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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108013838/gg3153sup1.cif
Contains datablocks global, II, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108013838/gg3153Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108013838/gg3153IIsup3.hkl
Contains datablock II

CCDC references: 692673; 692674

Comment top

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 top

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).

Experimental top

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, Rf = 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.

Refinement top

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) Uiso(H) = 1.2Ueq(C) and 0.97 Å (methyl CH3), Uiso(H) = 1.5Ueq(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 top

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 top
[Figure 1] Fig. 1. A view of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level for non-H atoms.
[Figure 2] 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.
[Figure 3] Fig. 3. A view of the packing of (I), showing the pattern of channels along the b axis.
[Figure 4] Fig. 4. The hydrogen-bonded one-dimensional chains of (II), viewed along the c axis with R22(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 top
Crystal data top
C52H64O12S4F(000) = 2144
Mr = 1009.27Dx = 1.272 Mg m3
Monoclinic, C2/cMelting point: 583 K
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 23.060 (4) ÅCell parameters from 3304 reflections
b = 13.547 (2) Åθ = 2.5–27.1°
c = 20.083 (4) ŵ = 0.24 mm1
β = 122.890 (2)°T = 173 K
V = 5268.3 (16) Å3Block, colourless
Z = 40.34 × 0.23 × 0.16 mm
Data collection top
CCD area-detector
diffractometer
4893 independent reflections
Radiation source: fine-focus sealed tube3834 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
ϕ and ω scansθmax = 25.5°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 2724
Tmin = 0.923, Tmax = 0.963k = 1416
13453 measured reflectionsl = 2424
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.061Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.164H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0714P)2 + 12.3991P]
where P = (Fo2 + 2Fc2)/3
4893 reflections(Δ/σ)max = 0.001
360 parametersΔρmax = 0.47 e Å3
51 restraintsΔρmin = 0.30 e Å3
Crystal data top
C52H64O12S4V = 5268.3 (16) Å3
Mr = 1009.27Z = 4
Monoclinic, C2/cMo Kα radiation
a = 23.060 (4) ŵ = 0.24 mm1
b = 13.547 (2) ÅT = 173 K
c = 20.083 (4) Å0.34 × 0.23 × 0.16 mm
β = 122.890 (2)°
Data collection top
CCD area-detector
diffractometer
4893 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
3834 reflections with I > 2σ(I)
Tmin = 0.923, Tmax = 0.963Rint = 0.035
13453 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06151 restraints
wR(F2) = 0.164H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0714P)2 + 12.3991P]
where P = (Fo2 + 2Fc2)/3
4893 reflectionsΔρmax = 0.47 e Å3
360 parametersΔρmin = 0.30 e Å3
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
S10.99878 (4)0.21639 (7)0.44360 (5)0.0366 (2)
S20.79969 (4)0.23303 (6)0.12342 (5)0.0311 (2)
O11.1161 (8)0.0627 (7)0.4389 (6)0.065 (3)0.47 (3)
O21.19587 (16)0.0360 (2)0.56977 (16)0.0638 (8)
O30.8866 (2)0.5131 (2)0.2833 (3)0.0972 (14)
O40.82860 (17)0.49964 (19)0.3393 (2)0.0670 (9)
O51.10215 (10)0.13481 (15)0.41260 (12)0.0313 (5)
O60.90236 (10)0.31546 (15)0.28476 (12)0.0300 (5)
C50.89228 (15)0.0062 (2)0.27746 (18)0.0296 (7)
C60.85261 (14)0.0627 (2)0.20969 (17)0.0276 (7)
H60.82260.03110.16180.033*
C70.85638 (14)0.1646 (2)0.21130 (17)0.0260 (6)
C80.90054 (14)0.2136 (2)0.28239 (17)0.0262 (6)
C90.94319 (15)0.1580 (2)0.35053 (17)0.0276 (7)
C100.93877 (15)0.0562 (2)0.34727 (17)0.0293 (7)
H100.96770.02000.39300.035*
C110.85576 (19)0.3539 (2)0.3036 (2)0.0415 (8)
H11A0.86770.32940.35490.050*
H11B0.80920.33240.26430.050*
