)	O3—H3A	0.8200
C19—C24	1.516 (4)	O4—H4	0.8200
N3—C1—C2	115.9 (3)	C21—C20—C19	122.6 (3)
N3—C1—H1A	108.3	C21—C20—H20	118.7
C2—C1—H1A	108.3	C19—C20—H20	118.7
N3—C1—H1B	108.3	C20—C21—C22	118.0 (3)
C2—C1—H1B	108.3	C20—C21—C23	121.0 (3)
H1A—C1—H1B	107.4	C22—C21—C23	121.0 (3)
C3—C2—C7	118.4 (3)	C17—C22—C21	121.9 (3)
C3—C2—C1	123.5 (3)	C17—C22—H22	119.0
C7—C2—C1	118.0 (3)	C21—C22—H22	119.0
C2—C3—C4	122.0 (3)	O5—C23—C21	121.7 (10)
C2—C3—H3	119.0	N9—C23—C21	112.3 (3)
C4—C3—H3	119.0	O5—C23—H23A	129.2
C3—C4—C5	117.9 (3)	N9—C23—H23A	109.1
C3—C4—C32	120.4 (3)	C21—C23—H23A	109.1
C5—C4—C32	121.6 (2)	O5—C23—H23B	57.0
O1—C5—C4	120.5 (2)	N9—C23—H23B	109.1
O1—C5—C6	117.8 (2)	C21—C23—H23B	109.1
C4—C5—C6	121.7 (3)	H23A—C23—H23B	107.9
C7—C6—C5	117.8 (3)	O5—C23—H23C	119.2
C7—C6—C8	120.5 (3)	C21—C23—H23C	119.2
C5—C6—C8	121.7 (2)	C25—C24—C19	113.0 (2)
C6—C7—C2	122.2 (3)	C25—C24—H24A	109.0
C6—C7—H7	118.9	C19—C24—H24A	109.0
C2—C7—H7	118.9	C25—C24—H24B	109.0
C6—C8—C9	112.1 (2)	C19—C24—H24B	109.0
C6—C8—H8A	109.2	H24A—C24—H24B	107.8
C9—C8—H8A	109.2	C30—C25—C26	117.8 (2)
C6—C8—H8B	109.2	C30—C25—C24	120.0 (2)
C9—C8—H8B	109.2	C26—C25—C24	122.1 (2)
H8A—C8—H8B	107.9	O4—C26—C25	120.1 (2)
C14—C9—C10	117.6 (3)	O4—C26—C27	117.6 (2)
C14—C9—C8	119.9 (3)	C25—C26—C27	122.3 (3)
C10—C9—C8	122.4 (3)	C28—C27—C26	117.2 (3)
O2—C10—C9	120.5 (2)	C28—C27—C32	121.2 (2)
O2—C10—C11	117.6 (2)	C26—C27—C32	121.5 (3)
C9—C10—C11	121.9 (3)	C29—C28—C27	122.4 (2)
C12—C11—C10	117.7 (3)	C29—C28—H28	118.8
C12—C11—C16	120.7 (2)	C27—C28—H28	118.8
C10—C11—C16	121.5 (3)	C28—C29—C30	118.6 (3)
C13—C12—C11	122.3 (3)	C28—C29—C31	121.3 (3)
C13—C12—H12	118.9	C30—C29—C31	120.1 (3)
C11—C12—H12	118.9	C29—C30—C25	121.7 (3)
C12—C13—C14	118.1 (3)	C29—C30—H30	119.2
C12—C13—C15	121.1 (3)	C25—C30—H30	119.2
C14—C13—C15	120.7 (3)	N6—C31—C29	111.2 (3)
C9—C14—C13	122.3 (3)	N6—C31—H31A	109.4
C9—C14—H14	118.8	C29—C31—H31A	109.4
C13—C14—H14	118.8	N6—C31—H31B	109.4
N12—C15—C13	113.1 (3)	C29—C31—H31B	109.4
N12—C15—H15A	109.0	H31A—C31—H31B	108.0
C13—C15—H15A	109.0	C4—C32—C27	112.5 (2)
N12—C15—H15B	109.0	C4—C32—H32A	109.1
C13—C15—H15B	109.0	C27—C32—H32A	109.1
H15A—C15—H15B	107.8	C4—C32—H32B	109.1
C17—C16—C11	111.1 (2)	C27—C32—H32B	109.1
C17—C16—H16A	109.4	H32A—C32—H32B	107.8
C11—C16—H16A	109.4	N1—N2—N3	172.5 (4)
C17—C16—H16B	109.4	N2—N3—C1	114.8 (3)
C11—C16—H16B	109.4	N4—N5—N6	172.9 (4)
H16A—C16—H16B	108.0	N5—N6—C31	115.9 (3)
C22—C17—C18	118.1 (2)	N7—N8—N9	168.9 (5)
C22—C17—C16	119.8 (2)	N8—N9—C23	113.8 (4)
C18—C17—C16	122.1 (2)	N10—N11—N12	174.0 (6)
O3—C18—C17	120.5 (2)	N11—N12—C15	114.0 (4)
O3—C18—C19	117.7 (2)	C5—O1—H1	109.5
C17—C18—C19	121.8 (2)	C10—O2—H2	109.5
C20—C19—C18	117.5 (2)	C18—O3—H3A	109.5
C20—C19—C24	120.0 (2)	C26—O4—H4	109.5
C18—C19—C24	122.4 (2)
N3—C1—C2—C3	14.4 (4)	O3—C18—C19—C20	−178.9 (2)
N3—C1—C2—C7	−169.8 (3)	C17—C18—C19—C20	0.9 (4)
C7—C2—C3—C4	−0.4 (4)	O3—C18—C19—C24	4.4 (3)
C1—C2—C3—C4	175.4 (2)	C17—C18—C19—C24	−175.9 (2)
C2—C3—C4—C5	0.8 (4)	C18—C19—C20—C21	−0.9 (4)
C2—C3—C4—C32	−176.5 (2)	C24—C19—C20—C21	175.9 (2)
C3—C4—C5—O1	178.6 (2)	C19—C20—C21—C22	0.4 (4)
C32—C4—C5—O1	−4.1 (4)	C19—C20—C21—C23	179.5 (3)
C3—C4—C5—C6	−1.0 (4)	C18—C17—C22—C21	−0.2 (4)
C32—C4—C5—C6	176.3 (2)	C16—C17—C22—C21	−176.9 (3)
O1—C5—C6—C7	−178.8 (2)	C20—C21—C22—C17	0.1 (4)
C4—C5—C6—C7	0.9 (4)	C23—C21—C22—C17	−178.9 (3)
O1—C5—C6—C8	4.7 (4)	C20—C21—C23—O5	−155.1 (11)
C4—C5—C6—C8	−175.7 (2)	C22—C21—C23—O5	24.0 (11)
C5—C6—C7—C2	−0.4 (4)	C20—C21—C23—N9	−96.4 (4)
C8—C6—C7—C2	176.2 (2)	C22—C21—C23—N9	82.7 (4)
C3—C2—C7—C6	0.2 (4)	C20—C19—C24—C25	−85.8 (3)
C1—C2—C7—C6	−175.8 (2)	C18—C19—C24—C25	90.9 (3)
C7—C6—C8—C9	−85.6 (3)	C19—C24—C25—C30	94.2 (3)
C5—C6—C8—C9	90.8 (3)	C19—C24—C25—C26	−85.9 (3)
C6—C8—C9—C14	89.9 (3)	C30—C25—C26—O4	176.4 (2)
C6—C8—C9—C10	−88.7 (3)	C24—C25—C26—O4	−3.5 (4)
C14—C9—C10—O2	178.6 (2)	C30—C25—C26—C27	−1.3 (4)
C8—C9—C10—O2	−2.8 (4)	C24—C25—C26—C27	178.8 (2)
C14—C9—C10—C11	−0.4 (4)	O4—C26—C27—C28	−176.7 (2)
C8—C9—C10—C11	178.3 (2)	C25—C26—C27—C28	1.1 (4)
O2—C10—C11—C12	−179.6 (2)	O4—C26—C27—C32	4.8 (4)
C9—C10—C11—C12	−0.6 (4)	C25—C26—C27—C32	−177.4 (2)
O2—C10—C11—C16	3.9 (4)	C26—C27—C28—C29	−0.2 (4)
C9—C10—C11—C16	−177.0 (2)	C32—C27—C28—C29	178.3 (2)
