1,3-Alternate and partial cone conformers of tetra­methyl (5,11,17,23-tetra-tert-butyl-2,8,14,20-tetra­thia­calix[4]arene-25,26,27,28-tetra­yltetra­oxy)tetra­acetate and tetra­methyl (5,11,17,23-tetra­bromo-2,8,14,20-tetra­thia­calix[4]arene-25,26,27,28-tetra­yltetra­oxy)tetra­acetate

The crystal structures of the two title thia­calix[4]arene derivatives, C₅₂H₆₄O₁₂S₄, (I), and C₃₆H₂₈Br₄O₁₂S₄, (II), are reported. Compound (I) has crystallographic C₂ symmetry and adopts a 1,3-alternate conformation where the four –OCH₂­CO₂Me groups are located alternately above and below the virtual plane (R) defined by the four bridging S atoms. The dihedral angles between the plane (R) and the aromatic rings are 87.17 (7) and 87.60 (8)°. Compound (II) has a partial cone conformation in which the pendant –OCH₂CO₂Me group of the rotated aryl ring is oriented away from the thia­calixarene cavity formed by the other three aryl rings. The dihedral angles between the plane (R) and the aryl rings range from 17.47 (10) to 85.98 (6)°. In the supra­molecular structure of (II), the mol­ecular components are linked into a two-dimensional framework by a combination of C—H...O hydrogen bonds and C—Br...C inter­actions. This study demonstrates the usefulness of these motif-generating ­interactions and thiacalix[4]arene derivatives in crystal engineering.

S1. Comment

Thiacalix[4]arenes have attracted much interest in recent years as useful building blocks for highly preorganized receptors (Kumagai et al., 1997; Shokova & Kovalev, 2003; Lhoták, 2004; Morohashi et al., 2006; Guo et al., 2007). Compared with classical calix[4]arenes, the presence of four bridging S atoms results in differing complexation ability (with S contribution), diverse cavity and conformational behaviour. Among both calix[4]arenes and thiacalix[4]arenes, their ethyl ester derivatives are one of the most versatile intermediates because the acetate group is easily converted into carboxylic acids, amides and other esters. It has been found that the conformational distribution in the exhaustive O-alkylation of calix[4]arenes (Pappalardo et al., 1992; Ferguson et al., 1993, 1994) and thiacalix[4]arenes (Akdas et al., 1999) depends largely upon the reaction conditions, the para substituent of the starting calix[4]arene or thiacalix[4]arene, and the steric requirement of the derivatizing agent. Several crystal stuctures of the ethyl ester derivatives of both calix[4]arenes (McKervey et al., 1985; Genorio et al., 2003) and thiacalix[4]arenes (Iki et al., 1998; Akdas et al., 1999) have been described. We now report the crystal structures of two thiacalix[4]arene methyl ester derivatives, 5,11,17,23-tetra-tert-butyl- and 5,11,17,23-tetrabromo-25,26,27,28-tetrakis[(methoxycarbonyl)methoxy]-2,8,14,20-tetrathiacalix[4]arenes, viz. (I) and (II), respectively.

The two title thiacalix[4]arene compounds, (I) and (II), are shown in Figs. 1 and 2. Structural analysis reveals that (I) adopts a 1,3-alternate conformation in which four OCH₂CO₂Me groups are located alternately above and below the virtual plane (R) defined by four bridging S atoms. Compound (II), where four bromine atoms replace the four tert-butyl groups, has a partial cone conformation in which the pendant OCH₂COMe group of the rotated aryl ring is oriented away from the thiacalixarene cavity made by the other three aryl rings. The geometric parameters of both molecules are comparable to those reported for similar structures (Akdas et al., 1999) and most bond lengths and angles in (I) and (II) are in agreement with the values reported for the 1,3-alternate and partial cone conformers of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(ethoxycarbonyl)methoxy]-2,8,14,20-tetrathiacalix[4]arene, except for some C?O, C—O (methyl) bond lengths (Akdas et al., 1999). In the packing of (I), 1,3-alternate molecules are packed along the b axis, forming a type of a nanotubular array extending in the b direction (Fig. 3).

The conformations of both molecules are defined by the angles which the aromatic rings make with the plane (R). In (I), due to symmetry, the dihedral angles between the plane (R) and the aryl rings consisting of C5–C10 and C18–C23 are 87.17 (7) and 87.60 (8)°, respectively. Two pairs of opposite aromatic rings are almost parallel to each other, with interplanar angles of 4.95 (13) and 5.35 (41)°. In (II), the dihedral angles between the plane (R) and the aromatic rings containing C1–C6, C10–C15, C19–C24 and C28–C33 are 75.73 (7), 82.40 (7), 85.98 (6) and 17.47 (10)°, respectively. The aryl rings C10–C15 and C28–C33 are located with an interplanar angle of 80.65 (9)° but oriented in opposite directions. Moreover, the latter ring is tilted away from the cavity and almost coplanar with the plane (R), at 17.47 (10)° (Fig. 2). The aromatic rings C1–C6 and C19–C24 are almost parallel to one another, with a Br3···Br4 distance of 4.207 (7) Å. The O···O separations of the ethereal O atoms are O1···O4 3.087 (3), O1···O10 3.844 (3), O7···O4 4.718 (3) and O7···O10 4.829 (5) Å.

No classical hydrogen bonds are present in either structure, but a number of intra- and intermolecular short contacts exist in the crystal structure of (II), involving weak C—H···O, C—H···S and C—H···π interactions (Table 1). These stabilize the partial cone conformation and packing. The intramolecular hydrogen bonds C11—H11···O12 and C13—H13···O5, as well as C34—H34A···π interactions, result in a dihedral angle of 82.40 (7)°, smaller than the reported value of 93.5 (4)° (Ferguson et al., 1993) between the plane (R) and the C10–C15 ring. The separation of H34A···Cg1 (the centroid of the C10–C15 ring) is 2.73 Å (Tsuzuki et al., 2000). In the supramolecular structure of (II), hydrogen-bonded one-dimensional chains consisting of an R²₂(8) motif (Bernstein et al., 1995) are formed by a combination of two C—H···O hydrogen bonds (Fig. 4). These one-dimensional chains are further linked into a two-dimensional framework by C—Br···E (E = electrophile; Lommerse et al., 1996; Bosch & Barnes, 2002) interactions. In the first substructure, atoms C25 and C16 at (x, y, z) in the molecule act as hydrogen-bond donors, via H25B and H16A, to atoms O9 at (x + 1, y, z) and O6 at (x - 1, y, z), respectively, thus forming an R²₂(8) motif. An interesting feature of (II) is that such chains are weakly augmented by the uncommon C—Br···C (Santos-Contreras et al., 2007) interactions between Br4 and C29ⁱⁱⁱ, C30ⁱⁱⁱ [symmetry code: (iii) -x + 2, -y + 1, -z + 1]. The Br4···C29ⁱⁱⁱ and Br4···C30ⁱⁱⁱ distances are 3.480 (3) and 3.423 (3) Å, respectively, which are less than the sum of the van der Waals radii for Br and C (C = 1.70 Å, Br = 1.90 Å; Bondi, 1964).

Related literature

For related literature, see: Akdas et al. (1999); Bernstein et al. (1995); Bondi (1964); Bosch & Barnes (2002); Ferguson et al. (1993, 1994); Genorio et al. (2003); Guo et al. (2007); Iki et al. (1998); Kumagai et al. (1997); Lhoták (2004); Lommerse et al. (1996); McKervey et al. (1985); Morohashi et al. (2006); Pappalardo et al. (1992); Santos-Contreras, Martínez-Martínez, García-Báez, Padilla-Martínez, Peraza & Höpfl (2007); Shokova & Kovalev (2003); Thuéry et al. (2000); Tsuzuki et al. (2000).

S2. Experimental

For the synthesis of (I), to a suspension of p-tetra-tert-butylthiacalix[4]arene (0.200 g, 0.28 mmol) and anhydrous Cs₂CO₃ (0.543 g, 1.66 mmol) in dry acetone (15 ml) was added methyl bromoacetate (0.21 ml, 2.22 mmol). The resulting mixture was stirred for 70 h at 343 K and cooled to room temperature. The solvent was removed under reduced pressure. The residue was neutralized with 5% aqueous HCl, and extracted with CH₂Cl₂. The organic layer was separated and washed with saturated sodium hydrogen carbonate and brine, and dried over anhydrous MgSO₄. Removal of the solvent under reduced pressure gave (I) as a white solid (yield 81%) by recrystallization from CH₂Cl₂/CH₃OH solution. ¹H NMR (300 MHz, CDCl₃): δ1.25 (s, 36H, t-Bu), 3.76 (s, 12H, CH₃), 4.56 (s, 8H, CH₂), 7.49 (s, 8H, ArH). IR (KBr pellets, cm^-1): 1770 (C?O). Single crystals of (I) suitable for X-ray diffraction analysis were obtained by slow diffusion of CH₃OH methanol into a CHCL₃ solution at 273 K.