C120.85917 (17)0.4638 (2)0.30506 (19)0.0345 (7)
C130.8274 (2)0.6050 (3)0.3460 (3)0.0626 (12)
H13A0.87210.63140.36370.094*
H13B0.81540.62140.38360.094*
H13C0.79380.63260.29530.094*
C161.10502 (18)0.5566 (2)0.4295 (2)0.0399 (8)
C151.0585 (2)0.5975 (3)0.4553 (3)0.0644 (12)
H15A1.01120.58310.41540.097*
H15B1.06460.66770.46230.097*
H15C1.07040.56740.50450.097*
C171.1793 (2)0.5844 (3)0.4938 (3)0.0709 (14)
H17A1.20980.56410.47760.106*
H17B1.19220.55200.54250.106*
H17C1.18250.65460.50160.106*
C181.10045 (15)0.4442 (2)0.42054 (17)0.0300 (7)
C191.05575 (15)0.3876 (2)0.43053 (17)0.0307 (7)
H191.02560.41890.44090.037*
C201.05459 (15)0.2856 (2)0.42544 (17)0.0295 (7)
C211.09976 (14)0.2363 (2)0.41101 (16)0.0267 (6)
C221.14171 (14)0.2926 (2)0.39551 (16)0.0267 (6)
C231.14167 (15)0.3942 (2)0.40002 (17)0.0282 (7)
H231.16980.43050.38910.034*
C241.15612 (18)0.0996 (3)0.4874 (2)0.0452 (9)
H24A1.15780.13860.52890.054*
H24B1.19990.10760.49180.054*
C261.1938 (3)0.1352 (3)0.5920 (3)0.0785 (15)
H26A1.16360.17340.54540.118*
H26B1.17720.13600.62660.118*
H26C1.23940.16290.61900.118*
C251.14652 (18)0.0056 (3)0.4989 (2)0.0454 (9)0.47 (3)
C141.0665 (11)0.5985 (12)0.3425 (9)0.058 (4)0.47 (3)
H14A1.01910.57780.31370.086*0.47 (3)
H14B1.08830.57410.31640.086*0.47 (3)
H14C1.06860.66930.34420.086*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)
H14D1.05370.60020.31280.104*0.53 (3)
H14E1.13250.58160.34920.104*0.53 (3)
H14F1.10840.67820.37040.104*0.53 (3)
C10.88511 (18)0.1059 (2)0.2783 (2)0.0443 (9)0.742 (10)
C20.8307 (3)0.1480 (4)0.1996 (3)0.0489 (17)0.742 (10)
H2A0.84450.13990.16260.073*0.742 (10)
H2B0.78780.11410.18020.073*0.742 (10)
H2C0.82490.21690.20550.073*0.742 (10)
C40.8590 (4)0.1265 (4)0.3352 (4)0.064 (2)0.742 (10)
H4A0.84960.19560.33440.096*0.742 (10)
H4B0.81760.08940.31750.096*0.742 (10)
H4C0.89400.10690.38820.096*0.742 (10)
C30.9535 (5)0.1568 (9)0.3112 (7)0.091 (4)0.742 (10)
H3'10.98640.13130.36300.136*0.742 (10)
H3'20.96970.14510.27680.136*0.742 (10)
H3'30.94800.22640.31460.136*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)
H2'10.90900.12490.19330.119*0.258 (10)
H2'20.82930.11530.15550.119*0.258 (10)
H2'30.86730.21430.19620.119*0.258 (10)
C3'0.9476 (16)0.157 (2)0.3371 (16)0.061 (7)0.258 (10)
H3A0.94460.22490.32240.091*0.258 (10)
H3B0.95290.15230.38790.091*0.258 (10)
H3C0.98660.12680.34010.091*0.258 (10)
C4'0.8198 (11)0.1328 (15)0.2701 (15)0.083 (7)0.258 (10)
H4'10.81080.20180.25760.124*0.258 (10)
H4'20.78280.09460.22840.124*0.258 (10)
H4'30.82300.11970.31900.124*0.258 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0378 (5)0.0459 (5)0.0272 (4)0.0096 (4)0.0184 (4)0.0075 (3)
S20.0215 (4)0.0300 (4)0.0335 (4)0.0002 (3)0.0096 (3)0.0100 (3)
O10.070 (6)0.036 (4)0.064 (5)0.002 (4)0.021 (4)0.006 (3)
O20.079 (2)0.0411 (16)0.0500 (16)0.0063 (14)0.0215 (15)0.0166 (13)
O30.180 (4)0.0353 (17)0.170 (4)0.001 (2)0.156 (4)0.003 (2)
O40.099 (2)0.0302 (14)0.118 (3)0.0067 (14)0.089 (2)0.0006 (15)
O50.0285 (11)0.0228 (11)0.0273 (11)0.0005 (9)0.0053 (9)0.0026 (9)
O60.0326 (11)0.0235 (11)0.0393 (12)0.0021 (9)0.0230 (10)0.0014 (9)
C50.0271 (15)0.0246 (16)0.0356 (17)0.0006 (12)0.0160 (14)0.0035 (13)
C60.0236 (15)0.0274 (16)0.0251 (15)0.0033 (12)0.0089 (12)0.0013 (12)
C70.0238 (15)0.0237 (16)0.0305 (16)0.0000 (12)0.0147 (13)0.0039 (12)
C80.0267 (15)0.0232 (16)0.0330 (16)0.0027 (12)0.0191 (13)0.0016 (12)
C90.0242 (15)0.0308 (17)0.0289 (16)0.0021 (12)0.0152 (13)0.0006 (13)
C100.0243 (15)0.0345 (18)0.0269 (15)0.0018 (13)0.0125 (13)0.0074 (13)
C110.047 (2)0.0269 (18)0.064 (2)0.0003 (15)0.0395 (19)0.0014 (16)
C120.0408 (18)0.0291 (18)0.0381 (18)0.0018 (14)0.0244 (16)0.0033 (14)
C130.074 (3)0.030 (2)0.097 (3)0.008 (2)0.056 (3)0.005 (2)
C160.050 (2)0.0256 (18)0.0419 (19)0.0043 (15)0.0235 (17)0.0071 (14)
C150.065 (3)0.037 (2)0.090 (3)0.008 (2)0.042 (3)0.018 (2)
C170.062 (3)0.038 (2)0.110 (4)0.017 (2)0.045 (3)0.035 (2)
