5,11,17,23-Tetra­bromo-25,26,27,28-tetra­kis(4-tolyl­sulfon­yloxy)-2,8,14,20-tetra­thia­calix[4]arene dichloro­methane solvate

Chen, Y.-F.; Liu, Y.; Ma, J.-P.; Guo, D.-S.

doi:10.1107/S1600536810009554

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 4| April 2010| Pages o871-o872

doi:10.1107/S1600536810009554

Open

access

5,11,17,23-Tetrabromo-25,26,27,28-tetrakis(4-tolylsulfonyloxy)-2,8,14,20-tetrathiacalix[4]arene dichloromethane solvate

Yue-Feng Chen,^a Yang Liu,^a Jian-Ping Ma ^a and Dian-Shun Guo ^a ^*

^aDepartment of Chemistry, Shandong Normal University, Jinan 250014, People's Republic of China
^*Correspondence e-mail: chdsguo@sdnu.edu.cn

(Received 5 March 2010; accepted 12 March 2010; online 20 March 2010)

In the crystal structure of the title compound, C₅₂H₃₆Br₄O₁₂S₈·CH₂Cl₂, the thiacalix[4]arene unit adopts a 1,3-alternate conformation with an intramolecular C—H⋯O hydrogen bond and four C—H⋯π interactions, with the four 4-MeC₆H₄SO₃ groups located alternately above and below the virtual plane (R) defined by the four bridging S atoms. The benzene ring of each 4-MeC₆H₄SO₃ unit is nearly perpendicular to one of the two neighboring phenol rings with interplanar angles varying from 72.97 (13) to 78.70 (13)°, while the dihedral angles between the plane (R) and the phenol rings range from 83.04 (7) to 84.30 (9)°. In the supramolecular structure, a solvent-bridged dimer composed of two main molecules is formed by four intermolecular C—H⋯O hydrogen bonds and locally creates an R₄⁴(26) motif. Such dimers associate further into chains by interdimer C—Cl⋯O short contacts [Cl⋯O 3.182 (5) Å]. Finally, these chains are linked into a two-dimensional network by a combination of interchain C—Br⋯O interactions [Br⋯O = 3.183 (3) and 2.966 (4) Å] as well as C—H⋯O hydrogen bonds.

Related literature

For general background to the chemistry of thiacalix[4]arenes, see: Kumagai et al. (1997 ); Shokova & Kovalev (2003 ); Lhoták (2004 ); Morohashi et al. (2006 ); Guo et al. (2007 ). For the synthesis and related structures, see: Lhoták et al. (2001 ); Kasyan et al. (2003 ); Xu et al. (2008 ). For C—H⋯π interactions, see: Tsuzuki et al. (2000 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For C—X⋯O (X = Cl, Br) short contacts, see: Lommerse et al. (1996 ); Metrangolo & Resnati (2001 ). For atomic radii, see: Bondi (1964 ).

Experimental

Crystal data

C₅₂H₃₆Br₄O₁₂S₈·CH₂Cl₂
M_r = 1513.85
Monoclinic, P 2₁ /c
a = 12.6945 (14) Å
b = 20.793 (2) Å
c = 23.190 (3) Å
β = 103.350 (2)°
V = 5955.8 (12) Å³
Z = 4
Mo Kα radiation
μ = 3.13 mm⁻¹
T = 173 K
0.30 × 0.21 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.453, T_max = 0.705
30976 measured reflections
11092 independent reflections
7807 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.107
S = 1.06
11092 reflections
715 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1, Cg2, Cg3 and Cg4 are the centroids of the C14–C19, C1–C6, C51–C56 and C33–C38 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O8	0.95	2.51	3.303 (5)	141
C53—H53A⋯O5ⁱ	0.99	2.38	3.175 (5)	137
C53—H53B⋯O4ⁱⁱ	0.99	2.37	3.249 (5)	147
C17—H17⋯O2ⁱⁱⁱ	0.95	2.38	3.266 (5)	155
C10—H10⋯Cg1	0.95	2.75	3.698 (1)	178
C23—H23⋯Cg2	0.95	2.65	3.602 (1)	176
C30—H30⋯Cg3	0.95	2.80	3.742 (1)	174
C41—H41⋯Cg4	0.95	2.85	3.794 (1)	172
Symmetry codes: (i) -x+1, -y+2, -z; (ii) x-1, y, z; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810009554/bg2335sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810009554/bg2335Isup2.hkl

checkCIF report

Comment top

Thiacalix[4]arenes have attracted considerable interest in recent years as versatile scaffolds for highly organized receptors (Kumagai et al., 1997; Shokova & Kovalev, 2003; Lhoták, 2004; Morohashi et al., 2006; Guo et al., 2007). Moreover, they are able to undergo electrophilic bromination at the upper rim and generate the corresponding dibromo or tetrabromo thiacalix[4]arene derivatives (Lhoták et al., 2001; Kasyan et al., 2003; Xu et al., 2008), which can be further applied to construct more elaborate receptors as well as novel supramolecular systems. We report here the crystal structure of a new tetrabromo thiacalix[4]arene derivative, 5,11,17,23-tetrabromo-25,26,27,28-tetrakis(4-toluenesulfonyloxy)-2,8,14,20-tetrathiacalix[4]arene dichloromethylene solvate.