For the synthesis of (II), the same procedure was followed as for (I), but p-tetrabromothiacalix[4]arene was used instead of p-tetra-tert-butylthiacalix[4]arene to afford (II) as a white solid (yield 43%, isolated by flash column chromatography, silica gel, EtOAc/petroleum ether = 1:5, R_f = 0.4). ¹ H NMR (300 MHz, CDCl₃): δ 8.09 (s, 2H, Ar—H), 7.78 (s, 2H, Ar—H), 7.63 (s, 2H, Ar—H), 7.10 (s, 2H, Ar—H), 4.78 (s, 2H, ArOCH₂), 4.68 (s, 2H, ArOCH₂), 4.66 (s, 2H, ArOCH₂), 4.19 (s, 2H, ArOCH₂), 4.09 (s, 3H, OCH₃), 3.86 (s, 6H, OCH₃), 3.62 (s, 3H, OCH₃). Single crystals of (II) suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution in CH₃OH and CH₂Cl₂ at 273 K.

S3. Refinement

All non-H atoms were refined with anisotropic displacement parameters. H atoms were placed in geometrically idealized positions and refined using a riding model. [0.93 (aromatic CH) U_iso(H) = 1.2U_eq(C) and 0.97 Å (methyl CH₃), U_iso(H) = 1.5U_eq(C)]. In (I), some t-butyl groups are disordered (Thuéry et al., 2000) and even at low temperatures (173 K) show a large anisotropic displacement, implying large thermal motion. In the structure of (II), a carbonyl O atom is also disordered and the occupancy factors for O5/O5' are 56%/44%, respectively.

Computing details

For both compounds, data collection: SMART (Bruker, 1999); cell refinement: SMART (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 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A view of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level for non-H atoms.
	Fig. 2. A view of (II)), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level for non-H atoms. The disordered carbonyl group is also shown.
	Fig. 3. A view of the packing of (I), showing the pattern of channels along the b axis.
	Fig. 4. The hydrogen-bonded one-dimensional chains of (II), viewed along the c axis with R^22(8) motifs along [001]. Some H atoms and the disordered carbonyl have been omitted for clarity. Atoms marked with (i) and (ii) are at the symmetry positions (x + 1, y, z) and (x - 1, y, z), respectively.

(I) tetramethyl (5,11,17,23-tetra-tert-butyl-2,8,14,20-tetrathiacalix[4]arene- 25,26,27,28-tetrayltetraoxy)tetraacetate

Crystal data

C52H64O12S4	F(000) = 2144
Mr = 1009.27	Dx = 1.272 Mg m^−3
Monoclinic, C2/c	Melting point: 583 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 23.060 (4) Å	Cell parameters from 3304 reflections
b = 13.547 (2) Å	θ = 2.5–27.1°
c = 20.083 (4) Å	µ = 0.24 mm^−1
β = 122.890 (2)°	T = 173 K
V = 5268.3 (16) Å^3	Block, colourless
Z = 4	0.34 × 0.23 × 0.16 mm

Data collection

CCD area-detector diffractometer	4893 independent reflections
Radiation source: fine-focus sealed tube	3834 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ϕ and ω scans	θmax = 25.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −27→24
Tmin = 0.923, Tmax = 0.963	k = −14→16
13453 measured reflections	l = −24→24