C10—C11—C12—C13	0.4 (4)	C27—C28—C29—C30	−0.4 (4)
C16—C11—C12—C13	176.9 (3)	C27—C28—C29—C31	178.6 (3)
C11—C12—C13—C14	0.7 (4)	C28—C29—C30—C25	0.2 (4)
C11—C12—C13—C15	−177.5 (3)	C31—C29—C30—C25	−178.8 (3)
C10—C9—C14—C13	1.6 (4)	C26—C25—C30—C29	0.7 (4)
C8—C9—C14—C13	−177.1 (3)	C24—C25—C30—C29	−179.4 (2)
C12—C13—C14—C9	−1.8 (4)	C28—C29—C31—N6	115.2 (3)
C15—C13—C14—C9	176.4 (3)	C30—C29—C31—N6	−65.8 (4)
C12—C13—C15—N12	103.5 (4)	C3—C4—C32—C27	84.8 (3)
C14—C13—C15—N12	−74.7 (4)	C5—C4—C32—C27	−92.4 (3)
C12—C11—C16—C17	−88.7 (3)	C28—C27—C32—C4	−92.4 (3)
C10—C11—C16—C17	87.6 (3)	C26—C27—C32—C4	86.0 (3)
C11—C16—C17—C22	84.9 (3)	C2—C1—N3—N2	63.8 (4)
C11—C16—C17—C18	−91.6 (3)	C29—C31—N6—N5	−114.2 (3)
C22—C17—C18—O3	179.4 (2)	N7—N8—N9—C23	166 (2)
C16—C17—C18—O3	−4.0 (4)	O5—C23—N9—N8	45.0 (12)
C22—C17—C18—C19	−0.3 (4)	C21—C23—N9—N8	−68.6 (5)
C16—C17—C18—C19	176.3 (2)	C13—C15—N12—N11	68.0 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2	0.82	1.88	2.695 (3)	172
O4—H4···O3	0.82	1.88	2.687 (3)	170
O1—H1···O4	0.82	1.88	2.690 (3)	167
O2—H2···O1	0.82	1.92	2.726 (3)	169
C20—H20···N12^i	0.93	2.66	3.472 (4)	146
C15—H15A···N7^ii	0.97	2.43	3.346 (5)	157
C32—H32A···N4^iii	0.97	2.64	3.386 (5)	134

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

(II) 5,11,17,23-tetra-tert-butyl-25,27-bis(chloroacetoxy)- 26,28-bis(2-pyridylmethoxy)calix[4]arene

Crystal data

C60H68Cl2N2O6	Dx = 1.147 Mg m^−3
Mr = 984.06	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 6800 reflections
a = 19.280 (3) Å	θ = 2.3–21.6°
b = 21.358 (4) Å	µ = 0.16 mm^−1
c = 27.670 (5) Å	T = 173 K
V = 11394 (3) Å^3	Block, colourless
Z = 8	0.45 × 0.21 × 0.15 mm
F(000) = 4192

Data collection

Bruker SMART CCD area-detector diffractometer	10602 independent reflections
Radiation source: fine-focus sealed tube	6355 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.082
phi and ω scans	θmax = 25.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −23→17
Tmin = 0.930, Tmax = 0.976	k = −25→25
57503 measured reflections	l = −27→33

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.192	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.097P)^2 + 2.1062P] where P = (Fo^2 + 2Fc^2)/3
10602 reflections	(Δ/σ)max = 0.005
729 parameters	Δρmax = 0.65 e Å^−3
219 restraints	Δρmin = −0.39 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	Occ. (<1)
C1	0.27395 (12)	0.37545 (14)	0.42051 (10)	0.0895 (6)	0.5554 (13)
H1A	0.2778	0.3320	0.4316	0.134*	0.5554 (13)
H1B	0.2503	0.3765	0.3892	0.134*	0.5554 (13)
H1C	0.2473	0.3998	0.4441	0.134*	0.5554 (13)
C2	0.33282 (16)	0.47384 (10)	0.40101 (10)	0.0900 (8)	0.5554 (13)
H2A	0.3069	0.4945	0.4269	0.135*	0.5554 (13)
H2B	0.3058	0.4753	0.3710	0.135*	0.5554 (13)
H2C	0.3772	0.4954	0.3962	0.135*	0.5554 (13)
C3	0.38874 (15)	0.39897 (17)	0.46104 (8)	0.0942 (7)	0.5554 (13)
H3A	0.3629	0.4180	0.4878	0.141*	0.5554 (13)
H3B	0.4329	0.4210	0.4568	0.141*	0.5554 (13)
H3C	0.3977	0.3548	0.4683	0.141*	0.5554 (13)
C1'	0.38924 (18)	0.45015 (15)	0.44644 (11)	0.0946 (9)	0.4446 (13)
H1'1	0.3883	0.4917	0.4314	0.142*	0.4446 (13)
H1'2	0.4373	0.4355	0.4487	0.142*	0.4446 (13)
H1'3	0.3690	0.4526	0.4789	0.142*	0.4446 (13)
C2'	0.3367 (2)	0.34994 (14)	0.45394 (9)	0.0904 (7)	0.4446 (13)
H2'1	0.3204	0.3681	0.4844	0.136*	0.4446 (13)
H2'2	0.3811	0.3287	0.4593	0.136*	0.4446 (13)
H2'3	0.3025	0.3197	0.4420	0.136*	0.4446 (13)
C3'	0.27429 (13)	0.42358 (18)	0.40034 (12)	0.0926 (7)	0.4446 (13)
H3'1	0.2504	0.3882	0.3852	0.139*	0.4446 (13)
H3'2	0.2774	0.4583	0.3773	0.139*	0.4446 (13)
H3'3	0.2483	0.4371	0.4289	0.139*	0.4446 (13)
C4	0.34671 (6)	0.40374 (6)	0.41527 (4)	0.0567 (4)
C5	0.38737 (6)	0.37502 (6)	0.37349 (4)	0.0424 (4)
C6	0.45232 (6)	0.39737 (5)	0.36099 (4)	0.0410 (4)
H6	0.4727	0.4292	0.3803	0.049*
C7	0.48890 (6)	0.37492 (5)	0.32112 (4)	0.0358 (3)
C8	0.45675 (6)	0.32964 (5)	0.29307 (4)	0.0328 (3)
C9	0.39628 (6)	0.30022 (5)	0.30749 (4)	0.0351 (3)
C10	0.36242 (6)	0.32520 (5)	0.34761 (4)	0.0373 (3)
H10	0.3199	0.3067	0.3575	0.045*
C11	0.37162 (6)	0.23968 (5)	0.28397 (4)	0.0369 (3)
H11A	0.3207	0.2359	0.2875	0.044*
H11B	0.3828	0.2403	0.2490	0.044*
C12	0.40692 (5)	0.18390 (5)	0.30783 (4)	0.0312 (3)