In the crystal structure of the title compound, as shown in Fig. 1, the thiacalix[4]arene platform adopts a 1,3-alternate conformation in which the four 4-MeC₆H₄SO₃ groups are located alternately above and below the virtual plane (R) defined by four bridging S atoms. The dihedral angles between the plane (R) and the phenol rings vary from 83.04 (7) to 84.30 (9)°. Such an arrangement is different from that of its analogue where four OCH₂CO₂Me moieties replace the four 4-MeC₆H₄SO₃ units, possessing a partial cone conformation (Xu et al., 2008). Interestingly, four C—H···π interactions as well as one intramolecular C12—H12···O8 hydrogen bond (Table 1) in each thiacalix[4]arene molecule result in the benzene ring of each 4-MeC₆H₄SO₃ group leaning aslant and being nearly perpendicular to one of both neighboring phenolic rings, with dihedral angles ranging from 72.97 (13) to 78.70 (13)°. The distances of H10···Cg1, H23···Cg2, H30···Cg3 and H41···Cg4 (Cg1, Cg2, Cg3 and Cg4 are the centroids of the rings C14–C19, C1–C6, C51–C56 and C33–C38, respectively) are 2.749 (1), 2.654 (1), 2.795 (1) and 2.851 (1) Å , respectively, which are consistent with the calculations for such interactions conducted by Tsuzuki et al. (2000).

In the supramolecular structure, non-classical C—H···O hydrogen bonds (Table 1) and C—X···O (X = Cl, Br) short contacts (Lommerse et al. 1996; Metrangolo & Resnati, 2001) are observed. Pairs of the thiacalix[4]arene molecules are bridged by two dichloromethylene solvents with four intermolecular C—H···O hydrogen bonds and form a solvent-bridged centrosymmetric dimer (Fig. 2), locally creating an R₄⁴(26) motif (Bernstein et al., 1995) from atoms C53—H53A and C53—H53B at (x, y, z) and (-x, -y + 2, -z), respectively, acting as hydrogen-bond donors to atoms O5 at (-x + 1, -y +2, -z) and (x - 1, y, z), and O4 at (x - 1, y, z) and (-x + 1, -y +2, -z). Such dimers associate further into one-dimensional chains (Fig. 3), approximatively along the crystallographic b axis, by interdimer C53—Cl2···O1 short contacts (Metrangolo et al. 2001). Finally, these chains are linked into a two-dimensional network by a combination of interchain C11—Br1···O2 and C29—Br2···O1 interactions as well as C17—H17···O2 hydrogen bonds (Table 1). The separations between Cl2 and O1, Br1 at (-x + 1, y - 1/2, -z + 1/2) and O2, and Br2 at (-x + 1, y - 1/2, -z + 1/2) and O1 are 3.182 (5), 3.183 (3) and 2.966 (4) Å, respectively, which are shorter than the sum of the van derWaals radii of the halogen and O atoms (O = 1.52 Å, Br = 1.85 Å, Cl = 1.75 Å; Bondi, 1964).

Related literature top

For general background to the chemistry of thiacalix[4]arenes, see: Kumagai et al. (1997); Shokova & Kovalev (2003); Lhoták (2004); Morohashi et al. (2006); Guo et al. (2007). For the synthesis and related structures, see: Lhoták et al. (2001); Kasyan et al. (2003); Xu et al. (2008). For C—H···π interactions, see: Tsuzuki et al. (2000). For hydrogen-bond motifs, see: Bernstein et al. (1995). For C—X···O (X = Cl, Br) short contacts, see: Lommerse et al. (1996); Metrangolo & Resnati (2001). For atomic radii, see: Bondi (1964).

Experimental top

A suspension of p-tetrabromothiacalix[4]arene (0.250 g, 0.308 mmol), anhydrous Cs₂CO₃(0.610 g, 1.846 mmol) and p-toluenesulfonyl chloride (0.620 g, 3.078 mmol) in dry acetonitrile (15 ml) was refluxed for 20 h and cooled to room temperature. After removal of the volatile under reduced pressure, the residue was neutralized with 5% aqueous HCl and extracted with CH₂Cl₂. The organic layer was washed with saturated sodium hydrogen carbonate and brine, and dried over anhydrous MgSO₄. After removal of the solvent under reduced pressure, the residue was purified by flash column chromatography (silica gel, ethyl acetate/hexane = 1:5, R_f = 0.5) to give the title compound in 58 % yield as a white solid. ¹H NMR (300 MHz, CDCl₃): δ 8.00 (d, 8H, J = 8.03 Hz), 7.51 (d, 8H, J = 8.00 Hz), 7.28 (s, 8H), 2.55 (s, 12H). Single crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution in CH₃OH and CH₂Cl₂ at 273 K.