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.164	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0714P)^2 + 12.3991P] where P = (Fo^2 + 2Fc^2)/3
4893 reflections	(Δ/σ)max = 0.001
360 parameters	Δρmax = 0.47 e Å^−3
51 restraints	Δρmin = −0.30 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)
S1	0.99878 (4)	0.21639 (7)	0.44360 (5)	0.0366 (2)
S2	0.79969 (4)	0.23303 (6)	0.12342 (5)	0.0311 (2)
O1	1.1161 (8)	−0.0627 (7)	0.4389 (6)	0.065 (3)	0.47 (3)
O2	1.19587 (16)	−0.0360 (2)	0.56977 (16)	0.0638 (8)
O3	0.8866 (2)	0.5131 (2)	0.2833 (3)	0.0972 (14)
O4	0.82860 (17)	0.49964 (19)	0.3393 (2)	0.0670 (9)
O5	1.10215 (10)	0.13481 (15)	0.41260 (12)	0.0313 (5)
O6	0.90236 (10)	0.31546 (15)	0.28476 (12)	0.0300 (5)
C5	0.89228 (15)	0.0062 (2)	0.27746 (18)	0.0296 (7)
C6	0.85261 (14)	0.0627 (2)	0.20969 (17)	0.0276 (7)
H6	0.8226	0.0311	0.1618	0.033*
C7	0.85638 (14)	0.1646 (2)	0.21130 (17)	0.0260 (6)
C8	0.90054 (14)	0.2136 (2)	0.28239 (17)	0.0262 (6)
C9	0.94319 (15)	0.1580 (2)	0.35053 (17)	0.0276 (7)
C10	0.93877 (15)	0.0562 (2)	0.34727 (17)	0.0293 (7)
H10	0.9677	0.0200	0.3930	0.035*
C11	0.85576 (19)	0.3539 (2)	0.3036 (2)	0.0415 (8)
H11A	0.8677	0.3294	0.3549	0.050*
H11B	0.8092	0.3324	0.2643	0.050*
C12	0.85917 (17)	0.4638 (2)	0.30506 (19)	0.0345 (7)
C13	0.8274 (2)	0.6050 (3)	0.3460 (3)	0.0626 (12)
H13A	0.8721	0.6314	0.3637	0.094*
H13B	0.8154	0.6214	0.3836	0.094*
H13C	0.7938	0.6326	0.2953	0.094*
C16	1.10502 (18)	0.5566 (2)	0.4295 (2)	0.0399 (8)
C15	1.0585 (2)	0.5975 (3)	0.4553 (3)	0.0644 (12)
H15A	1.0112	0.5831	0.4154	0.097*
H15B	1.0646	0.6677	0.4623	0.097*
H15C	1.0704	0.5674	0.5045	0.097*
C17	1.1793 (2)	0.5844 (3)	0.4938 (3)	0.0709 (14)
H17A	1.2098	0.5641	0.4776	0.106*
H17B	1.1922	0.5520	0.5425	0.106*
H17C	1.1825	0.6546	0.5016	0.106*
C18	1.10045 (15)	0.4442 (2)	0.42054 (17)	0.0300 (7)
C19	1.05575 (15)	0.3876 (2)	0.43053 (17)	0.0307 (7)
H19	1.0256	0.4189	0.4409	0.037*
C20	1.05459 (15)	0.2856 (2)	0.42544 (17)	0.0295 (7)
C21	1.09976 (14)	0.2363 (2)	0.41101 (16)	0.0267 (6)
C22	1.14171 (14)	0.2926 (2)	0.39551 (16)	0.0267 (6)
C23	1.14167 (15)	0.3942 (2)	0.40002 (17)	0.0282 (7)
H23	1.1698	0.4305	0.3891	0.034*
C24	1.15612 (18)	0.0996 (3)	0.4874 (2)	0.0452 (9)
H24A	1.1578	0.1386	0.5289	0.054*
H24B	1.1999	0.1076	0.4918	0.054*
C26	1.1938 (3)	−0.1352 (3)	0.5920 (3)	0.0785 (15)
H26A	1.1636	−0.1734	0.5454	0.118*
H26B	1.1772	−0.1360	0.6266	0.118*
H26C	1.2394	−0.1629	0.6190	0.118*
C25	1.14652 (18)	−0.0056 (3)	0.4989 (2)	0.0454 (9)	0.47 (3)
C14	1.0665 (11)	0.5985 (12)	0.3425 (9)	0.058 (4)	0.47 (3)
H14A	1.0191	0.5778	0.3137	0.086*	0.47 (3)
H14B	1.0883	0.5741	0.3164	0.086*	0.47 (3)
H14C	1.0686	0.6693	0.3442	0.086*	0.47 (3)
O1'	1.0953 (7)	−0.0503 (9)	0.4672 (13)	0.098 (8)	0.53 (3)
C25'	1.14652 (18)	−0.0056 (3)	0.4989 (2)	0.0454 (9)	0.53 (3)
C14'	1.0994 (12)	0.6090 (10)	0.3589 (7)	0.069 (4)	0.53 (3)
H14D	1.0537	0.6002	0.3128	0.104*	0.53 (3)
H14E	1.1325	0.5816	0.3492	0.104*	0.53 (3)
H14F	1.1084	0.6782	0.3704	0.104*	0.53 (3)
C1	0.88511 (18)	−0.1059 (2)	0.2783 (2)	0.0443 (9)	0.742 (10)
C2	0.8307 (3)	−0.1480 (4)	0.1996 (3)	0.0489 (17)	0.742 (10)
H2A	0.8445	−0.1399	0.1626	0.073*	0.742 (10)
H2B	0.7878	−0.1141	0.1802	0.073*	0.742 (10)
H2C	0.8249	−0.2169	0.2055	0.073*	0.742 (10)
C4	0.8590 (4)	−0.1265 (4)	0.3352 (4)	0.064 (2)	0.742 (10)
H4A	0.8496	−0.1956	0.3344	0.096*	0.742 (10)
H4B	0.8176	−0.0894	0.3175	0.096*	0.742 (10)
H4C	0.8940	−0.1069	0.3882	0.096*	0.742 (10)
C3	0.9535 (5)	−0.1568 (9)	0.3112 (7)	0.091 (4)	0.742 (10)
H3'1	0.9864	−0.1313	0.3630	0.136*	0.742 (10)
H3'2	0.9697	−0.1451	0.2768	0.136*	0.742 (10)
H3'3	0.9480	−0.2264	0.3146	0.136*	0.742 (10)
C1'	0.88511 (18)	−0.1059 (2)	0.2783 (2)	0.0443 (9)	0.258 (10)
C2'	0.8713 (13)	−0.1437 (14)	0.1982 (8)	0.079 (7)	0.258 (10)
H2'1	0.9090	−0.1249	0.1933	0.119*	0.258 (10)
H2'2	0.8293	−0.1153	0.1555	0.119*	0.258 (10)
H2'3	0.8673	−0.2143	0.1962	0.119*	0.258 (10)
C3'	0.9476 (16)	−0.157 (2)	0.3371 (16)	0.061 (7)	0.258 (10)
H3A	0.9446	−0.2249	0.3224	0.091*	0.258 (10)
H3B	0.9529	−0.1523	0.3879	0.091*	0.258 (10)
H3C	0.9866	−0.1268	0.3401	0.091*	0.258 (10)
C4'	0.8198 (11)	−0.1328 (15)	0.2701 (15)	0.083 (7)	0.258 (10)
H4'1	0.8108	−0.2018	0.2576	0.124*	0.258 (10)
H4'2	0.7828	−0.0946	0.2284	0.124*	0.258 (10)
H4'3	0.8230	−0.1197	0.3190	0.124*	0.258 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0378 (5)	0.0459 (5)	0.0272 (4)	−0.0096 (4)	0.0184 (4)	−0.0075 (3)
S2	0.0215 (4)	0.0300 (4)	0.0335 (4)	−0.0002 (3)	0.0096 (3)	0.0100 (3)
O1	0.070 (6)	0.036 (4)	0.064 (5)	−0.002 (4)	0.021 (4)	−0.006 (3)
O2	0.079 (2)	0.0411 (16)	0.0500 (16)	0.0063 (14)	0.0215 (15)	0.0166 (13)
O3	0.180 (4)	0.0353 (17)	0.170 (4)	−0.001 (2)	0.156 (4)	0.003 (2)
O4	0.099 (2)	0.0302 (14)	0.118 (3)	0.0067 (14)	0.089 (2)	0.0006 (15)
O5	0.0285 (11)	0.0228 (11)	0.0273 (11)	−0.0005 (9)	0.0053 (9)	−0.0026 (9)
O6	0.0326 (11)	0.0235 (11)	0.0393 (12)	−0.0021 (9)	0.0230 (10)	−0.0014 (9)
C5	0.0271 (15)	0.0246 (16)	0.0356 (17)	−0.0006 (12)	0.0160 (14)	0.0035 (13)
C6	0.0236 (15)	0.0274 (16)	0.0251 (15)	−0.0033 (12)	0.0089 (12)	−0.0013 (12)
C7	0.0238 (15)	0.0237 (16)	0.0305 (16)	0.0000 (12)	0.0147 (13)	0.0039 (12)
C8	0.0267 (15)	0.0232 (16)	0.0330 (16)	−0.0027 (12)	0.0191 (13)	−0.0016 (12)
C9	0.0242 (15)	0.0308 (17)	0.0289 (16)	−0.0021 (12)	0.0152 (13)	−0.0006 (13)
C10	0.0243 (15)	0.0345 (18)	0.0269 (15)	0.0018 (13)	0.0125 (13)	0.0074 (13)
C11	0.047 (2)	0.0269 (18)	0.064 (2)	0.0003 (15)	0.0395 (19)	−0.0014 (16)
C12	0.0408 (18)	0.0291 (18)	0.0381 (18)	0.0018 (14)	0.0244 (16)	0.0033 (14)
C13	0.074 (3)	0.030 (2)	0.097 (3)	0.008 (2)	0.056 (3)	−0.005 (2)
C16	0.050 (2)	0.0256 (18)	0.0419 (19)	0.0043 (15)	0.0235 (17)	−0.0071 (14)
C15	0.065 (3)	0.037 (2)	0.090 (3)	0.008 (2)	0.042 (3)	−0.018 (2)
C17	0.062 (3)	0.038 (2)	0.110 (4)	−0.017 (2)	0.045 (3)	−0.035 (2)
C18	0.0278 (15)	0.0278 (17)	0.0235 (15)	0.0028 (13)	0.0068 (13)	−0.0067 (12)
C19	0.0280 (16)	0.0334 (18)	0.0267 (15)	0.0016 (13)	0.0122 (13)	−0.0093 (13)
C20	0.0262 (15)	0.0342 (18)	0.0228 (15)	−0.0033 (13)	0.0098 (13)	−0.0077 (12)
C21	0.0254 (15)	0.0233 (16)	0.0205 (14)	−0.0014 (12)	0.0053 (12)	−0.0061 (12)
C22	0.0205 (14)	0.0273 (16)	0.0218 (14)	0.0009 (12)	0.0047 (12)	−0.0051 (12)
C23	0.0250 (15)	0.0281 (17)	0.0255 (15)	−0.0027 (12)	0.0098 (12)	−0.0050 (12)
C24	0.043 (2)	0.036 (2)	0.0329 (18)	−0.0023 (16)	0.0056 (15)	0.0069 (15)
C26	0.086 (3)	0.052 (3)	0.095 (4)	0.020 (2)	0.048 (3)	0.041 (3)
C25	0.0315 (19)	0.034 (2)	0.052 (2)	0.0028 (15)	0.0102 (17)	0.0070 (17)
C14	0.077 (8)	0.042 (6)	0.061 (6)	0.022 (6)	0.042 (6)	0.013 (5)
O1'	0.052 (6)	0.044 (5)	0.105 (10)	−0.016 (4)	−0.018 (5)	0.031 (6)
C25'	0.0315 (19)	0.034 (2)	0.052 (2)	0.0028 (15)	0.0102 (17)	0.0070 (17)
C14'	0.085 (9)	0.039 (5)	0.057 (6)	0.008 (6)	0.022 (6)	0.009 (4)
C1	0.044 (2)	0.0239 (18)	0.048 (2)	0.0033 (15)	0.0136 (17)	0.0072 (15)
C2	0.058 (4)	0.022 (2)	0.052 (3)	−0.007 (2)	0.020 (3)	−0.003 (2)
C4	0.092 (5)	0.041 (3)	0.058 (4)	−0.022 (3)	0.040 (3)	0.002 (3)
C3	0.064 (5)	0.048 (5)	0.117 (8)	0.018 (3)	0.021 (5)	−0.022 (6)
C1'	0.044 (2)	0.0239 (18)	0.048 (2)	0.0033 (15)	0.0136 (17)	0.0072 (15)
C2'	0.072 (10)	0.047 (8)	0.088 (10)	0.011 (7)	0.023 (7)	0.002 (7)
C3'	0.071 (10)	0.024 (9)	0.062 (10)	0.002 (7)	0.019 (7)	0.013 (7)
C4'	0.070 (10)	0.072 (10)	0.095 (12)	−0.007 (7)	0.037 (8)	0.008 (8)

Geometric parameters (Å, º)