C180.0278 (15)0.0278 (17)0.0235 (15)0.0028 (13)0.0068 (13)0.0067 (12)
C190.0280 (16)0.0334 (18)0.0267 (15)0.0016 (13)0.0122 (13)0.0093 (13)
C200.0262 (15)0.0342 (18)0.0228 (15)0.0033 (13)0.0098 (13)0.0077 (12)
C210.0254 (15)0.0233 (16)0.0205 (14)0.0014 (12)0.0053 (12)0.0061 (12)
C220.0205 (14)0.0273 (16)0.0218 (14)0.0009 (12)0.0047 (12)0.0051 (12)
C230.0250 (15)0.0281 (17)0.0255 (15)0.0027 (12)0.0098 (12)0.0050 (12)
C240.043 (2)0.036 (2)0.0329 (18)0.0023 (16)0.0056 (15)0.0069 (15)
C260.086 (3)0.052 (3)0.095 (4)0.020 (2)0.048 (3)0.041 (3)
C250.0315 (19)0.034 (2)0.052 (2)0.0028 (15)0.0102 (17)0.0070 (17)
C140.077 (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)
C10.044 (2)0.0239 (18)0.048 (2)0.0033 (15)0.0136 (17)0.0072 (15)
C20.058 (4)0.022 (2)0.052 (3)0.007 (2)0.020 (3)0.003 (2)
C40.092 (5)0.041 (3)0.058 (4)0.022 (3)0.040 (3)0.002 (3)
C30.064 (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) top
C5—C61.387 (4)C22—C231.380 (4)
C5—C101.393 (4)C22—S2i1.783 (3)
C5—C11.528 (4)C23—H230.9300
C6—C71.383 (4)C24—O51.415 (4)
C6—H60.9300C24—C251.479 (5)
C7—C81.391 (4)C24—H24A0.9700
C7—S21.782 (3)C24—H24B0.9700
C8—O61.381 (4)C26—O21.424 (5)
C8—C91.395 (4)C26—H26A0.9600
C9—C101.382 (4)C26—H26B0.9600
C9—S11.778 (3)C26—H26C0.9600
C10—H100.9300O2—C251.316 (4)
C11—O61.417 (4)S2—C22i1.783 (3)
C11—C121.491 (4)O1—C251.275 (10)
C11—H11A0.9700C14—H14A0.9600
C11—H11B0.9700C14—H14B0.9600
C12—O31.157 (4)C14—H14C0.9600
C12—O41.316 (4)C14'—H14D0.9600
C13—O41.435 (4)C14'—H14E0.9600
C13—H13A0.9600C14'—H14F0.9600
C13—H13B0.9600C1—C21.498 (6)
C13—H13C0.9600C1—C31.506 (11)
C16—C14'1.526 (9)C1—C41.578 (6)
C16—C151.527 (5)C2—H2A0.9600
C16—C181.530 (4)C2—H2B0.9600
C16—C171.530 (5)C2—H2C0.9600
C16—C141.574 (13)C4—H4A0.9600
C15—H15A0.9600C4—H4B0.9600
C15—H15B0.9600C4—H4C0.9600
C15—H15C0.9600C3—H3'10.9600
C17—H17A0.9600C3—H3'20.9600
C17—H17B0.9600C3—H3'30.9600
C17—H17C0.9600C2'—H2'10.9600
C18—C191.384 (4)C2'—H2'20.9600
C18—C231.399 (4)C2'—H2'30.9600
C19—C201.385 (4)C3'—H3A0.9600
C19—H190.9300C3'—H3B0.9600
C20—C211.394 (4)C3'—H3C0.9600
C20—S11.782 (3)C4'—H4'10.9600
C21—O51.376 (3)C4'—H4'20.9600
C21—C221.394 (4)C4'—H4'30.9600
C6—C5—C10117.2 (3)C23—C22—C21120.4 (3)
C6—C5—C1122.8 (3)C23—C22—S2i119.6 (2)
C10—C5—C1120.0 (3)C21—C22—S2i119.9 (2)
C7—C6—C5121.9 (3)C22—C23—C18121.8 (3)
C7—C6—H6119.0C22—C23—H23119.1
C5—C6—H6119.0C18—C23—H23119.1
C6—C7—C8120.1 (3)O5—C24—C25111.7 (3)
C6—C7—S2119.5 (2)O5—C24—H24A109.3
C8—C7—S2120.2 (2)C25—C24—H24A109.3
O6—C8—C7120.2 (3)O5—C24—H24B109.3
O6—C8—C9120.9 (3)C25—C24—H24B109.3
C7—C8—C9118.9 (3)H24A—C24—H24B107.9
C10—C9—C8119.9 (3)O2—C26—H26A109.5
C10—C9—S1119.1 (2)O2—C26—H26B109.5
C8—C9—S1120.9 (2)H26A—C26—H26B109.5
C9—C10—C5122.0 (3)O2—C26—H26C109.5
C9—C10—H10119.0H26A—C26—H26C109.5
C5—C10—H10119.0H26B—C26—H26C109.5
O6—C11—C12109.4 (3)C25—O2—C26118.6 (3)
O6—C11—H11A109.8C12—O4—C13117.4 (3)
C12—C11—H11A109.8C21—O5—C24111.3 (2)
O6—C11—H11B109.8C8—O6—C11111.3 (2)
C12—C11—H11B109.8C9—S1—C20101.96 (13)
H11A—C11—H11B108.2C7—S2—C22i102.31 (13)
O3—C12—O4122.8 (3)O1—C25—O2122.7 (5)
O3—C12—C11127.1 (3)O1—C25—C24119.3 (7)
O4—C12—C11110.0 (3)O2—C25—C24110.9 (3)
O4—C13—H13A109.5C16—C14—H14A109.5
O4—C13—H13B109.5C16—C14—H14B109.5
H13A—C13—H13B109.5C16—C14—H14C109.5
O4—C13—H13C109.5C16—C14'—H14D109.5
H13A—C13—H13C109.5C16—C14'—H14E109.5
H13B—C13—H13C109.5H14D—C14'—H14E109.5
C14'—C16—C15115.2 (8)C16—C14'—H14F109.5
C14'—C16—C18112.9 (6)H14D—C14'—H14F109.5
C15—C16—C18112.6 (3)H14E—C14'—H14F109.5
C14'—C16—C1799.3 (9)C2—C1—C3111.4 (5)
C15—C16—C17107.2 (3)C2—C1—C5113.6 (3)
C18—C16—C17108.6 (3)C3—C1—C5111.5 (5)
C15—C16—C1499.7 (7)C2—C1—C4105.5 (4)
C18—C16—C14105.5 (7)C3—C1—C4108.8 (6)
C17—C16—C14123.1 (9)C5—C1—C4105.7 (3)
C16—C15—H15A109.5C1—C2—H2A109.5
C16—C15—H15B109.5C1—C2—H2B109.5
H15A—C15—H15B109.5H2A—C2—H2B109.5
C16—C15—H15C109.5C1—C2—H2C109.5