Computing details top

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 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level for non-H atoms.
	Fig. 2. A view of the hydrogen-bonded dimer of the title compound approximatively along the b axis with an R₄⁴(26) motif. Some hydrogen atoms are omitted for clarity. [Symmetry codes: (i) -x + 1, -y + 2, -z; (ii) x - 1, y, z; (iv) -x, -y + 2, -z].
	Fig. 3. A view of the one-dimensional chain of the dimers approximatively along the b axis. Some hydrogen atoms are omitted for clarity. [Symmetry codes: (i) -x + 1, -y + 2, -z; (ii) x - 1, y, z; (iv) -x, -y + 2, -z].

5,11,17,23-Tetrabromo-25,26,27,28-tetrakis(4-tolylsulfonyloxy)-2,8,14,20- tetrathiacalix[4]arene dichloromethane solvate top

Crystal data top

C₅₂H₃₆Br₄O₁₂S₈·CH₂Cl₂	F(000) = 3016
M_r = 1513.85	D_x = 1.688 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7685 reflections
a = 12.6945 (14) Å	θ = 2.4–26.5°
b = 20.793 (2) Å	µ = 3.13 mm⁻¹
c = 23.190 (3) Å	T = 173 K
β = 103.350 (2)°	Block, colourless
V = 5955.8 (12) Å³	0.30 × 0.21 × 0.12 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	11092 independent reflections
Radiation source: fine-focus sealed tube	7807 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
phi and ω scans	θ_max = 25.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −10→15
T_min = 0.453, T_max = 0.705	k = −25→25
30976 measured reflections	l = −27→28

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0524P)²] where P = (F_o² + 2F_c²)/3
11092 reflections	(Δ/σ)_max = 0.002
715 parameters	Δρ_max = 0.86 e Å⁻³
6 restraints	Δρ_min = −0.68 e Å⁻³

Crystal data top

C₅₂H₃₆Br₄O₁₂S₈·CH₂Cl₂	V = 5955.8 (12) Å³
M_r = 1513.85	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.6945 (14) Å	µ = 3.13 mm⁻¹
b = 20.793 (2) Å	T = 173 K
c = 23.190 (3) Å	0.30 × 0.21 × 0.12 mm
β = 103.350 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	11092 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	7807 reflections with I > 2σ(I)
T_min = 0.453, T_max = 0.705	R_int = 0.039
30976 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	6 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.06	Δρ_max = 0.86 e Å⁻³
11092 reflections	Δρ_min = −0.68 e Å⁻³
715 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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