C13	0.39348 (6)	0.17075 (5)	0.35611 (4)	0.0362 (3)
H13	0.3605	0.1956	0.3729	0.043*
C14	0.42663 (6)	0.12237 (5)	0.38094 (4)	0.0354 (3)
C15	0.40669 (7)	0.10824 (6)	0.43342 (4)	0.0502 (4)
C16	0.33079 (9)	0.08601 (9)	0.43500 (6)	0.0931 (6)
H16A	0.3274	0.0442	0.4206	0.140*
H16B	0.3017	0.1153	0.4168	0.140*
H16C	0.3150	0.0844	0.4686	0.140*
C17	0.41044 (10)	0.16788 (7)	0.46416 (5)	0.0826 (6)
H17A	0.3963	0.1583	0.4974	0.124*
H17B	0.3793	0.1996	0.4506	0.124*
H17C	0.4581	0.1839	0.4641	0.124*
C18	0.45294 (11)	0.05901 (9)	0.45582 (6)	0.1245 (8)
H18A	0.4506	0.0205	0.4366	0.187*
H18B	0.4373	0.0503	0.4888	0.187*
H18C	0.5009	0.0743	0.4566	0.187*
C19	0.47492 (6)	0.08790 (5)	0.35545 (4)	0.0339 (3)
H19	0.4994	0.0557	0.3718	0.041*
C20	0.48918 (5)	0.09821 (5)	0.30711 (4)	0.0299 (3)
C21	0.45332 (6)	0.14606 (5)	0.28322 (4)	0.0300 (3)
C22	0.41721 (6)	0.12021 (6)	0.20468 (4)	0.0448 (4)
H22C	0.4223	0.0749	0.2111	0.054*	0.5165 (13)
H22D	0.3688	0.1326	0.2118	0.054*	0.5165 (13)
H22A	0.3688	0.1281	0.2148	0.054*	0.4835 (13)
H22B	0.4268	0.0748	0.2073	0.054*	0.4835 (13)
C23	0.43374 (12)	0.13369 (11)	0.15553 (8)	0.0615 (4)	0.5165 (13)
C24	0.47668 (14)	0.09230 (13)	0.13104 (8)	0.0693 (5)	0.5165 (13)
H24	0.4935	0.0554	0.1462	0.083*	0.5165 (13)
C25	0.49456 (15)	0.10698 (11)	0.08260 (9)	0.0767 (5)	0.5165 (13)
H25A	0.5227	0.0797	0.0638	0.092*	0.5165 (13)
C26	0.46964 (14)	0.16200 (11)	0.06398 (8)	0.0751 (5)	0.5165 (13)
H26A	0.4835	0.1740	0.0324	0.090*	0.5165 (13)
C27	0.42547 (14)	0.20051 (13)	0.08921 (7)	0.0717 (5)	0.5165 (13)
H27A	0.4077	0.2375	0.0747	0.086*	0.5165 (13)
N2	0.40769 (11)	0.18499 (11)	0.13483 (6)	0.0662 (4)	0.5165 (13)
C23'	0.42926 (16)	0.14275 (16)	0.15228 (9)	0.0605 (4)	0.4835 (13)
C24'	0.46313 (16)	0.11110 (17)	0.11663 (9)	0.0684 (5)	0.4835 (13)
H24'	0.4847	0.0724	0.1246	0.082*	0.4835 (13)
C25'	0.46776 (18)	0.13197 (17)	0.07018 (11)	0.0766 (5)	0.4835 (13)
H25B	0.4869	0.1074	0.0449	0.092*	0.4835 (13)
C26'	0.44179 (17)	0.19318 (17)	0.06260 (11)	0.0755 (5)	0.4835 (13)
H26B	0.4467	0.2117	0.0316	0.091*	0.4835 (13)
C27'	0.40720 (16)	0.22936 (17)	0.10144 (10)	0.0712 (5)	0.4835 (13)
H27B	0.3890	0.2699	0.0952	0.085*	0.4835 (13)
N2'	0.40208 (13)	0.20336 (13)	0.14599 (8)	0.0648 (4)	0.4835 (13)
C29	0.54527 (6)	0.05932 (5)	0.28236 (4)	0.0330 (3)
H29A	0.5346	0.0142	0.2858	0.040*
H29B	0.5468	0.0695	0.2475	0.040*
C30	0.61448 (6)	0.07369 (5)	0.30539 (4)	0.0296 (3)
C31	0.64430 (6)	0.03450 (5)	0.33961 (4)	0.0320 (3)
H31	0.6228	−0.0046	0.3464	0.038*
C32	0.70397 (6)	0.05041 (5)	0.36404 (4)	0.0321 (3)
C33	0.73387 (6)	0.10879 (5)	0.35397 (4)	0.0333 (3)
H33	0.7743	0.1209	0.3712	0.040*
C34	0.70679 (5)	0.14937 (5)	0.32001 (4)	0.0292 (3)
C35	0.64811 (5)	0.12994 (5)	0.29578 (4)	0.0287 (3)
C36	0.73591 (6)	0.00799 (5)	0.40259 (4)	0.0432 (4)
C37	0.70933 (9)	−0.05835 (7)	0.40024 (6)	0.1027 (6)
H37A	0.7219	−0.0769	0.3690	0.154*
H37B	0.6587	−0.0583	0.4037	0.154*
H37C	0.7301	−0.0830	0.4264	0.154*
C38	0.81332 (8)	0.00612 (8)	0.39791 (7)	0.1034 (6)
H38A	0.8325	−0.0229	0.4219	0.155*
H38B	0.8323	0.0481	0.4034	0.155*
H38C	0.8259	−0.0081	0.3654	0.155*
C39	0.71857 (12)	0.03580 (8)	0.45221 (5)	0.1144 (8)
H39A	0.6681	0.0392	0.4557	0.172*
H39B	0.7395	0.0774	0.4550	0.172*
H39C	0.7370	0.0085	0.4776	0.172*
C40	0.64913 (7)	0.17189 (5)	0.21712 (4)	0.0410 (4)
C41	0.60600 (7)	0.21265 (6)	0.18484 (4)	0.0423 (4)
H41A	0.5967	0.2529	0.2014	0.051*
H41B	0.5609	0.1919	0.1788	0.051*
C42	0.73754 (6)	0.21369 (5)	0.31144 (4)	0.0333 (3)
H42A	0.7382	0.2226	0.2763	0.040*
H42B	0.7860	0.2145	0.3233	0.040*
C43	0.69560 (5)	0.26366 (5)	0.33726 (4)	0.0309 (3)
C44	0.69381 (6)	0.26339 (5)	0.38727 (4)	0.0338 (3)
H44	0.7218	0.2340	0.4040	0.041*
C45	0.65298 (6)	0.30414 (5)	0.41403 (4)	0.0352 (3)
C46	0.64951 (7)	0.29977 (6)	0.46890 (4)	0.0452 (4)
C47	0.59420 (11)	0.25230 (8)	0.48189 (6)	0.1198 (7)
H47A	0.5884	0.2511	0.5171	0.180*
H47B	0.6082	0.2108	0.4703	0.180*
H47C	0.5502	0.2643	0.4667	0.180*
C48	0.71944 (9)	0.28010 (10)	0.48994 (5)	0.1028 (7)
H48A	0.7558	0.3080	0.4777	0.154*
H48B	0.7297	0.2369	0.4803	0.154*
H48C	0.7177	0.2828	0.5253	0.154*
C49	0.63195 (10)	0.36182 (8)	0.49275 (5)	0.0783 (6)
H49A	0.6657	0.3936	0.4827	0.117*
H49B	0.6336	0.3570	0.5280	0.117*
H49C	0.5853	0.3749	0.4830	0.117*