C5—C6	1.387 (4)	C22—C23	1.380 (4)
C5—C10	1.393 (4)	C22—S2^i	1.783 (3)
C5—C1	1.528 (4)	C23—H23	0.9300
C6—C7	1.383 (4)	C24—O5	1.415 (4)
C6—H6	0.9300	C24—C25	1.479 (5)
C7—C8	1.391 (4)	C24—H24A	0.9700
C7—S2	1.782 (3)	C24—H24B	0.9700
C8—O6	1.381 (4)	C26—O2	1.424 (5)
C8—C9	1.395 (4)	C26—H26A	0.9600
C9—C10	1.382 (4)	C26—H26B	0.9600
C9—S1	1.778 (3)	C26—H26C	0.9600
C10—H10	0.9300	O2—C25	1.316 (4)
C11—O6	1.417 (4)	S2—C22^i	1.783 (3)
C11—C12	1.491 (4)	O1—C25	1.275 (10)
C11—H11A	0.9700	C14—H14A	0.9600
C11—H11B	0.9700	C14—H14B	0.9600
C12—O3	1.157 (4)	C14—H14C	0.9600
C12—O4	1.316 (4)	C14'—H14D	0.9600
C13—O4	1.435 (4)	C14'—H14E	0.9600
C13—H13A	0.9600	C14'—H14F	0.9600
C13—H13B	0.9600	C1—C2	1.498 (6)
C13—H13C	0.9600	C1—C3	1.506 (11)
C16—C14'	1.526 (9)	C1—C4	1.578 (6)
C16—C15	1.527 (5)	C2—H2A	0.9600
C16—C18	1.530 (4)	C2—H2B	0.9600
C16—C17	1.530 (5)	C2—H2C	0.9600
C16—C14	1.574 (13)	C4—H4A	0.9600
C15—H15A	0.9600	C4—H4B	0.9600
C15—H15B	0.9600	C4—H4C	0.9600
C15—H15C	0.9600	C3—H3'1	0.9600
C17—H17A	0.9600	C3—H3'2	0.9600
C17—H17B	0.9600	C3—H3'3	0.9600
C17—H17C	0.9600	C2'—H2'1	0.9600
C18—C19	1.384 (4)	C2'—H2'2	0.9600
C18—C23	1.399 (4)	C2'—H2'3	0.9600
C19—C20	1.385 (4)	C3'—H3A	0.9600
C19—H19	0.9300	C3'—H3B	0.9600
C20—C21	1.394 (4)	C3'—H3C	0.9600
C20—S1	1.782 (3)	C4'—H4'1	0.9600
C21—O5	1.376 (3)	C4'—H4'2	0.9600
C21—C22	1.394 (4)	C4'—H4'3	0.9600
C6—C5—C10	117.2 (3)	C23—C22—C21	120.4 (3)
C6—C5—C1	122.8 (3)	C23—C22—S2^i	119.6 (2)
C10—C5—C1	120.0 (3)	C21—C22—S2^i	119.9 (2)
C7—C6—C5	121.9 (3)	C22—C23—C18	121.8 (3)
C7—C6—H6	119.0	C22—C23—H23	119.1
C5—C6—H6	119.0	C18—C23—H23	119.1
C6—C7—C8	120.1 (3)	O5—C24—C25	111.7 (3)
C6—C7—S2	119.5 (2)	O5—C24—H24A	109.3
C8—C7—S2	120.2 (2)	C25—C24—H24A	109.3
O6—C8—C7	120.2 (3)	O5—C24—H24B	109.3
O6—C8—C9	120.9 (3)	C25—C24—H24B	109.3
C7—C8—C9	118.9 (3)	H24A—C24—H24B	107.9
C10—C9—C8	119.9 (3)	O2—C26—H26A	109.5
C10—C9—S1	119.1 (2)	O2—C26—H26B	109.5
C8—C9—S1	120.9 (2)	H26A—C26—H26B	109.5
C9—C10—C5	122.0 (3)	O2—C26—H26C	109.5
C9—C10—H10	119.0	H26A—C26—H26C	109.5
C5—C10—H10	119.0	H26B—C26—H26C	109.5
O6—C11—C12	109.4 (3)	C25—O2—C26	118.6 (3)
O6—C11—H11A	109.8	C12—O4—C13	117.4 (3)
C12—C11—H11A	109.8	C21—O5—C24	111.3 (2)
O6—C11—H11B	109.8	C8—O6—C11	111.3 (2)
C12—C11—H11B	109.8	C9—S1—C20	101.96 (13)
H11A—C11—H11B	108.2	C7—S2—C22^i	102.31 (13)
O3—C12—O4	122.8 (3)	O1—C25—O2	122.7 (5)
O3—C12—C11	127.1 (3)	O1—C25—C24	119.3 (7)
O4—C12—C11	110.0 (3)	O2—C25—C24	110.9 (3)
O4—C13—H13A	109.5	C16—C14—H14A	109.5
O4—C13—H13B	109.5	C16—C14—H14B	109.5
H13A—C13—H13B	109.5	C16—C14—H14C	109.5
O4—C13—H13C	109.5	C16—C14'—H14D	109.5
H13A—C13—H13C	109.5	C16—C14'—H14E	109.5
H13B—C13—H13C	109.5	H14D—C14'—H14E	109.5
C14'—C16—C15	115.2 (8)	C16—C14'—H14F	109.5
C14'—C16—C18	112.9 (6)	H14D—C14'—H14F	109.5
C15—C16—C18	112.6 (3)	H14E—C14'—H14F	109.5
C14'—C16—C17	99.3 (9)	C2—C1—C3	111.4 (5)
C15—C16—C17	107.2 (3)	C2—C1—C5	113.6 (3)
C18—C16—C17	108.6 (3)	C3—C1—C5	111.5 (5)
C15—C16—C14	99.7 (7)	C2—C1—C4	105.5 (4)
C18—C16—C14	105.5 (7)	C3—C1—C4	108.8 (6)
C17—C16—C14	123.1 (9)	C5—C1—C4	105.7 (3)
C16—C15—H15A	109.5	C1—C2—H2A	109.5
C16—C15—H15B	109.5	C1—C2—H2B	109.5
H15A—C15—H15B	109.5	H2A—C2—H2B	109.5
C16—C15—H15C	109.5	C1—C2—H2C	109.5
H15A—C15—H15C	109.5	H2A—C2—H2C	109.5
H15B—C15—H15C	109.5	H2B—C2—H2C	109.5
C16—C17—H17A	109.5	C1—C4—H4A	109.5
C16—C17—H17B	109.5	C1—C4—H4B	109.5
H17A—C17—H17B	109.5	H4A—C4—H4B	109.5
C16—C17—H17C	109.5	C1—C4—H4C	109.5
H17A—C17—H17C	109.5	H4A—C4—H4C	109.5
H17B—C17—H17C	109.5	H4B—C4—H4C	109.5
C19—C18—C23	116.9 (3)	C1—C3—H3'1	109.5
C19—C18—C16	123.0 (3)	C1—C3—H3'2	109.5
C23—C18—C16	120.1 (3)	H3'1—C3—H3'2	109.5
C18—C19—C20	121.9 (3)	C1—C3—H3'3	109.5
C18—C19—H19	119.0	H3'1—C3—H3'3	109.5
C20—C19—H19	119.0	H3'2—C3—H3'3	109.5
C19—C20—C21	120.4 (3)	H2'1—C2'—H2'2	109.5
C19—C20—S1	119.8 (2)	H2'1—C2'—H2'3	109.5
C21—C20—S1	119.7 (2)	H2'2—C2'—H2'3	109.5
O5—C21—C22	121.9 (3)	H4'1—C4'—H4'2	109.5
O5—C21—C20	119.9 (3)	H4'1—C4'—H4'3	109.5
C22—C21—C20	118.2 (3)	H4'2—C4'—H4'3	109.5
C10—C5—C6—C7	−2.8 (4)	S1—C20—C21—C22	178.8 (2)
C1—C5—C6—C7	175.3 (3)	O5—C21—C22—C23	−175.3 (2)
C5—C6—C7—C8	−0.4 (4)	C20—C21—C22—C23	4.5 (4)
C5—C6—C7—S2	−175.7 (2)	O5—C21—C22—S2^i	0.3 (4)
C6—C7—C8—O6	−177.4 (3)	C20—C21—C22—S2^i	−179.9 (2)
S2—C7—C8—O6	−2.1 (4)	C21—C22—C23—C18	0.4 (4)
C6—C7—C8—C9	3.3 (4)	S2^i—C22—C23—C18	−175.2 (2)
S2—C7—C8—C9	178.6 (2)	C19—C18—C23—C22	−4.6 (4)
O6—C8—C9—C10	177.8 (3)	C16—C18—C23—C22	176.5 (3)
C7—C8—C9—C10	−2.9 (4)	O3—C12—O4—C13	2.7 (6)
O6—C8—C9—S1	2.6 (4)	C11—C12—O4—C13	179.8 (3)
C7—C8—C9—S1	−178.1 (2)	C22—C21—O5—C24	83.7 (3)
C8—C9—C10—C5	−0.4 (4)	C20—C21—O5—C24	−96.1 (3)
S1—C9—C10—C5	174.9 (2)	C25—C24—O5—C21	162.3 (3)
C6—C5—C10—C9	3.2 (4)	C7—C8—O6—C11	91.9 (3)
C1—C5—C10—C9	−175.0 (3)	C9—C8—O6—C11	−88.8 (3)
O6—C11—C12—O3	10.9 (6)	C12—C11—O6—C8	−179.7 (3)
O6—C11—C12—O4	−166.0 (3)	C10—C9—S1—C20	122.3 (2)
C14'—C16—C18—C19	−129.0 (10)	C8—C9—S1—C20	−62.5 (3)
C15—C16—C18—C19	3.5 (5)	C19—C20—S1—C9	117.5 (2)
C17—C16—C18—C19	122.0 (4)	C21—C20—S1—C9	−66.4 (3)
C14—C16—C18—C19	−104.3 (8)	C6—C7—S2—C22^i	−117.1 (2)
C14'—C16—C18—C23	49.8 (10)	C8—C7—S2—C22^i	67.6 (3)
C15—C16—C18—C23	−177.7 (3)	C26—O2—C25—O1	−31.6 (12)
C17—C16—C18—C23	−59.2 (4)	C26—O2—C25—C24	178.3 (4)
C14—C16—C18—C23	74.5 (8)	O5—C24—C25—O1	30.9 (11)
C23—C18—C19—C20	3.9 (4)	O5—C24—C25—O2	−177.8 (3)
C16—C18—C19—C20	−177.2 (3)	C6—C5—C1—C2	−0.8 (5)
C18—C19—C20—C21	0.9 (4)	C10—C5—C1—C2	177.2 (4)
C18—C19—C20—S1	177.0 (2)	C6—C5—C1—C3	126.0 (6)
C19—C20—C21—O5	174.6 (2)	C10—C5—C1—C3	−55.9 (7)
S1—C20—C21—O5	−1.4 (4)	C6—C5—C1—C4	−115.9 (4)
C19—C20—C21—C22	−5.2 (4)	C10—C5—C1—C4	62.1 (4)