	x	y	z	U_iso*/U_eq
Br1	0.43943 (3)	1.109304 (19)	0.27234 (2)	0.04887 (13)
Br3	1.02769 (5)	0.78011 (2)	0.30945 (3)	0.07916 (19)
Br4	0.95485 (4)	0.83143 (2)	0.11261 (3)	0.07435 (18)
C1	0.7126 (4)	0.72823 (17)	0.15746 (18)	0.0462 (10)
H1	0.7560	0.7213	0.1962	0.055*
C2	0.7437 (4)	0.70462 (18)	0.1088 (2)	0.0532 (11)
H2	0.8095	0.6812	0.1142	0.064*
C3	0.6821 (4)	0.7139 (2)	0.0523 (2)	0.0566 (12)
C4	0.5861 (4)	0.7474 (2)	0.0453 (2)	0.0592 (13)
H4	0.5422	0.7536	0.0065	0.071*
C5	0.5526 (4)	0.77185 (18)	0.09320 (19)	0.0499 (11)
H5	0.4863	0.7948	0.0878	0.060*
C6	0.6169 (3)	0.76234 (16)	0.14918 (17)	0.0395 (9)
C7	0.7211 (5)	0.6888 (3)	−0.0003 (2)	0.0857 (18)
H7A	0.7078	0.6424	−0.0042	0.129*
H7B	0.7988	0.6972	0.0056	0.129*
H7C	0.6818	0.7106	−0.0364	0.129*
C8	0.5929 (3)	0.91727 (15)	0.23204 (15)	0.0294 (8)
C9	0.5510 (3)	0.95961 (16)	0.18624 (15)	0.0289 (8)
C10	0.5032 (3)	1.01623 (16)	0.19828 (16)	0.0320 (8)
H10	0.4744	1.0456	0.1673	0.038*
C11	0.4978 (3)	1.02969 (16)	0.25583 (17)	0.0336 (8)
C12	0.5404 (3)	0.98801 (16)	0.30179 (16)	0.0327 (8)
H12	0.5362	0.9981	0.3412	0.039*
C13	0.5890 (3)	0.93175 (16)	0.29019 (16)	0.0315 (8)
C14	0.4205 (3)	1.08761 (18)	0.03965 (16)	0.0368 (9)
H14	0.4355	1.0557	0.0133	0.044*
C15	0.3154 (3)	1.1000 (2)	0.04305 (18)	0.0469 (10)
H15	0.2576	1.0777	0.0176	0.056*
C16	0.2926 (4)	1.1446 (2)	0.0831 (2)	0.0539 (12)
C17	0.3775 (4)	1.1780 (2)	0.11757 (19)	0.0545 (12)
H17	0.3629	1.2091	0.1446	0.065*
C18	0.4823 (4)	1.16789 (19)	0.11438 (17)	0.0478 (10)
H18	0.5396	1.1918	0.1386	0.057*
C19	0.5034 (3)	1.12220 (17)	0.07513 (16)	0.0329 (8)
C20	0.1768 (4)	1.1552 (3)	0.0878 (3)	0.0891 (19)
H20A	0.1673	1.1380	0.1256	0.134*
H20B	0.1275	1.1331	0.0550	0.134*
H20C	0.1607	1.2013	0.0857	0.134*
C21	0.7461 (3)	1.01215 (16)	0.12285 (14)	0.0301 (8)
C22	0.6975 (3)	0.95190 (17)	0.11682 (15)	0.0319 (8)
C23	0.7602 (3)	0.89818 (17)	0.11292 (16)	0.0362 (9)
H23	0.7281	0.8567	0.1080	0.043*
C24	0.8693 (3)	0.90537 (17)	0.11629 (17)	0.0399 (9)
C25	0.9191 (3)	0.96488 (17)	0.12485 (16)	0.0354 (9)
H25	0.9948	0.9687	0.1280	0.043*
C26	0.8572 (3)	1.01866 (16)	0.12870 (15)	0.0303 (8)
C27	0.9046 (3)	1.10806 (16)	0.21337 (16)	0.0308 (8)
C28	0.8342 (3)	1.15600 (16)	0.22221 (16)	0.0337 (8)
H28	0.7958	1.1810	0.1899	0.040*
C29	0.8207 (3)	1.16681 (17)	0.27889 (18)	0.0385 (9)
C30	0.8731 (3)	1.13048 (17)	0.32628 (17)	0.0373 (9)
H30	0.8619	1.1386	0.3647	0.045*
C31	0.9428 (3)	1.08162 (16)	0.31765 (15)	0.0312 (8)
C32	0.9604 (3)	1.07211 (15)	0.26131 (15)	0.0292 (8)
C33	1.2307 (3)	0.99037 (18)	0.30119 (17)	0.0382 (9)
C34	1.2480 (3)	0.9286 (2)	0.2833 (2)	0.0501 (11)
H34	1.2192	0.9157	0.2435	0.060*
C35	1.3071 (4)	0.8862 (2)	0.3234 (3)	0.0652 (14)
H35	1.3184	0.8437	0.3111	0.078*
C36	1.3498 (4)	0.9038 (3)	0.3804 (2)	0.0649 (14)