C50	0.61199 (6)	0.34576 (5)	0.38780 (4)	0.0348 (3)
H50	0.5825	0.3734	0.4051	0.042*
C51	0.61214 (6)	0.34878 (5)	0.33771 (4)	0.0306 (3)
C52	0.65562 (6)	0.30813 (5)	0.31282 (4)	0.0288 (3)
O2	0.65609 (4)	0.30856 (3)	0.26247 (2)	0.0321 (2)
C53	0.71757 (6)	0.33499 (5)	0.24075 (4)	0.0339 (3)
H53A	0.7291	0.3115	0.2110	0.041*
H53B	0.7570	0.3309	0.2634	0.041*
C54	0.70710 (6)	0.40284 (5)	0.22849 (4)	0.0290 (3)
C55	0.74836 (7)	0.44927 (5)	0.24704 (4)	0.0438 (4)
H55	0.7851	0.4394	0.2686	0.053*
C56	0.73564 (8)	0.51019 (6)	0.23396 (5)	0.0582 (5)
H56	0.7633	0.5431	0.2467	0.070*
C57	0.68322 (7)	0.52330 (6)	0.20262 (4)	0.0488 (4)
H57	0.6739	0.5651	0.1928	0.059*
C58	0.64483 (7)	0.47493 (5)	0.18592 (4)	0.0462 (4)
H58	0.6080	0.4842	0.1642	0.055*
N1	0.65524 (5)	0.41467 (4)	0.19793 (3)	0.0406 (3)
C59	0.56322 (6)	0.39393 (5)	0.31181 (4)	0.0352 (3)
H59A	0.5710	0.4371	0.3237	0.042*
H59B	0.5727	0.3932	0.2766	0.042*
C60	0.46480 (7)	0.35110 (6)	0.21107 (4)	0.0435 (4)
C61	0.50687 (7)	0.33853 (6)	0.16687 (4)	0.0476 (4)
H61A	0.5015	0.2940	0.1576	0.057*
H61B	0.5565	0.3459	0.1742	0.057*
Cl1	0.48204 (2)	0.386347 (19)	0.117946 (13)	0.07868 (14)
Cl2	0.64671 (2)	0.22763 (2)	0.129509 (12)	0.07814 (14)
O1	0.61772 (4)	0.16970 (3)	0.26075 (2)	0.0313 (2)
O3	0.46492 (4)	0.15558 (3)	0.23417 (2)	0.0345 (2)
O4	0.48723 (4)	0.31410 (3)	0.24811 (2)	0.0353 (2)
O5	0.70226 (5)	0.14692 (4)	0.20739 (3)	0.0690 (3)
O6	0.41963 (5)	0.38855 (5)	0.21474 (3)	0.0763 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0852 (12)	0.1191 (12)	0.0641 (11)	0.0226 (11)	0.0303 (10)	−0.0249 (11)
C2	0.0948 (14)	0.0973 (14)	0.0778 (13)	0.0492 (12)	0.0320 (12)	−0.0209 (12)
C3	0.0965 (12)	0.1340 (12)	0.0523 (10)	0.0239 (12)	0.0151 (10)	−0.0239 (11)
C1'	0.1012 (17)	0.1250 (17)	0.0577 (14)	0.0147 (16)	0.0212 (14)	−0.0407 (14)
C2'	0.0936 (13)	0.1263 (13)	0.0515 (11)	0.0178 (12)	0.0276 (11)	−0.0251 (12)
C3'	0.0901 (13)	0.1139 (13)	0.0737 (12)	0.0411 (12)	0.0241 (12)	−0.0232 (12)
C4	0.0517 (8)	0.0717 (9)	0.0467 (7)	0.0125 (7)	0.0069 (6)	−0.0151 (7)
C5	0.0412 (7)	0.0432 (7)	0.0428 (6)	0.0108 (6)	0.0021 (5)	−0.0046 (5)
C6	0.0424 (7)	0.0357 (6)	0.0448 (6)	0.0098 (6)	−0.0041 (6)	−0.0092 (5)
C7	0.0389 (6)	0.0293 (5)	0.0392 (6)	0.0074 (5)	−0.0013 (5)	0.0024 (5)
C8	0.0347 (6)	0.0326 (6)	0.0313 (5)	0.0095 (5)	−0.0005 (5)	−0.0014 (5)
C9	0.0337 (6)	0.0336 (6)	0.0378 (6)	0.0085 (5)	−0.0077 (5)	0.0000 (5)
C10	0.0277 (6)	0.0451 (6)	0.0391 (6)	0.0069 (5)	0.0028 (5)	0.0016 (5)
C11	0.0265 (6)	0.0426 (6)	0.0416 (6)	0.0036 (5)	−0.0048 (5)	−0.0022 (5)
C12	0.0237 (5)	0.0317 (6)	0.0383 (6)	−0.0058 (5)	−0.0051 (5)	−0.0038 (5)
C13	0.0304 (6)	0.0373 (6)	0.0409 (6)	−0.0017 (5)	0.0029 (5)	−0.0061 (5)
C14	0.0347 (6)	0.0370 (6)	0.0344 (6)	−0.0061 (5)	0.0001 (5)	−0.0024 (5)
C15	0.0596 (8)	0.0543 (7)	0.0365 (6)	−0.0045 (7)	0.0087 (6)	0.0026 (6)
C16	0.1004 (12)	0.1120 (12)	0.0668 (10)	−0.0431 (11)	0.0255 (9)	0.0066 (9)
C17	0.1086 (13)	0.0929 (11)	0.0463 (8)	−0.0146 (11)	0.0107 (9)	−0.0130 (8)
C18	0.1755 (18)	0.1456 (14)	0.0525 (9)	0.0825 (13)	0.0431 (10)	0.0468 (9)
C19	0.0328 (6)	0.0300 (5)	0.0390 (6)	−0.0037 (5)	−0.0067 (5)	0.0029 (5)
C20	0.0261 (6)	0.0289 (5)	0.0348 (6)	−0.0050 (5)	−0.0022 (5)	−0.0029 (5)
C21	0.0278 (6)	0.0320 (6)	0.0304 (5)	−0.0042 (5)	−0.0015 (5)	−0.0020 (5)
C22	0.0401 (7)	0.0562 (7)	0.0381 (6)	−0.0033 (6)	−0.0078 (5)	−0.0096 (6)
C23	0.0458 (8)	0.1063 (8)	0.0323 (7)	−0.0159 (8)	0.0004 (7)	−0.0091 (7)
C24	0.0585 (9)	0.1109 (9)	0.0384 (8)	−0.0130 (9)	0.0038 (8)	−0.0147 (8)
C25	0.0659 (9)	0.1202 (9)	0.0439 (8)	−0.0111 (9)	0.0071 (8)	−0.0111 (8)
C26	0.0665 (9)	0.1178 (9)	0.0409 (8)	−0.0121 (9)	0.0047 (8)	−0.0039 (8)
C27	0.0614 (8)	0.1176 (8)	0.0362 (7)	−0.0109 (8)	0.0034 (7)	0.0003 (8)
N2	0.0539 (7)	0.1138 (8)	0.0309 (7)	−0.0100 (8)	0.0001 (7)	0.0019 (7)
C23'	0.0464 (8)	0.1042 (8)	0.0310 (7)	−0.0137 (8)	0.0008 (7)	−0.0061 (8)
C24'	0.0583 (8)	0.1127 (8)	0.0341 (8)	−0.0129 (8)	0.0023 (7)	−0.0106 (8)
C25'	0.0683 (9)	0.1200 (9)	0.0415 (8)	−0.0126 (9)	0.0007 (8)	−0.0021 (9)
C26'	0.0665 (9)	0.1214 (9)	0.0386 (8)	−0.0143 (9)	0.0011 (8)	0.0000 (9)
C27'	0.0612 (9)	0.1160 (9)	0.0363 (8)	−0.0141 (9)	0.0024 (8)	0.0050 (9)