Symmetry code: (i) −x+2, y, −z+1/2.

(II) tetramethyl (5,11,17,23-tetrabromo-2,8,14,20-tetrathiacalix[4]arene-25,26,27,28- tetrayltetraoxy)tetraacetate

Crystal data

C36H28Br4O12S4	Z = 2
Mr = 1100.46	F(000) = 1088
Triclinic, P1	Dx = 1.788 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.4298 (15) Å	Cell parameters from 3300 reflections
b = 13.960 (2) Å	θ = 2.5–27.5°
c = 14.701 (2) Å	µ = 4.20 mm^−1
α = 82.296 (2)°	T = 173 K
β = 84.921 (2)°	Block, colourless
γ = 74.872 (2)°	0.58 × 0.38 × 0.21 mm
V = 2044.5 (5) Å^3

Data collection

CCD area-detector diffractometer	7443 independent reflections
Radiation source: fine-focus sealed tube	5974 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ϕ and ω scans	θmax = 25.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −12→12
Tmin = 0.194, Tmax = 0.472	k = −16→16
10757 measured reflections	l = −17→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0459P)^2] where P = (Fo^2 + 2Fc^2)/3
7443 reflections	(Δ/σ)max = 0.001
518 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.67 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	0.6802 (3)	0.8611 (2)	0.5689 (2)	0.0238 (7)
C2	0.6953 (3)	0.7764 (2)	0.5241 (2)	0.0261 (7)
H2	0.7535	0.7657	0.4727	0.031*
C3	0.6222 (3)	0.7090 (2)	0.5579 (2)	0.0256 (7)
C4	0.5385 (3)	0.7203 (2)	0.6354 (2)	0.0251 (7)
H4	0.4931	0.6721	0.6579	0.030*
C5	0.5225 (3)	0.8048 (2)	0.6799 (2)	0.0216 (7)
C6	0.5902 (3)	0.8773 (2)	0.6439 (2)	0.0213 (7)
C7	0.4607 (4)	1.0390 (3)	0.6628 (3)	0.0375 (9)
H7A	0.3853	1.0112	0.6603	0.045*
H7B	0.4777	1.0724	0.6024	0.045*
C8	0.4304 (3)	1.1123 (2)	0.7320 (2)	0.0296 (8)
C9	0.2692 (5)	1.2555 (3)	0.7731 (3)	0.0577 (13)
H9A	0.2970	1.2290	0.8339	0.087*
H9B	0.1739	1.2766	0.7743	0.087*
H9C	0.3055	1.3115	0.7516	0.087*
C10	0.5604 (3)	0.7954 (2)	0.8590 (2)	0.0206 (7)
C11	0.5822 (3)	0.8738 (2)	0.8987 (2)	0.0232 (7)
H11	0.5279	0.9379	0.8867	0.028*
C12	0.6856 (3)	0.8555 (2)	0.9562 (2)	0.0244 (7)
C13	0.7714 (3)	0.7623 (2)	0.9724 (2)	0.0238 (7)
H13	0.8422	0.7522	1.0099	0.029*
C14	0.7505 (3)	0.6836 (2)	0.9317 (2)	0.0220 (7)
C15	0.6444 (3)	0.6993 (2)	0.8761 (2)	0.0225 (7)
C16	0.5513 (3)	0.5628 (2)	0.8914 (2)	0.0288 (8)
H16A	0.4745	0.6058	0.9204	0.035*
H16B	0.6069	0.5234	0.9396	0.035*
C17	0.5059 (3)	0.4942 (2)	0.8380 (2)	0.0292 (8)
C18	0.5316 (5)	0.4201 (3)	0.7018 (3)	0.0526 (11)
H18A	0.5503	0.3529	0.7320	0.079*
H18B	0.5793	0.4211	0.6429	0.079*
H18C	0.4379	0.4440	0.6936	0.079*
C19	0.9414 (3)	0.5495 (2)	0.8426 (2)	0.0223 (7)
C20	0.9134 (3)	0.4815 (2)	0.7916 (2)	0.0259 (7)
H20	0.8535	0.4441	0.8152	0.031*
C21	0.9754 (3)	0.4700 (2)	0.7056 (2)	0.0293 (8)
C22	1.0633 (3)	0.5253 (2)	0.6691 (2)	0.0276 (8)
H22	1.1036	0.5170	0.6107	0.033*
C23	1.0913 (3)	0.5934 (2)	0.7202 (2)	0.0231 (7)
C24	1.0307 (3)	0.6060 (2)	0.8076 (2)	0.0213 (7)
C25	1.1753 (3)	0.6632 (2)	0.8917 (2)	0.0244 (7)
H25A	1.2323	0.6887	0.8441	0.029*
H25B	1.2147	0.5925	0.9073	0.029*
C27	1.2947 (4)	0.7566 (3)	1.0813 (3)	0.0459 (10)
H27A	1.2490	0.8259	1.0701	0.069*
H27B	1.3867	0.7507	1.0902	0.069*
H27C	1.2551	0.7266	1.1354	0.069*
C28	1.1246 (3)	0.7444 (2)	0.5810 (2)	0.0240 (7)
C29	1.1969 (3)	0.7558 (2)	0.4987 (2)	0.0288 (8)
H29	1.2826	0.7157	0.4903	0.035*
C30	1.1412 (4)	0.8267 (2)	0.4292 (2)	0.0301 (8)
C31	1.0119 (4)	0.8832 (2)	0.4382 (2)	0.0298 (8)
H31	0.9745	0.9288	0.3897	0.036*
C32	0.9376 (3)	0.8714 (2)	0.5205 (2)	0.0246 (7)
C33	0.9955 (3)	0.8052 (2)	0.5939 (2)	0.0231 (7)
C34	0.8848 (3)	0.8685 (2)	0.7334 (2)	0.0261 (7)
H34A	0.8409	0.8446	0.7896	0.031*
H34B	0.8200	0.9223	0.7013	0.031*
C35	0.9953 (4)	0.9087 (3)	0.7579 (2)	0.0325 (8)
C36	1.0451 (5)	1.0105 (4)	0.8578 (4)	0.089 (2)
H36A	1.1265	0.9623	0.8734	0.133*
H36B	1.0069	1.0440	0.9104	0.133*
H36C	1.0632	1.0585	0.8085	0.133*
O1	0.9289 (2)	0.78889 (15)	0.67704 (14)	0.0238 (5)
O2	0.9527 (3)	0.9604 (2)	0.8292 (2)	0.0644 (10)
O3	1.1021 (3)	0.90080 (19)	0.71854 (19)	0.0440 (7)
O4	1.0472 (2)	0.67708 (15)	0.85840 (15)	0.0257 (5)
O6	1.2848 (2)	0.7064 (2)	1.00348 (18)	0.0407 (6)
O7	0.6244 (2)	0.62278 (15)	0.83352 (14)	0.0239 (5)
O8	0.5728 (3)	0.48356 (18)	0.75738 (17)	0.0397 (6)
O9	0.4221 (3)	0.45265 (19)	0.86803 (19)	0.0461 (7)
O10	0.5751 (2)	0.96088 (15)	0.68838 (15)	0.0247 (5)
O11	0.3162 (3)	1.17943 (19)	0.71228 (18)	0.0509 (8)
O12	0.4960 (3)	1.11270 (18)	0.79426 (18)	0.0380 (6)
Br1	0.71532 (4)	0.96270 (3)	1.01053 (3)	0.03689 (11)
Br2	1.24498 (4)	0.84485 (3)	0.31882 (3)	0.04272 (12)
Br3	0.63959 (4)	0.59478 (3)	0.49598 (3)	0.04558 (12)
Br4	0.93794 (4)	0.37639 (3)	0.63567 (3)	0.04964 (13)
S1	0.42566 (8)	0.81723 (6)	0.78538 (6)	0.02552 (19)
S2	0.86098 (8)	0.56359 (6)	0.95396 (6)	0.02645 (19)
S3	1.20822 (8)	0.66188 (6)	0.67184 (6)	0.0292 (2)
S4	0.77330 (9)	0.95014 (6)	0.52763 (6)	0.02753 (19)