C37	1.3352 (4)	0.9664 (3)	0.39852 (19)	0.0617 (13)
H37	1.3666	0.9793	0.4381	0.074*
C38	1.2746 (3)	1.0102 (2)	0.35870 (18)	0.0491 (10)
H38	1.2636	1.0528	0.3708	0.059*
C39	1.4138 (5)	0.8562 (3)	0.4245 (3)	0.0962 (19)
H39A	1.3637	0.8277	0.4387	0.144*
H39B	1.4584	0.8796	0.4581	0.144*
H39C	1.4606	0.8306	0.4052	0.144*
C40	0.9434 (3)	0.95975 (17)	0.36111 (15)	0.0347 (8)
C41	1.0005 (3)	0.90881 (19)	0.34477 (17)	0.0423 (10)
H41	1.0736	0.9143	0.3422	0.051*
C42	0.9503 (4)	0.85022 (19)	0.33231 (18)	0.0475 (11)
C43	0.8436 (3)	0.84099 (18)	0.33341 (17)	0.0423 (10)
H43	0.8100	0.8004	0.3231	0.051*
C44	0.7854 (3)	0.89146 (17)	0.34975 (16)	0.0350 (9)
C45	0.8365 (3)	0.95058 (16)	0.36448 (15)	0.0330 (8)
C46	0.8028 (3)	1.08666 (18)	0.46528 (16)	0.0371 (9)
C47	0.7283 (3)	1.1358 (2)	0.44931 (18)	0.0463 (10)
H47	0.6565	1.1267	0.4280	0.056*
C48	0.7595 (4)	1.1981 (2)	0.46472 (19)	0.0510 (11)
H48	0.7086	1.2320	0.4537	0.061*
C49	0.8637 (4)	1.2122 (2)	0.49601 (19)	0.0519 (11)
C50	0.9368 (4)	1.1623 (2)	0.51078 (18)	0.0512 (11)
H50	1.0086	1.1715	0.5319	0.061*
C51	0.9084 (3)	1.0994 (2)	0.49574 (17)	0.0451 (10)
H51	0.9598	1.0656	0.5060	0.054*
C52	0.8968 (4)	1.2802 (2)	0.5135 (2)	0.0706 (15)
H52A	0.9342	1.2814	0.5555	0.106*
H52B	0.8323	1.3076	0.5071	0.106*
H52C	0.9454	1.2960	0.4894	0.106*
C53	0.2434 (4)	0.9546 (2)	0.0855 (2)	0.0602 (12)
H53A	0.3040	0.9636	0.0664	0.072*
H53B	0.2442	0.9881	0.1160	0.072*
Cl1	0.12058 (11)	0.95976 (7)	0.03170 (6)	0.0723 (4)
Cl2	0.26337 (14)	0.88004 (7)	0.11968 (7)	0.0922 (5)
O3	1.1686 (2)	1.10828 (12)	0.27040 (13)	0.0498 (7)
O4	1.1667 (2)	1.02640 (14)	0.19338 (12)	0.0513 (7)
O5	0.6387 (2)	1.07104 (15)	0.01904 (12)	0.0562 (8)
O6	0.6901 (2)	1.16960 (14)	0.07755 (16)	0.0691 (10)
O7	0.8372 (2)	0.96353 (13)	0.48243 (11)	0.0497 (7)
O8	0.6506 (2)	1.00265 (14)	0.44481 (12)	0.0502 (7)
O9	0.6457 (2)	0.86122 (10)	0.21968 (10)	0.0335 (6)
O10	1.03130 (18)	1.02329 (11)	0.25253 (10)	0.0317 (5)
O11	0.68364 (19)	1.06686 (11)	0.12749 (10)	0.0326 (6)
O12	0.77790 (19)	1.00232 (11)	0.38031 (10)	0.0337 (6)
S1	0.57961 (10)	0.79407 (4)	0.21118 (5)	0.0466 (3)
S2	0.55608 (7)	0.94214 (4)	0.11169 (4)	0.0335 (2)
S3	0.63585 (8)	1.10942 (5)	0.06895 (5)	0.0420 (2)
S4	0.92238 (8)	1.09501 (4)	0.14036 (4)	0.0339 (2)
S5	1.15421 (7)	1.04388 (4)	0.25031 (4)	0.0362 (2)
S6	1.01038 (8)	1.03516 (5)	0.37934 (4)	0.0379 (2)
S7	0.76318 (8)	1.00733 (5)	0.44783 (4)	0.0392 (2)
S8	0.64672 (8)	0.88001 (4)	0.35001 (4)	0.0373 (2)
Br2	0.72092 (4)	1.23092 (2)	0.29012 (2)	0.06032 (15)
O1	0.4687 (3)	0.80924 (14)	0.19888 (16)	0.0672 (9)
O2	0.6272 (3)	0.75471 (13)	0.26017 (13)	0.0712 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0508 (3)	0.0352 (2)	0.0657 (3)	0.01028 (19)	0.0236 (2)	−0.00070 (19)