H15A—C15—H15C109.5H2A—C2—H2C109.5
H15B—C15—H15C109.5H2B—C2—H2C109.5
C16—C17—H17A109.5C1—C4—H4A109.5
C16—C17—H17B109.5C1—C4—H4B109.5
H17A—C17—H17B109.5H4A—C4—H4B109.5
C16—C17—H17C109.5C1—C4—H4C109.5
H17A—C17—H17C109.5H4A—C4—H4C109.5
H17B—C17—H17C109.5H4B—C4—H4C109.5
C19—C18—C23116.9 (3)C1—C3—H3'1109.5
C19—C18—C16123.0 (3)C1—C3—H3'2109.5
C23—C18—C16120.1 (3)H3'1—C3—H3'2109.5
C18—C19—C20121.9 (3)C1—C3—H3'3109.5
C18—C19—H19119.0H3'1—C3—H3'3109.5
C20—C19—H19119.0H3'2—C3—H3'3109.5
C19—C20—C21120.4 (3)H2'1—C2'—H2'2109.5
C19—C20—S1119.8 (2)H2'1—C2'—H2'3109.5
C21—C20—S1119.7 (2)H2'2—C2'—H2'3109.5
O5—C21—C22121.9 (3)H4'1—C4'—H4'2109.5
O5—C21—C20119.9 (3)H4'1—C4'—H4'3109.5
C22—C21—C20118.2 (3)H4'2—C4'—H4'3109.5
C10—C5—C6—C72.8 (4)S1—C20—C21—C22178.8 (2)
C1—C5—C6—C7175.3 (3)O5—C21—C22—C23175.3 (2)
C5—C6—C7—C80.4 (4)C20—C21—C22—C234.5 (4)
C5—C6—C7—S2175.7 (2)O5—C21—C22—S2i0.3 (4)
C6—C7—C8—O6177.4 (3)C20—C21—C22—S2i179.9 (2)
S2—C7—C8—O62.1 (4)C21—C22—C23—C180.4 (4)
C6—C7—C8—C93.3 (4)S2i—C22—C23—C18175.2 (2)
S2—C7—C8—C9178.6 (2)C19—C18—C23—C224.6 (4)
O6—C8—C9—C10177.8 (3)C16—C18—C23—C22176.5 (3)
C7—C8—C9—C102.9 (4)O3—C12—O4—C132.7 (6)
O6—C8—C9—S12.6 (4)C11—C12—O4—C13179.8 (3)
C7—C8—C9—S1178.1 (2)C22—C21—O5—C2483.7 (3)
C8—C9—C10—C50.4 (4)C20—C21—O5—C2496.1 (3)
S1—C9—C10—C5174.9 (2)C25—C24—O5—C21162.3 (3)
C6—C5—C10—C93.2 (4)C7—C8—O6—C1191.9 (3)
C1—C5—C10—C9175.0 (3)C9—C8—O6—C1188.8 (3)
O6—C11—C12—O310.9 (6)C12—C11—O6—C8179.7 (3)
O6—C11—C12—O4166.0 (3)C10—C9—S1—C20122.3 (2)
C14'—C16—C18—C19129.0 (10)C8—C9—S1—C2062.5 (3)
C15—C16—C18—C193.5 (5)C19—C20—S1—C9117.5 (2)
C17—C16—C18—C19122.0 (4)C21—C20—S1—C966.4 (3)
C14—C16—C18—C19104.3 (8)C6—C7—S2—C22i117.1 (2)
C14'—C16—C18—C2349.8 (10)C8—C7—S2—C22i67.6 (3)
C15—C16—C18—C23177.7 (3)C26—O2—C25—O131.6 (12)
C17—C16—C18—C2359.2 (4)C26—O2—C25—C24178.3 (4)
C14—C16—C18—C2374.5 (8)O5—C24—C25—O130.9 (11)
C23—C18—C19—C203.9 (4)O5—C24—C25—O2177.8 (3)
C16—C18—C19—C20177.2 (3)C6—C5—C1—C20.8 (5)
C18—C19—C20—C210.9 (4)C10—C5—C1—C2177.2 (4)
C18—C19—C20—S1177.0 (2)C6—C5—C1—C3126.0 (6)
C19—C20—C21—O5174.6 (2)C10—C5—C1—C355.9 (7)
S1—C20—C21—O51.4 (4)C6—C5—C1—C4115.9 (4)
C19—C20—C21—C225.2 (4)C10—C5—C1—C462.1 (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 top
Crystal data top
C36H28Br4O12S4Z = 2
Mr = 1100.46F(000) = 1088
Triclinic, P1Dx = 1.788 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.4298 (15) ÅCell parameters from 3300 reflections
b = 13.960 (2) Åθ = 2.5–27.5°
c = 14.701 (2) ŵ = 4.20 mm1
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) Å3
Data collection top
CCD area-detector
diffractometer
7443 independent reflections
Radiation source: fine-focus sealed tube5974 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
ϕ and ω scansθmax = 25.5°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 1212
Tmin = 0.194, Tmax = 0.472k = 1616
10757 measured reflectionsl = 1717
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0459P)2]
where P = (Fo2 + 2Fc2)/3
7443 reflections(Δ/σ)max = 0.001
518 parametersΔρmax = 0.53 e Å3
0 restraintsΔρmin = 0.67 e Å3
Crystal data top
C36H28Br4O12S4γ = 74.872 (2)°
Mr = 1100.46V = 2044.5 (5) Å3
Triclinic, P1Z = 2
a = 10.4298 (15) ÅMo Kα radiation
b = 13.960 (2) ŵ = 4.20 mm1
c = 14.701 (2) ÅT = 173 K
α = 82.296 (2)°0.58 × 0.38 × 0.21 mm
β = 84.921 (2)°
Data collection top
CCD area-detector
diffractometer
7443 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
5974 reflections with I > 2σ(I)
Tmin = 0.194, Tmax = 0.472Rint = 0.021
10757 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.091H-atom parameters constrained
S = 1.07Δρmax = 0.53 e Å3
7443 reflectionsΔρmin = 0.67 e Å3
518 parameters
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.6802 (3)0.8611 (2)0.5689 (2)0.0238 (7)
C20.6953 (3)0.7764 (2)0.5241 (2)0.0261 (7)
H20.75350.76570.47270.031*
C30.6222 (3)0.7090 (2)0.5579 (2)0.0256 (7)