C26	1.1657 (3)	0.7163 (3)	0.9745 (3)	0.0329 (8)	0.57 (8)
O5	1.072 (2)	0.782 (3)	0.995 (4)	0.077 (10)	0.57 (8)
C26'	1.1657 (3)	0.7163 (3)	0.9745 (3)	0.0329 (8)	0.43 (8)
O5'	1.0668 (17)	0.738 (4)	1.0277 (13)	0.043 (7)	0.43 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0204 (17)	0.0300 (17)	0.0212 (18)	−0.0079 (14)	−0.0064 (14)	0.0035 (14)
C2	0.0241 (18)	0.0379 (19)	0.0165 (17)	−0.0082 (15)	0.0001 (14)	−0.0033 (14)
C3	0.0307 (19)	0.0269 (17)	0.0213 (18)	−0.0081 (14)	−0.0047 (15)	−0.0063 (14)
C4	0.0197 (17)	0.0327 (18)	0.0245 (18)	−0.0104 (14)	−0.0030 (14)	−0.0007 (14)
C5	0.0137 (16)	0.0308 (17)	0.0205 (17)	−0.0049 (13)	−0.0036 (13)	−0.0032 (13)
C6	0.0169 (16)	0.0259 (17)	0.0191 (17)	−0.0012 (13)	−0.0063 (13)	0.0000 (13)
C7	0.037 (2)	0.036 (2)	0.033 (2)	0.0044 (16)	−0.0112 (17)	−0.0033 (16)
C8	0.031 (2)	0.0262 (18)	0.026 (2)	−0.0021 (15)	0.0026 (16)	0.0048 (14)
C9	0.063 (3)	0.043 (2)	0.050 (3)	0.020 (2)	0.002 (2)	−0.013 (2)
C10	0.0120 (15)	0.0323 (17)	0.0171 (16)	−0.0048 (13)	0.0016 (12)	−0.0044 (13)
C11	0.0196 (17)	0.0265 (17)	0.0196 (17)	0.0005 (13)	0.0045 (13)	−0.0049 (13)
C12	0.0228 (17)	0.0325 (18)	0.0202 (17)	−0.0093 (14)	0.0061 (14)	−0.0113 (14)
C13	0.0184 (16)	0.0343 (18)	0.0161 (16)	−0.0017 (14)	0.0013 (13)	−0.0049 (13)
C14	0.0185 (16)	0.0260 (17)	0.0171 (16)	0.0007 (13)	0.0027 (13)	−0.0014 (13)
C15	0.0212 (17)	0.0302 (17)	0.0162 (16)	−0.0075 (14)	0.0059 (13)	−0.0054 (13)
C16	0.0236 (18)	0.0362 (19)	0.0289 (19)	−0.0134 (15)	0.0055 (15)	−0.0051 (15)
C17	0.0216 (18)	0.0272 (18)	0.036 (2)	−0.0009 (15)	−0.0002 (16)	−0.0060 (15)
C18	0.072 (3)	0.050 (3)	0.046 (3)	−0.025 (2)	−0.006 (2)	−0.022 (2)
C19	0.0165 (16)	0.0222 (16)	0.0243 (18)	0.0006 (13)	0.0011 (13)	−0.0018 (13)
C20	0.0168 (17)	0.0228 (16)	0.037 (2)	−0.0045 (13)	0.0022 (14)	−0.0030 (14)
C21	0.0272 (19)	0.0284 (18)	0.035 (2)	−0.0081 (15)	−0.0021 (16)	−0.0123 (15)
C22	0.0234 (18)	0.0315 (18)	0.0258 (19)	−0.0017 (14)	0.0040 (14)	−0.0098 (14)
C23	0.0141 (16)	0.0240 (16)	0.0301 (19)	−0.0033 (13)	0.0018 (13)	−0.0045 (14)
C24	0.0135 (15)	0.0183 (15)	0.0301 (19)	0.0015 (12)	−0.0047 (13)	−0.0043 (13)
C25	0.0173 (16)	0.0340 (18)	0.0229 (18)	−0.0098 (14)	0.0006 (13)	−0.0019 (14)
C27	0.047 (2)	0.048 (2)	0.048 (3)	−0.0092 (19)	−0.018 (2)	−0.0199 (19)
C28	0.0221 (17)	0.0302 (18)	0.0233 (18)	−0.0119 (14)	0.0034 (14)	−0.0083 (14)
C29	0.0238 (18)	0.0348 (19)	0.033 (2)	−0.0149 (15)	0.0108 (15)	−0.0157 (16)
C30	0.041 (2)	0.0351 (19)	0.0211 (18)	−0.0229 (17)	0.0134 (15)	−0.0123 (15)
C31	0.039 (2)	0.0343 (19)	0.0223 (19)	−0.0212 (16)	0.0040 (15)	−0.0062 (14)
C32	0.0269 (18)	0.0280 (17)	0.0246 (18)	−0.0156 (14)	0.0016 (14)	−0.0075 (14)
C33	0.0240 (17)	0.0302 (17)	0.0195 (17)	−0.0147 (14)	0.0050 (14)	−0.0065 (13)
C34	0.0213 (17)	0.0348 (19)	0.0185 (17)	−0.0004 (14)	0.0007 (13)	−0.0047 (14)
C35	0.031 (2)	0.038 (2)	0.0260 (19)	0.0002 (16)	−0.0061 (16)	−0.0103 (15)
C36	0.063 (3)	0.120 (5)	0.102 (5)	−0.018 (3)	−0.016 (3)	−0.083 (4)
O1	0.0214 (12)	0.0307 (12)	0.0184 (12)	−0.0068 (9)	0.0052 (9)	−0.0027 (9)
O2	0.0404 (17)	0.105 (3)	0.055 (2)	−0.0083 (17)	−0.0042 (15)	−0.0567 (18)
O3	0.0308 (15)	0.0584 (17)	0.0498 (18)	−0.0171 (13)	0.0053 (13)	−0.0244 (14)
O4	0.0175 (11)	0.0276 (12)	0.0324 (13)	−0.0012 (9)	−0.0061 (10)	−0.0108 (10)
O6	0.0268 (14)	0.0596 (17)	0.0392 (16)	−0.0061 (12)	−0.0095 (12)	−0.0224 (13)
O7	0.0251 (12)	0.0281 (12)	0.0201 (12)	−0.0090 (10)	0.0039 (9)	−0.0071 (9)
O8	0.0498 (16)	0.0423 (15)	0.0347 (15)	−0.0211 (13)	0.0024 (13)	−0.0158 (12)
O9	0.0377 (16)	0.0484 (16)	0.0595 (19)	−0.0234 (13)	0.0145 (14)	−0.0184 (13)
O10	0.0211 (12)	0.0256 (12)	0.0260 (13)	−0.0010 (9)	−0.0039 (10)	−0.0054 (9)
O11	0.0541 (18)	0.0431 (16)	0.0411 (17)	0.0190 (13)	−0.0131 (14)	−0.0098 (13)
O12	0.0370 (15)	0.0414 (15)	0.0331 (15)	−0.0035 (12)	0.0012 (12)	−0.0098 (11)
Br1	0.0341 (2)	0.0404 (2)	0.0410 (2)	−0.01113 (16)	0.00331 (16)	−0.02203 (17)
Br2	0.0586 (3)	0.0412 (2)	0.0316 (2)	−0.02375 (19)	0.02556 (18)	−0.01169 (16)
Br3	0.0572 (3)	0.0490 (2)	0.0402 (2)	−0.0257 (2)	0.01046 (19)	−0.02358 (18)
Br4	0.0502 (3)	0.0504 (3)	0.0590 (3)	−0.0199 (2)	0.0023 (2)	−0.0331 (2)
S1	0.0138 (4)	0.0389 (5)	0.0224 (4)	−0.0044 (3)	0.0006 (3)	−0.0039 (3)
S2	0.0236 (4)	0.0289 (4)	0.0212 (4)	0.0004 (3)	0.0007 (3)	0.0019 (3)
S3	0.0170 (4)	0.0386 (5)	0.0316 (5)	−0.0087 (4)	0.0038 (3)	−0.0023 (4)
S4	0.0293 (5)	0.0285 (4)	0.0245 (5)	−0.0097 (4)	−0.0008 (4)	0.0027 (3)
C26	0.0241 (19)	0.033 (2)	0.042 (2)	−0.0029 (16)	−0.0087 (17)	−0.0117 (16)
O5	0.039 (5)	0.080 (14)	0.11 (2)	0.018 (7)	−0.028 (8)	−0.072 (15)
C26'	0.0241 (19)	0.033 (2)	0.042 (2)	−0.0029 (16)	−0.0087 (17)	−0.0117 (16)
O5'	0.018 (5)	0.073 (14)	0.040 (8)	−0.004 (6)	0.000 (4)	−0.032 (7)