Br3	0.0827 (4)	0.0475 (3)	0.1215 (5)	0.0245 (3)	0.0525 (4)	−0.0012 (3)
Br4	0.0645 (3)	0.0421 (3)	0.1291 (5)	0.0083 (2)	0.0485 (3)	−0.0082 (3)
C1	0.063 (3)	0.0278 (19)	0.042 (2)	−0.001 (2)	−0.001 (2)	−0.0005 (17)
C2	0.067 (3)	0.032 (2)	0.063 (3)	0.008 (2)	0.020 (2)	−0.005 (2)
C3	0.088 (4)	0.036 (2)	0.047 (3)	−0.004 (2)	0.018 (3)	−0.009 (2)
C4	0.088 (4)	0.039 (2)	0.042 (3)	−0.010 (2)	−0.002 (2)	−0.008 (2)
C5	0.055 (3)	0.032 (2)	0.056 (3)	−0.005 (2)	0.000 (2)	−0.002 (2)
C6	0.052 (3)	0.0226 (18)	0.044 (2)	−0.0067 (18)	0.0112 (19)	−0.0026 (16)
C7	0.137 (6)	0.071 (3)	0.058 (3)	0.007 (4)	0.039 (3)	−0.017 (3)
C8	0.0299 (19)	0.0239 (17)	0.035 (2)	−0.0016 (15)	0.0095 (16)	0.0010 (15)
C9	0.0266 (19)	0.0302 (18)	0.030 (2)	−0.0076 (15)	0.0079 (15)	−0.0013 (15)
C10	0.0252 (19)	0.0309 (19)	0.040 (2)	−0.0003 (15)	0.0080 (16)	0.0081 (16)
C11	0.029 (2)	0.0266 (18)	0.047 (2)	0.0013 (15)	0.0130 (17)	−0.0020 (16)
C12	0.032 (2)	0.0342 (19)	0.034 (2)	−0.0020 (16)	0.0124 (16)	−0.0034 (16)
C13	0.032 (2)	0.0303 (19)	0.034 (2)	−0.0035 (16)	0.0101 (16)	0.0032 (16)
C14	0.037 (2)	0.042 (2)	0.031 (2)	0.0025 (18)	0.0068 (17)	0.0034 (17)
C15	0.040 (2)	0.055 (3)	0.042 (2)	−0.002 (2)	0.0028 (19)	0.006 (2)
C16	0.049 (3)	0.064 (3)	0.054 (3)	0.017 (2)	0.023 (2)	0.020 (2)
C17	0.073 (3)	0.052 (3)	0.041 (3)	0.026 (2)	0.018 (2)	0.000 (2)
C18	0.057 (3)	0.044 (2)	0.038 (2)	0.007 (2)	0.002 (2)	−0.0011 (19)
C19	0.032 (2)	0.0336 (19)	0.032 (2)	0.0029 (16)	0.0068 (16)	0.0079 (16)
C20	0.060 (3)	0.109 (5)	0.108 (5)	0.034 (3)	0.040 (3)	0.035 (4)
C21	0.035 (2)	0.0316 (19)	0.0241 (19)	0.0019 (16)	0.0073 (15)	0.0024 (15)
C22	0.037 (2)	0.037 (2)	0.0225 (18)	−0.0049 (17)	0.0066 (15)	−0.0025 (15)
C23	0.045 (2)	0.0304 (19)	0.037 (2)	−0.0047 (17)	0.0159 (18)	−0.0014 (16)
C24	0.047 (2)	0.034 (2)	0.043 (2)	0.0083 (18)	0.0188 (19)	−0.0041 (17)
C25	0.035 (2)	0.040 (2)	0.034 (2)	0.0008 (17)	0.0138 (17)	−0.0012 (17)
C26	0.035 (2)	0.0304 (18)	0.0269 (19)	−0.0054 (16)	0.0096 (15)	−0.0014 (15)
C27	0.031 (2)	0.0266 (18)	0.036 (2)	−0.0074 (15)	0.0106 (16)	−0.0025 (15)
C28	0.034 (2)	0.0278 (18)	0.041 (2)	−0.0032 (16)	0.0124 (17)	0.0024 (16)
C29	0.033 (2)	0.0295 (19)	0.055 (3)	0.0014 (16)	0.0162 (19)	−0.0009 (18)
C30	0.039 (2)	0.036 (2)	0.039 (2)	−0.0001 (18)	0.0154 (18)	−0.0060 (17)
C31	0.030 (2)	0.0311 (18)	0.032 (2)	−0.0011 (16)	0.0057 (15)	−0.0013 (15)
C32	0.0292 (19)	0.0236 (17)	0.036 (2)	−0.0025 (15)	0.0094 (16)	−0.0028 (15)
C33	0.032 (2)	0.043 (2)	0.042 (2)	0.0081 (18)	0.0144 (17)	−0.0014 (18)
C34	0.049 (3)	0.047 (2)	0.058 (3)	0.005 (2)	0.020 (2)	0.000 (2)
C35	0.063 (3)	0.053 (3)	0.089 (4)	0.021 (2)	0.036 (3)	0.016 (3)
C36	0.054 (3)	0.079 (4)	0.072 (4)	0.028 (3)	0.036 (3)	0.033 (3)
C37	0.043 (3)	0.107 (4)	0.036 (3)	0.009 (3)	0.012 (2)	0.010 (3)