C40.5385 (3)0.7203 (2)0.6354 (2)0.0251 (7)
H40.49310.67210.65790.030*
C50.5225 (3)0.8048 (2)0.6799 (2)0.0216 (7)
C60.5902 (3)0.8773 (2)0.6439 (2)0.0213 (7)
C70.4607 (4)1.0390 (3)0.6628 (3)0.0375 (9)
H7A0.38531.01120.66030.045*
H7B0.47771.07240.60240.045*
C80.4304 (3)1.1123 (2)0.7320 (2)0.0296 (8)
C90.2692 (5)1.2555 (3)0.7731 (3)0.0577 (13)
H9A0.29701.22900.83390.087*
H9B0.17391.27660.77430.087*
H9C0.30551.31150.75160.087*
C100.5604 (3)0.7954 (2)0.8590 (2)0.0206 (7)
C110.5822 (3)0.8738 (2)0.8987 (2)0.0232 (7)
H110.52790.93790.88670.028*
C120.6856 (3)0.8555 (2)0.9562 (2)0.0244 (7)
C130.7714 (3)0.7623 (2)0.9724 (2)0.0238 (7)
H130.84220.75221.00990.029*
C140.7505 (3)0.6836 (2)0.9317 (2)0.0220 (7)
C150.6444 (3)0.6993 (2)0.8761 (2)0.0225 (7)
C160.5513 (3)0.5628 (2)0.8914 (2)0.0288 (8)
H16A0.47450.60580.92040.035*
H16B0.60690.52340.93960.035*
C170.5059 (3)0.4942 (2)0.8380 (2)0.0292 (8)
C180.5316 (5)0.4201 (3)0.7018 (3)0.0526 (11)
H18A0.55030.35290.73200.079*
H18B0.57930.42110.64290.079*
H18C0.43790.44400.69360.079*
C190.9414 (3)0.5495 (2)0.8426 (2)0.0223 (7)
C200.9134 (3)0.4815 (2)0.7916 (2)0.0259 (7)
H200.85350.44410.81520.031*
C210.9754 (3)0.4700 (2)0.7056 (2)0.0293 (8)
C221.0633 (3)0.5253 (2)0.6691 (2)0.0276 (8)
H221.10360.51700.61070.033*
C231.0913 (3)0.5934 (2)0.7202 (2)0.0231 (7)
C241.0307 (3)0.6060 (2)0.8076 (2)0.0213 (7)
C251.1753 (3)0.6632 (2)0.8917 (2)0.0244 (7)
H25A1.23230.68870.84410.029*
H25B1.21470.59250.90730.029*
C271.2947 (4)0.7566 (3)1.0813 (3)0.0459 (10)
H27A1.24900.82591.07010.069*
H27B1.38670.75071.09020.069*
H27C1.25510.72661.13540.069*
C281.1246 (3)0.7444 (2)0.5810 (2)0.0240 (7)
C291.1969 (3)0.7558 (2)0.4987 (2)0.0288 (8)
H291.28260.71570.49030.035*
C301.1412 (4)0.8267 (2)0.4292 (2)0.0301 (8)
C311.0119 (4)0.8832 (2)0.4382 (2)0.0298 (8)
H310.97450.92880.38970.036*
C320.9376 (3)0.8714 (2)0.5205 (2)0.0246 (7)
C330.9955 (3)0.8052 (2)0.5939 (2)0.0231 (7)
C340.8848 (3)0.8685 (2)0.7334 (2)0.0261 (7)
H34A0.84090.84460.78960.031*
H34B0.82000.92230.70130.031*
C350.9953 (4)0.9087 (3)0.7579 (2)0.0325 (8)
C361.0451 (5)1.0105 (4)0.8578 (4)0.089 (2)
H36A1.12650.96230.87340.133*
H36B1.00691.04400.91040.133*
H36C1.06321.05850.80850.133*
O10.9289 (2)0.78889 (15)0.67704 (14)0.0238 (5)
O20.9527 (3)0.9604 (2)0.8292 (2)0.0644 (10)
O31.1021 (3)0.90080 (19)0.71854 (19)0.0440 (7)
O41.0472 (2)0.67708 (15)0.85840 (15)0.0257 (5)
O61.2848 (2)0.7064 (2)1.00348 (18)0.0407 (6)
O70.6244 (2)0.62278 (15)0.83352 (14)0.0239 (5)
O80.5728 (3)0.48356 (18)0.75738 (17)0.0397 (6)
O90.4221 (3)0.45265 (19)0.86803 (19)0.0461 (7)
O100.5751 (2)0.96088 (15)0.68838 (15)0.0247 (5)
O110.3162 (3)1.17943 (19)0.71228 (18)0.0509 (8)
O120.4960 (3)1.11270 (18)0.79426 (18)0.0380 (6)
Br10.71532 (4)0.96270 (3)1.01053 (3)0.03689 (11)
Br21.24498 (4)0.84485 (3)0.31882 (3)0.04272 (12)
Br30.63959 (4)0.59478 (3)0.49598 (3)0.04558 (12)
Br40.93794 (4)0.37639 (3)0.63567 (3)0.04964 (13)
S10.42566 (8)0.81723 (6)0.78538 (6)0.02552 (19)
S20.86098 (8)0.56359 (6)0.95396 (6)0.02645 (19)
S31.20822 (8)0.66188 (6)0.67184 (6)0.0292 (2)
S40.77330 (9)0.95014 (6)0.52763 (6)0.02753 (19)
C261.1657 (3)0.7163 (3)0.9745 (3)0.0329 (8)0.57 (8)
O51.072 (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 (Å2) top
U11U22U33U12U13U23
C10.0204 (17)0.0300 (17)0.0212 (18)0.0079 (14)0.0064 (14)0.0035 (14)
C20.0241 (18)0.0379 (19)0.0165 (17)0.0082 (15)0.0001 (14)0.0033 (14)
C30.0307 (19)0.0269 (17)0.0213 (18)0.0081 (14)0.0047 (15)0.0063 (14)
C40.0197 (17)0.0327 (18)0.0245 (18)0.0104 (14)0.0030 (14)0.0007 (14)
C50.0137 (16)0.0308 (17)0.0205 (17)0.0049 (13)0.0036 (13)0.0032 (13)
C60.0169 (16)0.0259 (17)0.0191 (17)0.0012 (13)0.0063 (13)0.0000 (13)
C70.037 (2)0.036 (2)0.033 (2)0.0044 (16)0.0112 (17)0.0033 (16)
C80.031 (2)0.0262 (18)0.026 (2)0.0021 (15)0.0026 (16)0.0048 (14)
C90.063 (3)0.043 (2)0.050 (3)0.020 (2)0.002 (2)0.013 (2)