Geometric parameters (Å, º)

C1—C6	1.387 (4)	C19—C20	1.387 (4)
C1—C2	1.397 (4)	C19—C24	1.395 (4)
C1—S4	1.783 (3)	C19—S2	1.782 (3)
C2—C3	1.377 (5)	C20—C21	1.378 (5)
C2—H2	0.9300	C20—H20	0.9300
C3—C4	1.373 (4)	C21—C22	1.377 (5)
C3—Br3	1.901 (3)	C21—Br4	1.901 (3)
C4—C5	1.390 (4)	C22—C23	1.389 (4)
C4—H4	0.9300	C22—H22	0.9300
C5—C6	1.402 (4)	C23—C24	1.393 (4)
C5—S1	1.777 (3)	C23—S3	1.783 (3)
C6—O10	1.379 (4)	C24—O4	1.372 (4)
C7—O10	1.430 (4)	C25—O4	1.420 (4)
C7—C8	1.495 (5)	C25—C26	1.491 (5)
C7—H7A	0.9700	C25—H25A	0.9700
C7—H7B	0.9700	C25—H25B	0.9700
C8—O12	1.192 (4)	C27—O6	1.444 (4)
C8—O11	1.337 (4)	C27—H27A	0.9600
C9—O11	1.439 (4)	C27—H27B	0.9600
C9—H9A	0.9600	C27—H27C	0.9600
C9—H9B	0.9600	C28—C29	1.381 (4)
C9—H9C	0.9600	C28—C33	1.403 (4)
C10—C11	1.383 (4)	C28—S3	1.773 (3)
C10—C15	1.401 (4)	C29—C30	1.377 (5)
C10—S1	1.788 (3)	C29—H29	0.9300
C11—C12	1.379 (4)	C30—C31	1.378 (5)
C11—H11	0.9300	C30—Br2	1.895 (3)
C12—C13	1.378 (4)	C31—C32	1.391 (5)
C12—Br1	1.892 (3)	C31—H31	0.9300
C13—C14	1.392 (4)	C32—C33	1.394 (4)
C13—H13	0.9300	C32—S4	1.781 (3)
C14—C15	1.389 (4)	C33—O1	1.373 (4)
C14—S2	1.776 (3)	C34—O1	1.430 (4)
C15—O7	1.377 (4)	C34—C35	1.495 (5)
C16—O7	1.426 (4)	C34—H34A	0.9700
C16—C17	1.504 (5)	C34—H34B	0.9700
C16—H16A	0.9700	C35—O3	1.195 (4)
C16—H16B	0.9700	C35—O2	1.331 (4)
C17—O9	1.193 (4)	C36—O2	1.448 (5)
C17—O8	1.328 (4)	C36—H36A	0.9600
C18—O8	1.447 (4)	C36—H36B	0.9600
C18—H18A	0.9600	C36—H36C	0.9600
C18—H18B	0.9600	O6—C26	1.316 (4)
C18—H18C	0.9600	C26—O5	1.205 (11)
C6—C1—C2	120.0 (3)	C22—C21—C20	121.4 (3)
C6—C1—S4	120.0 (2)	C22—C21—Br4	119.3 (3)
C2—C1—S4	120.0 (3)	C20—C21—Br4	119.3 (3)
C3—C2—C1	118.5 (3)	C21—C22—C23	119.5 (3)
C3—C2—H2	120.7	C21—C22—H22	120.2
C1—C2—H2	120.7	C23—C22—H22	120.2
C4—C3—C2	122.6 (3)	C22—C23—C24	120.3 (3)
C4—C3—Br3	118.7 (2)	C22—C23—S3	118.4 (3)
C2—C3—Br3	118.8 (3)	C24—C23—S3	121.3 (2)
C3—C4—C5	119.1 (3)	O4—C24—C23	122.8 (3)
C3—C4—H4	120.5	O4—C24—C19	118.0 (3)
C5—C4—H4	120.5	C23—C24—C19	119.0 (3)
C4—C5—C6	119.4 (3)	O4—C25—C26	110.4 (3)
C4—C5—S1	120.3 (2)	O4—C25—H25A	109.6
C6—C5—S1	120.1 (2)	C26—C25—H25A	109.6
O10—C6—C1	120.1 (3)	O4—C25—H25B	109.6
O10—C6—C5	119.5 (3)	C26—C25—H25B	109.6
C1—C6—C5	120.2 (3)	H25A—C25—H25B	108.1
O10—C7—C8	109.2 (3)	O6—C27—H27A	109.5
O10—C7—H7A	109.8	O6—C27—H27B	109.5
C8—C7—H7A	109.8	H27A—C27—H27B	109.5
O10—C7—H7B	109.8	O6—C27—H27C	109.5
C8—C7—H7B	109.8	H27A—C27—H27C	109.5
H7A—C7—H7B	108.3	H27B—C27—H27C	109.5
O12—C8—O11	124.8 (3)	C29—C28—C33	120.3 (3)
O12—C8—C7	126.7 (3)	C29—C28—S3	117.2 (3)
O11—C8—C7	108.5 (3)	C33—C28—S3	122.1 (3)
O11—C9—H9A	109.5	C30—C29—C28	119.5 (3)
O11—C9—H9B	109.5	C30—C29—H29	120.2
H9A—C9—H9B	109.5	C28—C29—H29	120.2
O11—C9—H9C	109.5	C29—C30—C31	121.3 (3)
H9A—C9—H9C	109.5	C29—C30—Br2	118.8 (3)
H9B—C9—H9C	109.5	C31—C30—Br2	119.9 (3)
C11—C10—C15	120.0 (3)	C30—C31—C32	119.5 (3)
C11—C10—S1	119.8 (2)	C30—C31—H31	120.2
C15—C10—S1	120.2 (2)	C32—C31—H31	120.2
C12—C11—C10	119.1 (3)	C31—C32—C33	119.9 (3)
C12—C11—H11	120.4	C31—C32—S4	116.6 (3)
C10—C11—H11	120.4	C33—C32—S4	123.3 (3)
C13—C12—C11	122.0 (3)	O1—C33—C32	123.5 (3)
C13—C12—Br1	118.8 (2)	O1—C33—C28	117.1 (3)
C11—C12—Br1	119.1 (2)	C32—C33—C28	119.1 (3)
C12—C13—C14	118.9 (3)	O1—C34—C35	113.3 (3)
C12—C13—H13	120.6	O1—C34—H34A	108.9
C14—C13—H13	120.6	C35—C34—H34A	108.9
C15—C14—C13	120.2 (3)	O1—C34—H34B	108.9
C15—C14—S2	121.3 (2)	C35—C34—H34B	108.9
C13—C14—S2	118.5 (2)	H34A—C34—H34B	107.7
O7—C15—C14	120.9 (3)	O3—C35—O2	124.6 (3)
O7—C15—C10	119.3 (3)	O3—C35—C34	126.9 (3)
C14—C15—C10	119.7 (3)	O2—C35—C34	108.4 (3)
O7—C16—C17	111.4 (3)	O2—C36—H36A	109.5
O7—C16—H16A	109.3	O2—C36—H36B	109.5
C17—C16—H16A	109.3	H36A—C36—H36B	109.5
O7—C16—H16B	109.3	O2—C36—H36C	109.5
C17—C16—H16B	109.3	H36A—C36—H36C	109.5