C38	0.041 (2)	0.062 (3)	0.046 (3)	0.005 (2)	0.014 (2)	−0.005 (2)
C39	0.091 (4)	0.111 (4)	0.093 (4)	0.030 (3)	0.035 (3)	0.044 (3)
C40	0.041 (2)	0.037 (2)	0.027 (2)	0.0070 (17)	0.0105 (16)	0.0078 (16)
C41	0.041 (2)	0.047 (2)	0.043 (2)	0.0112 (19)	0.0201 (19)	0.0078 (19)
C42	0.057 (3)	0.039 (2)	0.051 (3)	0.020 (2)	0.021 (2)	0.0051 (19)
C43	0.057 (3)	0.033 (2)	0.039 (2)	0.0083 (19)	0.016 (2)	0.0041 (17)
C44	0.041 (2)	0.034 (2)	0.031 (2)	0.0066 (17)	0.0105 (17)	0.0056 (16)
C45	0.041 (2)	0.0326 (19)	0.0262 (19)	0.0104 (17)	0.0091 (16)	0.0059 (15)
C46	0.040 (2)	0.041 (2)	0.033 (2)	0.0027 (18)	0.0123 (17)	−0.0044 (17)
C47	0.040 (2)	0.052 (3)	0.048 (3)	0.005 (2)	0.0128 (19)	−0.008 (2)
C48	0.053 (3)	0.047 (2)	0.057 (3)	0.009 (2)	0.022 (2)	−0.005 (2)
C49	0.064 (3)	0.052 (3)	0.048 (3)	−0.008 (2)	0.029 (2)	−0.014 (2)
C50	0.043 (3)	0.069 (3)	0.042 (3)	−0.008 (2)	0.010 (2)	−0.011 (2)
C51	0.050 (3)	0.050 (2)	0.034 (2)	0.006 (2)	0.0080 (19)	−0.0065 (19)
C52	0.084 (4)	0.057 (3)	0.077 (4)	−0.018 (3)	0.032 (3)	−0.023 (3)
C53	0.063 (3)	0.071 (3)	0.054 (3)	0.004 (3)	0.028 (2)	−0.005 (2)
Cl1	0.0642 (8)	0.0817 (9)	0.0734 (9)	0.0079 (7)	0.0210 (7)	0.0129 (7)
Cl2	0.1032 (12)	0.0880 (10)	0.0814 (11)	0.0135 (9)	0.0135 (8)	0.0221 (8)
O3	0.0345 (16)	0.0359 (15)	0.079 (2)	−0.0035 (12)	0.0133 (14)	−0.0007 (14)
O4	0.0414 (17)	0.076 (2)	0.0404 (16)	0.0152 (15)	0.0182 (13)	0.0060 (14)
O5	0.0519 (18)	0.087 (2)	0.0340 (16)	0.0226 (16)	0.0194 (13)	0.0147 (15)
O6	0.0445 (19)	0.0490 (18)	0.108 (3)	−0.0096 (15)	0.0045 (17)	0.0377 (18)
O7	0.064 (2)	0.0514 (17)	0.0335 (16)	0.0069 (15)	0.0114 (13)	0.0064 (13)
O8	0.0486 (18)	0.0607 (18)	0.0476 (17)	−0.0062 (15)	0.0242 (14)	−0.0130 (14)
O9	0.0419 (15)	0.0242 (12)	0.0362 (14)	−0.0009 (11)	0.0124 (12)	−0.0009 (10)
O10	0.0299 (13)	0.0293 (13)	0.0365 (14)	0.0017 (10)	0.0088 (11)	−0.0030 (10)
O11	0.0349 (14)	0.0299 (13)	0.0316 (14)	0.0035 (11)	0.0047 (11)	0.0047 (10)
O12	0.0375 (15)	0.0351 (13)	0.0298 (14)	0.0077 (11)	0.0106 (11)	0.0000 (11)
S1	0.0672 (8)	0.0267 (5)	0.0518 (7)	−0.0111 (5)	0.0257 (6)	−0.0016 (4)
S2	0.0339 (5)	0.0351 (5)	0.0306 (5)	−0.0054 (4)	0.0057 (4)	0.0000 (4)
S3	0.0364 (6)	0.0448 (6)	0.0452 (6)	0.0024 (5)	0.0104 (5)	0.0167 (5)
S4	0.0348 (5)	0.0349 (5)	0.0333 (5)	−0.0059 (4)	0.0106 (4)	0.0016 (4)
S5	0.0310 (5)	0.0398 (5)	0.0397 (6)	0.0021 (4)	0.0124 (4)	0.0005 (4)
S6	0.0362 (5)	0.0461 (5)	0.0315 (5)	0.0035 (4)	0.0082 (4)	0.0009 (4)
S7	0.0444 (6)	0.0439 (5)	0.0321 (5)	0.0015 (5)	0.0146 (4)	−0.0026 (4)
S8	0.0449 (6)	0.0352 (5)	0.0335 (5)	0.0013 (4)	0.0127 (4)	0.0074 (4)
Br2	0.0705 (3)	0.0490 (3)	0.0703 (3)	0.0274 (2)	0.0344 (3)	0.0062 (2)
O1	0.058 (2)	0.0509 (18)	0.103 (3)	−0.0244 (16)	0.0409 (19)	−0.0173 (18)
O2	0.140 (3)	0.0304 (15)	0.049 (2)	−0.0058 (18)	0.034 (2)	0.0075 (14)