C100.0120 (15)0.0323 (17)0.0171 (16)0.0048 (13)0.0016 (12)0.0044 (13)
C110.0196 (17)0.0265 (17)0.0196 (17)0.0005 (13)0.0045 (13)0.0049 (13)
C120.0228 (17)0.0325 (18)0.0202 (17)0.0093 (14)0.0061 (14)0.0113 (14)
C130.0184 (16)0.0343 (18)0.0161 (16)0.0017 (14)0.0013 (13)0.0049 (13)
C140.0185 (16)0.0260 (17)0.0171 (16)0.0007 (13)0.0027 (13)0.0014 (13)
C150.0212 (17)0.0302 (17)0.0162 (16)0.0075 (14)0.0059 (13)0.0054 (13)
C160.0236 (18)0.0362 (19)0.0289 (19)0.0134 (15)0.0055 (15)0.0051 (15)
C170.0216 (18)0.0272 (18)0.036 (2)0.0009 (15)0.0002 (16)0.0060 (15)
C180.072 (3)0.050 (3)0.046 (3)0.025 (2)0.006 (2)0.022 (2)
C190.0165 (16)0.0222 (16)0.0243 (18)0.0006 (13)0.0011 (13)0.0018 (13)
C200.0168 (17)0.0228 (16)0.037 (2)0.0045 (13)0.0022 (14)0.0030 (14)
C210.0272 (19)0.0284 (18)0.035 (2)0.0081 (15)0.0021 (16)0.0123 (15)
C220.0234 (18)0.0315 (18)0.0258 (19)0.0017 (14)0.0040 (14)0.0098 (14)
C230.0141 (16)0.0240 (16)0.0301 (19)0.0033 (13)0.0018 (13)0.0045 (14)
C240.0135 (15)0.0183 (15)0.0301 (19)0.0015 (12)0.0047 (13)0.0043 (13)
C250.0173 (16)0.0340 (18)0.0229 (18)0.0098 (14)0.0006 (13)0.0019 (14)
C270.047 (2)0.048 (2)0.048 (3)0.0092 (19)0.018 (2)0.0199 (19)
C280.0221 (17)0.0302 (18)0.0233 (18)0.0119 (14)0.0034 (14)0.0083 (14)
C290.0238 (18)0.0348 (19)0.033 (2)0.0149 (15)0.0108 (15)0.0157 (16)
C300.041 (2)0.0351 (19)0.0211 (18)0.0229 (17)0.0134 (15)0.0123 (15)
C310.039 (2)0.0343 (19)0.0223 (19)0.0212 (16)0.0040 (15)0.0062 (14)
C320.0269 (18)0.0280 (17)0.0246 (18)0.0156 (14)0.0016 (14)0.0075 (14)
C330.0240 (17)0.0302 (17)0.0195 (17)0.0147 (14)0.0050 (14)0.0065 (13)
C340.0213 (17)0.0348 (19)0.0185 (17)0.0004 (14)0.0007 (13)0.0047 (14)
C350.031 (2)0.038 (2)0.0260 (19)0.0002 (16)0.0061 (16)0.0103 (15)
C360.063 (3)0.120 (5)0.102 (5)0.018 (3)0.016 (3)0.083 (4)
O10.0214 (12)0.0307 (12)0.0184 (12)0.0068 (9)0.0052 (9)0.0027 (9)
O20.0404 (17)0.105 (3)0.055 (2)0.0083 (17)0.0042 (15)0.0567 (18)
O30.0308 (15)0.0584 (17)0.0498 (18)0.0171 (13)0.0053 (13)0.0244 (14)
O40.0175 (11)0.0276 (12)0.0324 (13)0.0012 (9)0.0061 (10)0.0108 (10)
O60.0268 (14)0.0596 (17)0.0392 (16)0.0061 (12)0.0095 (12)0.0224 (13)
O70.0251 (12)0.0281 (12)0.0201 (12)0.0090 (10)0.0039 (9)0.0071 (9)
O80.0498 (16)0.0423 (15)0.0347 (15)0.0211 (13)0.0024 (13)0.0158 (12)
O90.0377 (16)0.0484 (16)0.0595 (19)0.0234 (13)0.0145 (14)0.0184 (13)
O100.0211 (12)0.0256 (12)0.0260 (13)0.0010 (9)0.0039 (10)0.0054 (9)
O110.0541 (18)0.0431 (16)0.0411 (17)0.0190 (13)0.0131 (14)0.0098 (13)
O120.0370 (15)0.0414 (15)0.0331 (15)0.0035 (12)0.0012 (12)0.0098 (11)
Br10.0341 (2)0.0404 (2)0.0410 (2)0.01113 (16)0.00331 (16)0.02203 (17)
Br20.0586 (3)0.0412 (2)0.0316 (2)0.02375 (19)0.02556 (18)0.01169 (16)
Br30.0572 (3)0.0490 (2)0.0402 (2)0.0257 (2)0.01046 (19)0.02358 (18)
Br40.0502 (3)0.0504 (3)0.0590 (3)0.0199 (2)0.0023 (2)0.0331 (2)
S10.0138 (4)0.0389 (5)0.0224 (4)0.0044 (3)0.0006 (3)0.0039 (3)
S20.0236 (4)0.0289 (4)0.0212 (4)0.0004 (3)0.0007 (3)0.0019 (3)
S30.0170 (4)0.0386 (5)0.0316 (5)0.0087 (4)0.0038 (3)0.0023 (4)
S40.0293 (5)0.0285 (4)0.0245 (5)0.0097 (4)0.0008 (4)0.0027 (3)
C260.0241 (19)0.033 (2)0.042 (2)0.0029 (16)0.0087 (17)0.0117 (16)
O50.039 (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) top
C1—C61.387 (4)C19—C201.387 (4)
C1—C21.397 (4)C19—C241.395 (4)
C1—S41.783 (3)C19—S21.782 (3)
C2—C31.377 (5)C20—C211.378 (5)
C2—H20.9300C20—H200.9300
C3—C41.373 (4)C21—C221.377 (5)
C3—Br31.901 (3)C21—Br41.901 (3)
C4—C51.390 (4)C22—C231.389 (4)
C4—H40.9300C22—H220.9300
C5—C61.402 (4)C23—C241.393 (4)
C5—S11.777 (3)C23—S31.783 (3)
C6—O101.379 (4)C24—O41.372 (4)
C7—O101.430 (4)C25—O41.420 (4)
C7—C81.495 (5)C25—C261.491 (5)
C7—H7A0.9700C25—H25A0.9700
C7—H7B0.9700C25—H25B0.9700
C8—O121.192 (4)C27—O61.444 (4)
C8—O111.337 (4)C27—H27A0.9600
C9—O111.439 (4)C27—H27B0.9600
C9—H9A0.9600C27—H27C0.9600
C9—H9B0.9600C28—C291.381 (4)
C9—H9C0.9600C28—C331.403 (4)
C10—C111.383 (4)C28—S31.773 (3)