N2'	0.0534 (8)	0.1083 (8)	0.0328 (7)	−0.0127 (8)	−0.0019 (7)	0.0030 (7)
C29	0.0391 (6)	0.0259 (5)	0.0341 (6)	−0.0002 (5)	−0.0021 (5)	0.0004 (5)
C30	0.0323 (6)	0.0266 (5)	0.0300 (5)	0.0038 (5)	0.0036 (5)	0.0009 (4)
C31	0.0306 (6)	0.0246 (5)	0.0409 (6)	0.0011 (5)	0.0065 (5)	0.0052 (5)
C32	0.0304 (6)	0.0310 (6)	0.0349 (6)	0.0023 (5)	0.0030 (5)	0.0064 (5)
C33	0.0270 (6)	0.0353 (6)	0.0375 (6)	0.0064 (5)	−0.0002 (5)	0.0058 (5)
C34	0.0275 (5)	0.0239 (5)	0.0362 (5)	0.0035 (5)	0.0089 (5)	0.0038 (5)
C35	0.0292 (6)	0.0293 (5)	0.0276 (5)	0.0088 (5)	0.0058 (4)	0.0043 (4)
C36	0.0409 (7)	0.0409 (6)	0.0477 (6)	0.0032 (6)	−0.0053 (6)	0.0190 (5)
C37	0.1125 (12)	0.0513 (8)	0.1444 (13)	−0.0224 (9)	−0.0728 (10)	0.0514 (8)
C38	0.0501 (9)	0.0971 (10)	0.1631 (14)	0.0118 (9)	−0.0173 (9)	0.0858 (9)
C39	0.190 (2)	0.1005 (12)	0.0529 (9)	0.0443 (14)	−0.0048 (11)	0.0324 (8)
C40	0.0507 (7)	0.0349 (6)	0.0374 (6)	0.0110 (6)	0.0067 (6)	0.0063 (5)
C41	0.0508 (7)	0.0436 (6)	0.0324 (6)	0.0020 (6)	−0.0016 (6)	0.0077 (5)
C42	0.0286 (6)	0.0290 (5)	0.0424 (6)	0.0017 (5)	0.0069 (5)	0.0059 (5)
C43	0.0268 (6)	0.0242 (5)	0.0415 (6)	−0.0030 (5)	0.0033 (5)	0.0053 (5)
C44	0.0306 (6)	0.0301 (6)	0.0406 (6)	−0.0007 (5)	−0.0022 (5)	0.0098 (5)
C45	0.0335 (6)	0.0339 (6)	0.0381 (6)	−0.0067 (5)	0.0002 (5)	0.0031 (5)
C46	0.0550 (8)	0.0456 (7)	0.0351 (6)	−0.0063 (6)	0.0018 (6)	0.0062 (5)
C47	0.1737 (16)	0.1305 (13)	0.0552 (10)	−0.0993 (11)	0.0172 (10)	0.0104 (9)
C48	0.1011 (13)	0.1614 (17)	0.0458 (9)	0.0450 (12)	−0.0226 (9)	−0.0127 (10)
C49	0.1213 (14)	0.0774 (10)	0.0361 (7)	0.0087 (10)	0.0149 (8)	−0.0002 (7)
C50	0.0328 (6)	0.0319 (6)	0.0396 (6)	−0.0013 (5)	0.0055 (5)	−0.0039 (5)
C51	0.0279 (6)	0.0239 (5)	0.0400 (6)	−0.0013 (5)	0.0000 (5)	0.0006 (5)
C52	0.0298 (6)	0.0250 (5)	0.0317 (5)	−0.0082 (5)	0.0019 (5)	0.0023 (4)
O2	0.0340 (4)	0.0277 (4)	0.0346 (4)	−0.0016 (3)	0.0035 (3)	0.0035 (3)
C53	0.0344 (6)	0.0300 (6)	0.0375 (6)	0.0022 (5)	0.0086 (5)	0.0058 (5)
C54	0.0299 (6)	0.0291 (5)	0.0280 (5)	0.0026 (5)	0.0036 (4)	0.0045 (4)
C55	0.0458 (7)	0.0389 (6)	0.0467 (6)	−0.0094 (6)	−0.0131 (6)	0.0087 (6)
C56	0.0680 (9)	0.0356 (7)	0.0710 (9)	−0.0154 (7)	−0.0138 (7)	0.0005 (6)
C57	0.0604 (8)	0.0300 (6)	0.0559 (7)	0.0065 (6)	0.0027 (7)	0.0089 (6)
C58	0.0483 (7)	0.0412 (6)	0.0492 (7)	0.0108 (6)	−0.0061 (6)	0.0115 (6)
N1	0.0441 (6)	0.0340 (5)	0.0438 (5)	0.0021 (5)	−0.0086 (5)	0.0046 (4)
C59	0.0374 (6)	0.0266 (5)	0.0415 (6)	0.0043 (5)	0.0022 (5)	−0.0012 (5)
C60	0.0468 (7)	0.0439 (7)	0.0397 (6)	0.0141 (6)	−0.0034 (6)	0.0028 (5)
C61	0.0546 (8)	0.0479 (7)	0.0401 (6)	0.0115 (6)	−0.0048 (6)	0.0048 (6)
Cl1	0.0960 (3)	0.0909 (3)	0.04915 (19)	0.0336 (2)	−0.00049 (19)	0.02293 (18)
Cl2	0.0995 (3)	0.0951 (3)	0.03986 (18)	0.0199 (2)	0.01232 (19)	0.02296 (18)
O1	0.0331 (4)	0.0306 (4)	0.0302 (4)	0.0074 (3)	0.0010 (3)	0.0073 (3)
O3	0.0336 (4)	0.0414 (4)	0.0284 (4)	−0.0005 (4)	−0.0046 (3)	−0.0009 (3)
O4	0.0392 (4)	0.0330 (4)	0.0336 (4)	0.0105 (4)	0.0014 (3)	0.0011 (3)
O5	0.0833 (6)	0.0756 (6)	0.0481 (5)	0.0410 (5)	0.0232 (5)	0.0158 (5)
O6	0.0908 (7)	0.0826 (6)	0.0554 (5)	0.0579 (5)	0.0096 (5)	0.0175 (5)

Geometric parameters (Å, º)

C1—C4	1.534 (3)	C26'—C27'	1.482 (4)
C1—H1A	0.9800	C26'—H26B	0.9500
C1—H1B	0.9800	C27'—N2'	1.355 (4)
C1—H1C	0.9800	C27'—H27B	0.9500
C2—C4	1.571 (2)	C29—C30	1.5104 (15)
C2—H2A	0.9800	C29—H29A	0.9900
C2—H2B	0.9800	C29—H29B	0.9900
C2—H2C	0.9800	C30—C31	1.3883 (15)
C3—C4	1.507 (3)	C30—C35	1.3908 (15)
C3—H3A	0.9800	C31—C32	1.3770 (15)
C3—H3B	0.9800	C31—H31	0.9500
C3—H3C	0.9800	C32—C33	1.4016 (15)
C1'—C4	1.549 (3)	C32—C36	1.5291 (16)
C1'—H1'1	0.9800	C33—C34	1.3809 (15)
C1'—H1'2	0.9800	C33—H33	0.9500
C1'—H1'3	0.9800	C34—C35	1.3788 (15)
C2'—C4	1.582 (3)	C34—C42	1.5150 (14)
C2'—H2'1	0.9800	C35—O1	1.4158 (12)
C2'—H2'2	0.9800	C36—C38	1.499 (2)
C2'—H2'3	0.9800	C36—C37	1.5082 (19)
C3'—C4	1.516 (3)	C36—C39	1.533 (2)
C3'—H3'1	0.9800	C37—H37A	0.9800
C3'—H3'2	0.9800	C37—H37B	0.9800
C3'—H3'3	0.9800	C37—H37C	0.9800
C4—C5	1.5256 (17)	C38—H38A	0.9800
C5—C10	1.3700 (16)	C38—H38B	0.9800
C5—C6	1.3839 (17)	C38—H38C	0.9800
C6—C7	1.3946 (16)	C39—H39A	0.9800
C6—H6	0.9500	C39—H39B	0.9800
C7—C8	1.3863 (15)	C39—H39C	0.9800
C7—C59	1.5113 (16)	C40—O5	1.1859 (16)
C8—C9	1.3834 (16)	C40—O1	1.3513 (13)