H16A—C16—H16B	108.0	H36B—C36—H36C	109.5
O9—C17—O8	125.3 (3)	C33—O1—C34	119.3 (2)
O9—C17—C16	122.4 (3)	C35—O2—C36	115.5 (4)
O8—C17—C16	112.2 (3)	C24—O4—C25	116.9 (2)
O8—C18—H18A	109.5	C26—O6—C27	117.9 (3)
O8—C18—H18B	109.5	C15—O7—C16	112.6 (2)
H18A—C18—H18B	109.5	C17—O8—C18	114.9 (3)
O8—C18—H18C	109.5	C6—O10—C7	113.3 (2)
H18A—C18—H18C	109.5	C8—O11—C9	116.5 (3)
H18B—C18—H18C	109.5	C5—S1—C10	97.36 (14)
C20—C19—C24	120.7 (3)	C14—S2—C19	100.02 (14)
C20—C19—S2	118.8 (2)	C28—S3—C23	104.01 (15)
C24—C19—S2	120.5 (2)	C32—S4—C1	101.08 (15)
C21—C20—C19	119.1 (3)	O5—C26—O6	122.1 (7)
C21—C20—H20	120.4	O5—C26—C25	124.0 (13)
C19—C20—H20	120.4	O6—C26—C25	110.4 (3)
C6—C1—C2—C3	−1.9 (4)	C28—C29—C30—C31	−3.5 (5)
S4—C1—C2—C3	179.8 (2)	C28—C29—C30—Br2	177.3 (2)
C1—C2—C3—C4	−2.2 (5)	C29—C30—C31—C32	2.7 (5)
C1—C2—C3—Br3	178.8 (2)	Br2—C30—C31—C32	−178.2 (2)
C2—C3—C4—C5	2.5 (5)	C30—C31—C32—C33	2.0 (5)
Br3—C3—C4—C5	−178.4 (2)	C30—C31—C32—S4	178.0 (2)
C3—C4—C5—C6	1.1 (4)	C31—C32—C33—O1	−179.6 (3)
C3—C4—C5—S1	−175.0 (2)	S4—C32—C33—O1	4.7 (4)
C2—C1—C6—O10	179.9 (3)	C31—C32—C33—C28	−5.8 (5)
S4—C1—C6—O10	−1.8 (4)	S4—C32—C33—C28	178.5 (2)
C2—C1—C6—C5	5.4 (4)	C29—C28—C33—O1	179.2 (3)
S4—C1—C6—C5	−176.3 (2)	S3—C28—C33—O1	−8.4 (4)
C4—C5—C6—O10	−179.6 (3)	C29—C28—C33—C32	5.0 (5)
S1—C5—C6—O10	−3.5 (4)	S3—C28—C33—C32	177.4 (2)
C4—C5—C6—C1	−5.0 (4)	O1—C34—C35—O3	20.6 (5)
S1—C5—C6—C1	171.0 (2)	O1—C34—C35—O2	−162.6 (3)
O10—C7—C8—O12	6.6 (5)	C32—C33—O1—C34	−65.4 (4)
O10—C7—C8—O11	−174.1 (3)	C28—C33—O1—C34	120.7 (3)
C15—C10—C11—C12	−1.2 (5)	C35—C34—O1—C33	−57.9 (4)
S1—C10—C11—C12	179.2 (2)	O3—C35—O2—C36	1.0 (6)
C10—C11—C12—C13	2.8 (5)	C34—C35—O2—C36	−175.9 (4)
C10—C11—C12—Br1	−180.0 (2)	C23—C24—O4—C25	−68.7 (4)
C11—C12—C13—C14	−2.1 (5)	C19—C24—O4—C25	116.3 (3)
Br1—C12—C13—C14	−179.3 (2)	C26—C25—O4—C24	−155.8 (3)
C12—C13—C14—C15	−0.2 (5)	C14—C15—O7—C16	84.9 (3)
C12—C13—C14—S2	−179.4 (2)	C10—C15—O7—C16	−98.4 (3)
C13—C14—C15—O7	178.4 (3)	C17—C16—O7—C15	167.9 (3)
S2—C14—C15—O7	−2.4 (4)	O9—C17—O8—C18	3.8 (5)
C13—C14—C15—C10	1.7 (5)	C16—C17—O8—C18	−178.7 (3)
S2—C14—C15—C10	−179.1 (2)	C1—C6—O10—C7	100.5 (3)
C11—C10—C15—O7	−177.7 (3)	C5—C6—O10—C7	−85.0 (3)
S1—C10—C15—O7	1.9 (4)	C8—C7—O10—C6	163.8 (3)
C11—C10—C15—C14	−1.0 (5)	O12—C8—O11—C9	−1.8 (6)
S1—C10—C15—C14	178.6 (2)	C7—C8—O11—C9	178.8 (4)
O7—C16—C17—O9	−164.6 (3)	C4—C5—S1—C10	106.6 (3)
O7—C16—C17—O8	17.8 (4)	C6—C5—S1—C10	−69.4 (3)
C24—C19—C20—C21	0.2 (5)	C11—C10—S1—C5	107.9 (3)
S2—C19—C20—C21	−179.8 (2)	C15—C10—S1—C5	−71.7 (3)
C19—C20—C21—C22	−0.6 (5)	C15—C14—S2—C19	68.3 (3)
C19—C20—C21—Br4	179.7 (2)	C13—C14—S2—C19	−112.5 (3)
C20—C21—C22—C23	0.6 (5)	C20—C19—S2—C14	−108.9 (3)
Br4—C21—C22—C23	−179.7 (2)	C24—C19—S2—C14	71.1 (3)
C21—C22—C23—C24	−0.1 (5)	C29—C28—S3—C23	−136.8 (3)
C21—C22—C23—S3	178.7 (2)	C33—C28—S3—C23	50.6 (3)
C22—C23—C24—O4	−175.2 (3)	C22—C23—S3—C28	70.0 (3)
S3—C23—C24—O4	6.0 (4)	C24—C23—S3—C28	−111.2 (3)
C22—C23—C24—C19	−0.3 (4)	C31—C32—S4—C1	130.3 (3)
S3—C23—C24—C19	−179.1 (2)	C33—C32—S4—C1	−53.8 (3)
C20—C19—C24—O4	175.4 (3)	C6—C1—S4—C32	130.2 (3)
S2—C19—C24—O4	−4.5 (4)	C2—C1—S4—C32	−51.5 (3)
C20—C19—C24—C23	0.3 (4)	C27—O6—C26—O5	18 (4)
S2—C19—C24—C23	−179.7 (2)	C27—O6—C26—C25	177.6 (3)
C33—C28—C29—C30	−0.4 (5)	O4—C25—C26—O5	−19 (4)
S3—C28—C29—C30	−173.1 (2)	O4—C25—C26—O6	−177.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C25—H25B···O9^i	0.97	2.59	3.399 (4)	141
C16—H16A···O6^ii	0.97	2.44	3.409 (4)	176
C34—H34B···O10	0.97	2.49	3.242 (4)	135
C34—H34B···S4	0.97	2.60	3.288 (3)	128
C25—H25A···S3	0.97	2.65	3.223 (3)	118
C13—H13···O5	0.93	2.52	3.26 (3)	137
C11—H11···O12	0.93	2.58	3.405 (4)	148
C34—H34A···Cg1	0.97	2.73	3.674 (3)	164

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