C10—C151.401 (4)C29—C301.377 (5)
C10—S11.788 (3)C29—H290.9300
C11—C121.379 (4)C30—C311.378 (5)
C11—H110.9300C30—Br21.895 (3)
C12—C131.378 (4)C31—C321.391 (5)
C12—Br11.892 (3)C31—H310.9300
C13—C141.392 (4)C32—C331.394 (4)
C13—H130.9300C32—S41.781 (3)
C14—C151.389 (4)C33—O11.373 (4)
C14—S21.776 (3)C34—O11.430 (4)
C15—O71.377 (4)C34—C351.495 (5)
C16—O71.426 (4)C34—H34A0.9700
C16—C171.504 (5)C34—H34B0.9700
C16—H16A0.9700C35—O31.195 (4)
C16—H16B0.9700C35—O21.331 (4)
C17—O91.193 (4)C36—O21.448 (5)
C17—O81.328 (4)C36—H36A0.9600
C18—O81.447 (4)C36—H36B0.9600
C18—H18A0.9600C36—H36C0.9600
C18—H18B0.9600O6—C261.316 (4)
C18—H18C0.9600C26—O51.205 (11)
C6—C1—C2120.0 (3)C22—C21—C20121.4 (3)
C6—C1—S4120.0 (2)C22—C21—Br4119.3 (3)
C2—C1—S4120.0 (3)C20—C21—Br4119.3 (3)
C3—C2—C1118.5 (3)C21—C22—C23119.5 (3)
C3—C2—H2120.7C21—C22—H22120.2
C1—C2—H2120.7C23—C22—H22120.2
C4—C3—C2122.6 (3)C22—C23—C24120.3 (3)
C4—C3—Br3118.7 (2)C22—C23—S3118.4 (3)
C2—C3—Br3118.8 (3)C24—C23—S3121.3 (2)
C3—C4—C5119.1 (3)O4—C24—C23122.8 (3)
C3—C4—H4120.5O4—C24—C19118.0 (3)
C5—C4—H4120.5C23—C24—C19119.0 (3)
C4—C5—C6119.4 (3)O4—C25—C26110.4 (3)
C4—C5—S1120.3 (2)O4—C25—H25A109.6
C6—C5—S1120.1 (2)C26—C25—H25A109.6
O10—C6—C1120.1 (3)O4—C25—H25B109.6
O10—C6—C5119.5 (3)C26—C25—H25B109.6
C1—C6—C5120.2 (3)H25A—C25—H25B108.1
O10—C7—C8109.2 (3)O6—C27—H27A109.5
O10—C7—H7A109.8O6—C27—H27B109.5
C8—C7—H7A109.8H27A—C27—H27B109.5
O10—C7—H7B109.8O6—C27—H27C109.5
C8—C7—H7B109.8H27A—C27—H27C109.5
H7A—C7—H7B108.3H27B—C27—H27C109.5
O12—C8—O11124.8 (3)C29—C28—C33120.3 (3)
O12—C8—C7126.7 (3)C29—C28—S3117.2 (3)
O11—C8—C7108.5 (3)C33—C28—S3122.1 (3)
O11—C9—H9A109.5C30—C29—C28119.5 (3)
O11—C9—H9B109.5C30—C29—H29120.2
H9A—C9—H9B109.5C28—C29—H29120.2
O11—C9—H9C109.5C29—C30—C31121.3 (3)
H9A—C9—H9C109.5C29—C30—Br2118.8 (3)
H9B—C9—H9C109.5C31—C30—Br2119.9 (3)
C11—C10—C15120.0 (3)C30—C31—C32119.5 (3)
C11—C10—S1119.8 (2)C30—C31—H31120.2
C15—C10—S1120.2 (2)C32—C31—H31120.2
C12—C11—C10119.1 (3)C31—C32—C33119.9 (3)
C12—C11—H11120.4C31—C32—S4116.6 (3)
C10—C11—H11120.4C33—C32—S4123.3 (3)
C13—C12—C11122.0 (3)O1—C33—C32123.5 (3)
C13—C12—Br1118.8 (2)O1—C33—C28117.1 (3)
C11—C12—Br1119.1 (2)C32—C33—C28119.1 (3)
C12—C13—C14118.9 (3)O1—C34—C35113.3 (3)
C12—C13—H13120.6O1—C34—H34A108.9
C14—C13—H13120.6C35—C34—H34A108.9
C15—C14—C13120.2 (3)O1—C34—H34B108.9
C15—C14—S2121.3 (2)C35—C34—H34B108.9
C13—C14—S2118.5 (2)H34A—C34—H34B107.7
O7—C15—C14120.9 (3)O3—C35—O2124.6 (3)
O7—C15—C10119.3 (3)O3—C35—C34126.9 (3)
C14—C15—C10119.7 (3)O2—C35—C34108.4 (3)
O7—C16—C17111.4 (3)O2—C36—H36A109.5
O7—C16—H16A109.3O2—C36—H36B109.5
C17—C16—H16A109.3H36A—C36—H36B109.5
O7—C16—H16B109.3O2—C36—H36C109.5
C17—C16—H16B109.3H36A—C36—H36C109.5
H16A—C16—H16B108.0H36B—C36—H36C109.5
O9—C17—O8125.3 (3)C33—O1—C34119.3 (2)
O9—C17—C16122.4 (3)C35—O2—C36115.5 (4)
O8—C17—C16112.2 (3)C24—O4—C25116.9 (2)
O8—C18—H18A109.5C26—O6—C27117.9 (3)
O8—C18—H18B109.5C15—O7—C16112.6 (2)
H18A—C18—H18B109.5C17—O8—C18114.9 (3)
O8—C18—H18C109.5C6—O10—C7113.3 (2)
H18A—C18—H18C109.5C8—O11—C9116.5 (3)
H18B—C18—H18C109.5C5—S1—C1097.36 (14)
C20—C19—C24120.7 (3)C14—S2—C19100.02 (14)
C20—C19—S2118.8 (2)C28—S3—C23104.01 (15)
C24—C19—S2120.5 (2)C32—S4—C1101.08 (15)
C21—C20—C19119.1 (3)O5—C26—O6122.1 (7)
C21—C20—H20120.4O5—C26—C25124.0 (13)
C19—C20—H20120.4O6—C26—C25110.4 (3)
C6—C1—C2—C31.9 (4)C28—C29—C30—C313.5 (5)
S4—C1—C2—C3179.8 (2)C28—C29—C30—Br2177.3 (2)
C1—C2—C3—C42.2 (5)C29—C30—C31—C322.7 (5)
C1—C2—C3—Br3178.8 (2)Br2—C30—C31—C32178.2 (2)
C2—C3—C4—C52.5 (5)C30—C31—C32—C332.0 (5)
Br3—C3—C4—C5178.4 (2)C30—C31—C32—S4178.0 (2)
C3—C4—C5—C61.1 (4)C31—C32—C33—O1179.6 (3)
C3—C4—C5—S1175.0 (2)S4—C32—C33—O14.7 (4)
C2—C1—C6—O10179.9 (3)C31—C32—C33—C285.8 (5)
S4—C1—C6—O101.8 (4)S4—C32—C33—C28178.5 (2)
C2—C1—C6—C55.4 (4)C29—C28—C33—O1179.2 (3)
S4—C1—C6—C5176.3 (2)S3—C28—C33—O18.4 (4)
C4—C5—C6—O10179.6 (3)C29—C28—C33—C325.0 (5)