C8—O4	1.4153 (13)	C40—C41	1.4992 (17)
C9—C10	1.3939 (16)	C41—Cl2	1.7499 (12)
C9—C11	1.5237 (16)	C41—H41A	0.9900
C10—H10	0.9500	C41—H41B	0.9900
C11—C12	1.5226 (15)	C42—C43	1.5177 (15)
C11—H11A	0.9900	C42—H42A	0.9900
C11—H11B	0.9900	C42—H42B	0.9900
C12—C21	1.3845 (15)	C43—C44	1.3840 (15)
C12—C13	1.3896 (15)	C43—C52	1.3978 (15)
C13—C14	1.3958 (16)	C44—C45	1.3877 (16)
C13—H13	0.9500	C44—H44	0.9500
C14—C19	1.3805 (16)	C45—C50	1.3932 (16)
C14—C15	1.5323 (16)	C45—C46	1.5225 (16)
C15—C18	1.512 (2)	C46—C47	1.514 (2)
C15—C17	1.533 (2)	C46—C49	1.519 (2)
C15—C16	1.539 (2)	C46—C48	1.527 (2)
C16—H16A	0.9800	C47—H47A	0.9800
C16—H16B	0.9800	C47—H47B	0.9800
C16—H16C	0.9800	C47—H47C	0.9800
C17—H17A	0.9800	C48—H48A	0.9800
C17—H17B	0.9800	C48—H48B	0.9800
C17—H17C	0.9800	C48—H48C	0.9800
C18—H18A	0.9800	C49—H49A	0.9800
C18—H18B	0.9800	C49—H49B	0.9800
C18—H18C	0.9800	C49—H49C	0.9800
C19—C20	1.3834 (15)	C50—C51	1.3875 (15)
C19—H19	0.9500	C50—H50	0.9500
C20—C21	1.3997 (15)	C51—C52	1.3896 (15)
C20—C29	1.5258 (15)	C51—C59	1.5275 (15)
C21—O3	1.3903 (12)	C52—O2	1.3931 (12)
C22—C23	1.426 (2)	O2—C53	1.4439 (13)
C22—O3	1.4432 (14)	C53—C54	1.5018 (15)
C22—C23'	1.545 (3)	C53—H53A	0.9900
C22—H22C	0.9900	C53—H53B	0.9900
C22—H22D	0.9900	C54—N1	1.3338 (14)
C22—H22A	0.9900	C54—C55	1.3710 (16)
C22—H22B	0.9900	C55—C56	1.3725 (17)
C23—N2	1.335 (3)	C55—H55	0.9500
C23—C24	1.388 (3)	C56—C57	1.3609 (19)
C24—C25	1.419 (3)	C56—H56	0.9500
C24—H24	0.9500	C57—C58	1.3523 (17)
C25—C26	1.370 (3)	C57—H57	0.9500
C25—H25A	0.9500	C58—N1	1.3444 (15)
C26—C27	1.374 (3)	C58—H58	0.9500
C26—H26A	0.9500	C59—H59A	0.9900
C27—N2	1.349 (3)	C59—H59B	0.9900
C27—H27A	0.9500	C60—O6	1.1869 (16)
C23'—C24'	1.363 (4)	C60—O4	1.3644 (14)
C23'—N2'	1.407 (4)	C60—C61	1.4917 (17)
C24'—C25'	1.363 (4)	C61—Cl1	1.7620 (12)
C24'—H24'	0.9500	C61—H61A	0.9900
C25'—C26'	1.415 (5)	C61—H61B	0.9900
C25'—H25B	0.9500
C4—C1—H1A	109.5	C27'—N2'—C23'	117.5 (3)
C4—C1—H1B	109.5	C30—C29—C20	109.04 (9)
C4—C1—H1C	109.5	C30—C29—H29A	109.9
C4—C2—H2A	109.5	C20—C29—H29A	109.9
C4—C2—H2B	109.5	C30—C29—H29B	109.9
C4—C2—H2C	109.5	C20—C29—H29B	109.9
C4—C3—H3A	109.5	H29A—C29—H29B	108.3
C4—C3—H3B	109.5	C31—C30—C35	117.26 (10)
C4—C3—H3C	109.5	C31—C30—C29	122.08 (9)
C4—C1'—H1'1	109.5	C35—C30—C29	120.45 (9)
C4—C1'—H1'2	109.5	C32—C31—C30	122.14 (10)
H1'1—C1'—H1'2	109.5	C32—C31—H31	118.9
C4—C1'—H1'3	109.5	C30—C31—H31	118.9
H1'1—C1'—H1'3	109.5	C31—C32—C33	117.75 (10)
H1'2—C1'—H1'3	109.5	C31—C32—C36	122.19 (10)
C4—C2'—H2'1	109.5	C33—C32—C36	120.01 (10)
C4—C2'—H2'2	109.5	C34—C33—C32	122.55 (10)
H2'1—C2'—H2'2	109.5	C34—C33—H33	118.7
C4—C2'—H2'3	109.5	C32—C33—H33	118.7
H2'1—C2'—H2'3	109.5	C35—C34—C33	116.89 (9)
H2'2—C2'—H2'3	109.5	C35—C34—C42	121.19 (9)
C4—C3'—H3'1	109.5	C33—C34—C42	121.84 (10)
C4—C3'—H3'2	109.5	C34—C35—C30	123.33 (9)
H3'1—C3'—H3'2	109.5	C34—C35—O1	119.47 (9)
C4—C3'—H3'3	109.5	C30—C35—O1	117.13 (9)
H3'1—C3'—H3'3	109.5	C38—C36—C37	108.04 (12)
H3'2—C3'—H3'3	109.5	C38—C36—C32	110.89 (11)
C3—C4—C5	109.46 (14)	C37—C36—C32	112.94 (11)
C3'—C4—C5	112.28 (15)	C38—C36—C39	107.76 (14)
C3—C4—C1	112.69 (17)	C37—C36—C39	109.18 (12)
C5—C4—C1	112.53 (14)	C32—C36—C39	107.90 (11)
C3'—C4—C1'	117.4 (2)	C36—C37—H37A	109.5
C5—C4—C1'	114.02 (15)	C36—C37—H37B	109.5
C3—C4—C2	111.53 (18)	H37A—C37—H37B	109.5
C5—C4—C2	106.28 (13)	C36—C37—H37C	109.5
C1—C4—C2	104.08 (17)	H37A—C37—H37C	109.5
C3'—C4—C2'	106.0 (2)	H37B—C37—H37C	109.5
C5—C4—C2'	106.44 (14)	C36—C38—H38A	109.5
C1'—C4—C2'	98.79 (18)	C36—C38—H38B	109.5
C10—C5—C6	117.07 (11)	H38A—C38—H38B	109.5
C10—C5—C4	121.87 (11)	C36—C38—H38C	109.5
C6—C5—C4	121.04 (11)	H38A—C38—H38C	109.5
C5—C6—C7	122.47 (11)	H38B—C38—H38C	109.5
C5—C6—H6	118.8	C36—C39—H39A	109.5
C7—C6—H6	118.8	C36—C39—H39B	109.5
C8—C7—C6	117.17 (11)	H39A—C39—H39B	109.5
C8—C7—C59	121.05 (10)	C36—C39—H39C	109.5
C6—C7—C59	121.47 (10)	H39A—C39—H39C	109.5
C9—C8—C7	122.16 (10)	H39B—C39—H39C	109.5
C9—C8—O4	119.80 (9)	O5—C40—O1	125.06 (11)
C7—C8—O4	118.04 (10)	O5—C40—C41	127.23 (11)
C8—C9—C10	116.78 (10)	O1—C40—C41	107.68 (10)
C8—C9—C11	121.69 (10)	C40—C41—Cl2	112.25 (9)
C10—C9—C11	121.25 (10)	C40—C41—H41A	109.2
C5—C10—C9	123.31 (11)	Cl2—C41—H41A	109.2
C5—C10—H10	118.3	C40—C41—H41B	109.2
C9—C10—H10	118.3	Cl2—C41—H41B	109.2
C12—C11—C9	109.83 (9)	H41A—C41—H41B	107.9
C12—C11—H11A	109.7	C34—C42—C43	110.82 (9)
C9—C11—H11A	109.7	C34—C42—H42A	109.5
C12—C11—H11B	109.7	C43—C42—H42A	109.5
C9—C11—H11B	109.7	C34—C42—H42B	109.5
H11A—C11—H11B	108.2	C43—C42—H42B	109.5
C21—C12—C13	118.38 (10)	H42A—C42—H42B	108.1
C21—C12—C11	122.16 (9)	C44—C43—C52	118.22 (10)
C13—C12—C11	119.45 (10)	C44—C43—C42	118.75 (9)
C12—C13—C14	122.50 (10)	C52—C43—C42	122.94 (10)
C12—C13—H13	118.7	C43—C44—C45	123.03 (10)
C14—C13—H13	118.7	C43—C44—H44	118.5
C19—C14—C13	116.89 (10)	C45—C44—H44	118.5
C19—C14—C15	123.25 (10)	C44—C45—C50	116.35 (10)
C13—C14—C15	119.83 (10)	C44—C45—C46	121.23 (10)
C18—C15—C14	112.19 (11)	C50—C45—C46	122.25 (10)
C18—C15—C17	108.82 (12)	C47—C46—C49	108.91 (12)
C14—C15—C17	110.49 (11)	C47—C46—C45	107.98 (11)
C18—C15—C16	109.56 (13)	C49—C46—C45	112.92 (10)
C14—C15—C16	109.04 (11)	C47—C46—C48	110.30 (13)
C17—C15—C16	106.58 (13)	C49—C46—C48	105.72 (12)
C15—C16—H16A	109.5	C45—C46—C48	110.99 (11)
C15—C16—H16B	109.5	C46—C47—H47A	109.5
H16A—C16—H16B	109.5	C46—C47—H47B	109.5
C15—C16—H16C	109.5	H47A—C47—H47B	109.5
H16A—C16—H16C	109.5	C46—C47—H47C	109.5
H16B—C16—H16C	109.5	H47A—C47—H47C	109.5
C15—C17—H17A	109.5	H47B—C47—H47C	109.5
C15—C17—H17B	109.5	C46—C48—H48A	109.5
H17A—C17—H17B	109.5	C46—C48—H48B	109.5
C15—C17—H17C	109.5	H48A—C48—H48B	109.5
H17A—C17—H17C	109.5	C46—C48—H48C	109.5
H17B—C17—H17C	109.5	H48A—C48—H48C	109.5
C15—C18—H18A	109.5	H48B—C48—H48C	109.5
C15—C18—H18B	109.5	C46—C49—H49A	109.5
H18A—C18—H18B	109.5	C46—C49—H49B	109.5
C15—C18—H18C	109.5	H49A—C49—H49B	109.5
H18A—C18—H18C	109.5	C46—C49—H49C	109.5
H18B—C18—H18C	109.5	H49A—C49—H49C	109.5
C14—C19—C20	122.89 (10)	H49B—C49—H49C	109.5
C14—C19—H19	118.6	C51—C50—C45	123.29 (10)
C20—C19—H19	118.6	C51—C50—H50	118.4
C19—C20—C21	118.34 (10)	C45—C50—H50	118.4
C19—C20—C29	119.22 (9)	C50—C51—C52	117.86 (10)
C21—C20—C29	122.39 (9)	C50—C51—C59	119.79 (9)
C12—C21—O3	119.90 (9)	C52—C51—C59	122.30 (9)
C12—C21—C20	120.87 (9)	C51—C52—O2	119.70 (9)
O3—C21—C20	119.23 (9)	C51—C52—C43	121.16 (10)
C23—C22—O3	106.93 (13)	O2—C52—C43	119.00 (9)
O3—C22—C23'	105.77 (14)	C52—O2—C53	115.10 (8)
O3—C22—H22C	110.3	O2—C53—C54	111.16 (9)
C23'—C22—H22C	117.3	O2—C53—H53A	109.4
O3—C22—H22D	110.3	C54—C53—H53A	109.4
C23'—C22—H22D	104.3	O2—C53—H53B	109.4
H22C—C22—H22D	108.6	C54—C53—H53B	109.4
C23—C22—H22A	116.6	H53A—C53—H53B	108.0
O3—C22—H22A	110.6	N1—C54—C55	122.36 (10)
C23—C22—H22B	103.1	N1—C54—C53	115.26 (9)
O3—C22—H22B	110.7	C55—C54—C53	122.38 (10)
H22A—C22—H22B	108.8	C54—C55—C56	118.91 (12)
N2—C23—C24	122.5 (2)	C54—C55—H55	120.5
N2—C23—C22	119.40 (19)	C56—C55—H55	120.5
C24—C23—C22	118.1 (2)	C57—C56—C55	119.72 (12)
C23—C24—C25	117.7 (2)	C57—C56—H56	120.1
C23—C24—H24	121.1	C55—C56—H56	120.1
C25—C24—H24	121.1	C58—C57—C56	117.85 (11)
C26—C25—C24	117.4 (2)	C58—C57—H57	121.1
C26—C25—H25A	121.3	C56—C57—H57	121.1
C24—C25—H25A	121.3	N1—C58—C57	124.42 (12)
C25—C26—C27	122.7 (2)	N1—C58—H58	117.8
C25—C26—H26A	118.7	C57—C58—H58	117.8
C27—C26—H26A	118.7	C54—N1—C58	116.75 (10)
N2—C27—C26	119.0 (2)	C7—C59—C51	109.62 (9)
N2—C27—H27A	120.5	C7—C59—H59A	109.7
C26—C27—H27A	120.5	C51—C59—H59A	109.7
C23—N2—C27	120.5 (2)	C7—C59—H59B	109.7
C24'—C23'—N2'	123.0 (3)	C51—C59—H59B	109.7
C24'—C23'—C22	126.6 (3)	H59A—C59—H59B	108.2
N2'—C23'—C22	110.3 (2)	O6—C60—O4	123.95 (11)
C23'—C24'—C25'	123.5 (3)	O6—C60—C61	126.19 (11)
C23'—C24'—H24'	118.3	O4—C60—C61	109.83 (10)
C25'—C24'—H24'	118.3	C60—C61—Cl1	112.20 (9)
C24'—C25'—C26'	114.7 (3)	C60—C61—H61A	109.2
C24'—C25'—H25B	122.6	Cl1—C61—H61A	109.2
C26'—C25'—H25B	122.6	C60—C61—H61B	109.2
C25'—C26'—C27'	122.2 (3)	Cl1—C61—H61B	109.2
C25'—C26'—H26B	118.9	H61A—C61—H61B	107.9
C27'—C26'—H26B	118.9	C40—O1—C35	116.55 (8)
N2'—C27'—C26'	118.6 (3)	C21—O3—C22	111.90 (8)
N2'—C27'—H27B	120.7	C60—O4—C8	113.13 (8)
C26'—C27'—H27B	120.7
C3—C4—C5—C10	119.95 (18)	C30—C31—C32—C33	1.11 (16)
C3'—C4—C5—C10	−55.2 (2)	C30—C31—C32—C36	178.51 (10)
C1—C4—C5—C10	−6.17 (19)	C31—C32—C33—C34	−1.69 (16)
C1'—C4—C5—C10	168.17 (16)	C36—C32—C33—C34	−179.15 (10)
C2—C4—C5—C10	−119.46 (16)	C32—C33—C34—C35	−0.12 (16)
C2'—C4—C5—C10	60.4 (2)	C32—C33—C34—C42	176.73 (10)