S1—C5—C6—O103.5 (4)S3—C28—C33—C32177.4 (2)
C4—C5—C6—C15.0 (4)O1—C34—C35—O320.6 (5)
S1—C5—C6—C1171.0 (2)O1—C34—C35—O2162.6 (3)
O10—C7—C8—O126.6 (5)C32—C33—O1—C3465.4 (4)
O10—C7—C8—O11174.1 (3)C28—C33—O1—C34120.7 (3)
C15—C10—C11—C121.2 (5)C35—C34—O1—C3357.9 (4)
S1—C10—C11—C12179.2 (2)O3—C35—O2—C361.0 (6)
C10—C11—C12—C132.8 (5)C34—C35—O2—C36175.9 (4)
C10—C11—C12—Br1180.0 (2)C23—C24—O4—C2568.7 (4)
C11—C12—C13—C142.1 (5)C19—C24—O4—C25116.3 (3)
Br1—C12—C13—C14179.3 (2)C26—C25—O4—C24155.8 (3)
C12—C13—C14—C150.2 (5)C14—C15—O7—C1684.9 (3)
C12—C13—C14—S2179.4 (2)C10—C15—O7—C1698.4 (3)
C13—C14—C15—O7178.4 (3)C17—C16—O7—C15167.9 (3)
S2—C14—C15—O72.4 (4)O9—C17—O8—C183.8 (5)
C13—C14—C15—C101.7 (5)C16—C17—O8—C18178.7 (3)
S2—C14—C15—C10179.1 (2)C1—C6—O10—C7100.5 (3)
C11—C10—C15—O7177.7 (3)C5—C6—O10—C785.0 (3)
S1—C10—C15—O71.9 (4)C8—C7—O10—C6163.8 (3)
C11—C10—C15—C141.0 (5)O12—C8—O11—C91.8 (6)
S1—C10—C15—C14178.6 (2)C7—C8—O11—C9178.8 (4)
O7—C16—C17—O9164.6 (3)C4—C5—S1—C10106.6 (3)
O7—C16—C17—O817.8 (4)C6—C5—S1—C1069.4 (3)
C24—C19—C20—C210.2 (5)C11—C10—S1—C5107.9 (3)
S2—C19—C20—C21179.8 (2)C15—C10—S1—C571.7 (3)
C19—C20—C21—C220.6 (5)C15—C14—S2—C1968.3 (3)
C19—C20—C21—Br4179.7 (2)C13—C14—S2—C19112.5 (3)
C20—C21—C22—C230.6 (5)C20—C19—S2—C14108.9 (3)
Br4—C21—C22—C23179.7 (2)C24—C19—S2—C1471.1 (3)
C21—C22—C23—C240.1 (5)C29—C28—S3—C23136.8 (3)
C21—C22—C23—S3178.7 (2)C33—C28—S3—C2350.6 (3)
C22—C23—C24—O4175.2 (3)C22—C23—S3—C2870.0 (3)
S3—C23—C24—O46.0 (4)C24—C23—S3—C28111.2 (3)
C22—C23—C24—C190.3 (4)C31—C32—S4—C1130.3 (3)
S3—C23—C24—C19179.1 (2)C33—C32—S4—C153.8 (3)
C20—C19—C24—O4175.4 (3)C6—C1—S4—C32130.2 (3)
S2—C19—C24—O44.5 (4)C2—C1—S4—C3251.5 (3)
C20—C19—C24—C230.3 (4)C27—O6—C26—O518 (4)
S2—C19—C24—C23179.7 (2)C27—O6—C26—C25177.6 (3)
C33—C28—C29—C300.4 (5)O4—C25—C26—O519 (4)
S3—C28—C29—C30173.1 (2)O4—C25—C26—O6177.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C25—H25B···O9i0.972.593.399 (4)141
C16—H16A···O6ii0.972.443.409 (4)176
C34—H34B···O100.972.493.242 (4)135
C34—H34B···S40.972.603.288 (3)128
C25—H25A···S30.972.653.223 (3)118
C13—H13···O50.932.523.26 (3)137
C11—H11···O120.932.583.405 (4)148
C34—H34A···Cg10.972.733.674 (3)164
Symmetry codes: (i) x+1, y, z; (ii) x1, y, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC52H64O12S4C36H28Br4O12S4
Mr1009.271100.46
Crystal system, space groupMonoclinic, C2/cTriclinic, P1
Temperature (K)173173
a, b, c (Å)23.060 (4), 13.547 (2), 20.083 (4)10.4298 (15), 13.960 (2), 14.701 (2)
α, β, γ (°)90, 122.890 (2), 9082.296 (2), 84.921 (2), 74.872 (2)
V3)5268.3 (16)2044.5 (5)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.244.20
Crystal size (mm)0.34 × 0.23 × 0.160.58 × 0.38 × 0.21
Data collection
DiffractometerCCD area-detector
diffractometer
CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Multi-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.923, 0.9630.194, 0.472
No. of measured, independent and
observed [I > 2σ(I)] reflections
13453, 4893, 3834 10757, 7443, 5974
Rint0.0350.021
(sin θ/λ)max1)0.6060.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.061, 0.164, 1.05 0.035, 0.091, 1.07
No. of reflections48937443
No. of parameters360518
No. of restraints510
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0714P)2 + 12.3991P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0459P)2]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.47, 0.300.53, 0.67

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C25—H25B···O9i0.972.593.399 (4)141.2
C16—H16A···O6ii0.972.443.409 (4)175.9
C34—H34B···O100.972.493.242 (4)134.5
C34—H34B···S40.972.603.288 (3)128.1
C25—H25A···S30.972.653.223 (3)118.0
C13—H13···O50.932.523.26 (3)137.0
C11—H11···O120.932.583.405 (4)147.5
C34—H34A···Cg10.972.733.674 (3)164.0
Symmetry codes: (i) x+1, y, z; (ii) x1, y, z.
 

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