C3—C4—C5—C6	−58.24 (19)	C33—C34—C35—C30	2.65 (16)
C3'—C4—C5—C6	126.63 (19)	C42—C34—C35—C30	−174.22 (10)
C1—C4—C5—C6	175.63 (15)	C33—C34—C35—O1	179.62 (9)
C1'—C4—C5—C6	−10.0 (2)	C42—C34—C35—O1	2.75 (15)
C2—C4—C5—C6	62.34 (17)	C31—C30—C35—C34	−3.19 (16)
C2'—C4—C5—C6	−117.84 (18)	C29—C30—C35—C34	171.69 (10)
C10—C5—C6—C7	5.97 (18)	C31—C30—C35—O1	179.77 (9)
C4—C5—C6—C7	−175.76 (11)	C29—C30—C35—O1	−5.35 (14)
C5—C6—C7—C8	1.60 (17)	C31—C32—C36—C38	138.60 (12)
C5—C6—C7—C59	−172.09 (11)	C33—C32—C36—C38	−44.05 (15)
C6—C7—C8—C9	−10.14 (16)	C31—C32—C36—C37	17.17 (16)
C59—C7—C8—C9	163.59 (10)	C33—C32—C36—C37	−165.48 (12)
C6—C7—C8—O4	169.24 (9)	C31—C32—C36—C39	−103.60 (14)
C59—C7—C8—O4	−17.04 (15)	C33—C32—C36—C39	73.74 (15)
C7—C8—C9—C10	10.45 (16)	O5—C40—C41—Cl2	−5.92 (17)
O4—C8—C9—C10	−168.92 (9)	O1—C40—C41—Cl2	172.30 (8)
C7—C8—C9—C11	−163.60 (10)	C35—C34—C42—C43	76.94 (13)
O4—C8—C9—C11	17.03 (16)	C33—C34—C42—C43	−99.78 (12)
C6—C5—C10—C9	−5.64 (18)	C34—C42—C43—C44	65.41 (13)
C4—C5—C10—C9	176.09 (11)	C34—C42—C43—C52	−111.12 (11)
C8—C9—C10—C5	−2.26 (17)	C52—C43—C44—C45	1.59 (16)
C11—C9—C10—C5	171.82 (11)	C42—C43—C44—C45	−175.11 (10)
C8—C9—C11—C12	84.67 (13)	C43—C44—C45—C50	0.99 (16)
C10—C9—C11—C12	−89.11 (13)	C43—C44—C45—C46	176.50 (10)
C9—C11—C12—C21	−113.94 (11)	C44—C45—C46—C47	−86.20 (15)
C9—C11—C12—C13	64.87 (13)	C50—C45—C46—C47	89.04 (14)
C21—C12—C13—C14	2.19 (17)	C44—C45—C46—C49	153.32 (12)
C11—C12—C13—C14	−176.67 (10)	C50—C45—C46—C49	−31.44 (17)
C12—C13—C14—C19	0.87 (17)	C44—C45—C46—C48	34.81 (16)
C12—C13—C14—C15	−176.87 (11)	C50—C45—C46—C48	−149.95 (13)
C19—C14—C15—C18	8.28 (18)	C44—C45—C50—C51	−1.78 (16)
C13—C14—C15—C18	−174.13 (13)	C46—C45—C50—C51	−177.24 (11)
C19—C14—C15—C17	129.90 (13)	C45—C50—C51—C52	−0.09 (16)
C13—C14—C15—C17	−52.51 (16)	C45—C50—C51—C59	177.38 (10)
C19—C14—C15—C16	−113.27 (14)	C50—C51—C52—O2	178.42 (9)
C13—C14—C15—C16	64.32 (15)	C59—C51—C52—O2	1.01 (15)
C13—C14—C19—C20	−2.23 (17)	C50—C51—C52—C43	2.83 (15)
C15—C14—C19—C20	175.42 (11)	C59—C51—C52—C43	−174.57 (10)
C14—C19—C20—C21	0.49 (16)	C44—C43—C52—C51	−3.56 (15)
C14—C19—C20—C29	177.84 (10)	C42—C43—C52—C51	172.99 (10)
C13—C12—C21—O3	176.24 (9)	C44—C43—C52—O2	−179.18 (9)
C11—C12—C21—O3	−4.94 (15)	C42—C43—C52—O2	−2.63 (15)
C13—C12—C21—C20	−4.00 (16)	C51—C52—O2—C53	108.29 (11)
C11—C12—C21—C20	174.82 (10)	C43—C52—O2—C53	−76.03 (11)
C19—C20—C21—C12	2.73 (16)	C52—O2—C53—C54	−95.31 (10)
C29—C20—C21—C12	−174.53 (10)	O2—C53—C54—N1	−59.23 (12)
C19—C20—C21—O3	−177.51 (9)	O2—C53—C54—C55	121.36 (11)
C29—C20—C21—O3	5.22 (15)	N1—C54—C55—C56	0.40 (18)
O3—C22—C23—N2	−83.8 (2)	C53—C54—C55—C56	179.77 (11)
O3—C22—C23—C24	96.3 (2)	C54—C55—C56—C57	−0.8 (2)
N2—C23—C24—C25	1.9 (4)	C55—C56—C57—C58	0.8 (2)
C22—C23—C24—C25	−178.2 (2)	C56—C57—C58—N1	−0.5 (2)
C23—C24—C25—C26	1.8 (4)	C55—C54—N1—C58	−0.08 (16)
C24—C25—C26—C27	−4.0 (4)	C53—C54—N1—C58	−179.49 (10)
C25—C26—C27—N2	2.5 (4)	C57—C58—N1—C54	0.13 (18)
C24—C23—N2—C27	−3.6 (4)	C8—C7—C59—C51	−84.69 (12)
C22—C23—N2—C27	176.5 (2)	C6—C7—C59—C51	88.77 (12)
C26—C27—N2—C23	1.4 (4)	C50—C51—C59—C7	−64.52 (13)
O3—C22—C23'—C24'	105.1 (3)	C52—C51—C59—C7	112.84 (11)
N2'—C23'—C24'—C25'	−7.1 (5)	O6—C60—C61—Cl1	−0.33 (18)
C22—C23'—C24'—C25'	175.3 (3)	O4—C60—C61—Cl1	−178.46 (8)
C23'—C24'—C25'—C26'	7.3 (5)	O5—C40—O1—C35	−5.76 (16)
C24'—C25'—C26'—C27'	−4.7 (5)	C41—C40—O1—C35	175.97 (9)
C25'—C26'—C27'—N2'	1.8 (5)	C34—C35—O1—C40	77.85 (12)
C26'—C27'—N2'—C23'	−1.0 (4)	C30—C35—O1—C40	−104.99 (11)
C24'—C23'—N2'—C27'	3.5 (4)	C12—C21—O3—C22	−88.99 (12)
C22—C23'—N2'—C27'	−178.6 (2)	C20—C21—O3—C22	91.25 (12)
C19—C20—C29—C30	−64.19 (12)	C23—C22—O3—C21	179.83 (13)
C21—C20—C29—C30	113.05 (11)	C23'—C22—O3—C21	172.00 (14)
C20—C29—C30—C31	100.25 (11)	O6—C60—O4—C8	−6.83 (16)
C20—C29—C30—C35	−74.38 (12)	C61—C60—O4—C8	171.35 (9)
C35—C30—C31—C32	1.20 (16)	C9—C8—O4—C60	91.26 (12)
C29—C30—C31—C32	−173.59 (10)	C7—C8—O4—C60	−88.14 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C41—H41A···O2	0.99	2.36	3.1214 (14)	133
C41—H41B···O3	0.99	2.52	3.2783 (15)	133
C42—H42A···O5	0.99	2.60	3.2842 (15)	127
C61—H61B···N1	0.99	2.49	3.4007 (17)	152
C56—H56···O5^i	0.95	2.56	3.2406 (17)	129

Symmetry code: (i) −x+3/2, y+1/2, z.