Geometric parameters (Å, º) top

Br1—C11	1.888 (3)	C30—C31	1.391 (5)
Br3—C42	1.900 (4)	C30—H30	0.9500
Br4—C24	1.896 (4)	C31—C32	1.389 (5)
C1—C2	1.370 (6)	C31—S6	1.775 (4)
C1—C6	1.381 (5)	C32—O10	1.403 (4)
C1—H1	0.9500	C33—C34	1.382 (5)
C2—C3	1.376 (6)	C33—C38	1.384 (5)
C2—H2	0.9500	C33—S5	1.745 (4)
C3—C4	1.380 (7)	C34—C35	1.373 (6)
C3—C7	1.510 (6)	C34—H34	0.9500
C4—C5	1.377 (6)	C35—C36	1.357 (7)
C4—H4	0.9500	C35—H35	0.9500
C5—C6	1.379 (6)	C36—C37	1.394 (7)
C5—H5	0.9500	C36—C39	1.518 (7)
C6—S1	1.744 (4)	C37—C38	1.395 (6)
C7—H7A	0.9800	C37—H37	0.9500
C7—H7B	0.9800	C38—H38	0.9500
C7—H7C	0.9800	C39—H39A	0.9800
C8—C9	1.387 (5)	C39—H39B	0.9800
C8—C13	1.394 (5)	C39—H39C	0.9800
C8—O9	1.407 (4)	C40—C41	1.385 (5)
C9—C10	1.382 (5)	C40—C45	1.391 (5)
C9—S2	1.782 (3)	C40—S6	1.787 (4)
C10—C11	1.381 (5)	C41—C42	1.374 (6)
C10—H10	0.9500	C41—H41	0.9500
C11—C12	1.383 (5)	C42—C43	1.375 (6)
C12—C13	1.377 (5)	C43—C44	1.386 (5)
C12—H12	0.9500	C43—H43	0.9500
C13—S8	1.775 (4)	C44—C45	1.395 (5)
C14—C15	1.378 (5)	C44—S8	1.778 (4)
C14—C19	1.379 (5)	C45—O12	1.404 (4)
C14—H14	0.9500	C46—C47	1.383 (5)
C15—C16	1.389 (6)	C46—C51	1.389 (6)
C15—H15	0.9500	C46—S7	1.744 (4)
C16—C17	1.373 (6)	C47—C48	1.378 (6)
C16—C20	1.515 (6)	C47—H47	0.9500
C17—C18	1.365 (6)	C48—C49	1.385 (6)
C17—H17	0.9500	C48—H48	0.9500
C18—C19	1.384 (5)	C49—C50	1.383 (6)
C18—H18	0.9500	C49—C52	1.504 (6)
C19—S3	1.741 (4)	C50—C51	1.380 (6)
C20—H20A	0.9800	C50—H50	0.9500
C20—H20B	0.9800	C51—H51	0.9500
C20—H20C	0.9800	C52—H52A	0.9800
C21—C22	1.389 (5)	C52—H52B	0.9800
C21—C26	1.391 (5)	C52—H52C	0.9800
C21—O11	1.405 (4)	C53—Cl2	1.734 (5)
C22—C23	1.387 (5)	C53—Cl1	1.760 (5)
C22—S2	1.783 (4)	C53—H53A	0.9900
C23—C24	1.378 (5)	C53—H53B	0.9900
C23—H23	0.9500	O3—S5	1.416 (3)
C24—C25	1.383 (5)	O4—S5	1.413 (3)
C25—C26	1.382 (5)	O5—S3	1.413 (3)
C25—H25	0.9500	O6—S3	1.420 (3)
C26—S4	1.782 (3)	O7—S7	1.417 (3)
C27—C28	1.385 (5)	O8—S7	1.418 (3)
C27—C32	1.390 (5)	O9—S1	1.618 (2)
C27—S4	1.780 (4)	O10—S5	1.630 (2)
C28—C29	1.383 (5)	O11—S3	1.617 (2)
C28—H28	0.9500	O12—S7	1.623 (2)
C29—C30	1.372 (5)	S1—O1	1.407 (3)
C29—Br2	1.898 (3)	S1—O2	1.417 (3)

C2—C1—C6	118.8 (4)	C34—C33—S5	119.4 (3)
C2—C1—H1	120.6	C38—C33—S5	119.9 (3)
C6—C1—H1	120.6	C35—C34—C33	119.5 (4)
C1—C2—C3	121.7 (4)	C35—C34—H34	120.2
C1—C2—H2	119.1	C33—C34—H34	120.2
C3—C2—H2	119.1	C36—C35—C34	121.3 (5)
C2—C3—C4	118.4 (4)	C36—C35—H35	119.3
C2—C3—C7	120.0 (5)	C34—C35—H35	119.3
C4—C3—C7	121.6 (5)	C35—C36—C37	119.7 (4)
C5—C4—C3	121.4 (4)	C35—C36—C39	120.8 (5)
C5—C4—H4	119.3	C37—C36—C39	119.5 (5)
C3—C4—H4	119.3	C36—C37—C38	120.1 (4)
C4—C5—C6	118.8 (4)	C36—C37—H37	120.0
C4—C5—H5	120.6	C38—C37—H37	120.0
C6—C5—H5	120.6	C33—C38—C37	118.8 (4)
C5—C6—C1	121.0 (4)	C33—C38—H38	120.6
C5—C6—S1	120.5 (3)	C37—C38—H38	120.6
C1—C6—S1	118.5 (3)	C36—C39—H39A	109.5
C3—C7—H7A	109.5	C36—C39—H39B	109.5
C3—C7—H7B	109.5	H39A—C39—H39B	109.5
H7A—C7—H7B	109.5	C36—C39—H39C	109.5
C3—C7—H7C	109.5	H39A—C39—H39C	109.5
H7A—C7—H7C	109.5	H39B—C39—H39C	109.5
H7B—C7—H7C	109.5	C41—C40—C45	119.3 (4)
C9—C8—C13	120.7 (3)	C41—C40—S6	119.0 (3)
C9—C8—O9	119.1 (3)	C45—C40—S6	121.6 (3)
C13—C8—O9	120.1 (3)	C42—C41—C40	119.3 (4)
C10—C9—C8	119.6 (3)	C42—C41—H41	120.4
C10—C9—S2	119.0 (3)	C40—C41—H41	120.4
C8—C9—S2	121.3 (3)	C41—C42—C43	122.1 (3)
C11—C10—C9	119.4 (3)	C41—C42—Br3	119.6 (3)
C11—C10—H10	120.3	C43—C42—Br3	118.2 (3)
C9—C10—H10	120.3	C42—C43—C44	119.3 (4)
C10—C11—C12	121.3 (3)	C42—C43—H43	120.3
C10—C11—Br1	118.9 (3)	C44—C43—H43	120.3
C12—C11—Br1	119.7 (3)	C43—C44—C45	119.2 (3)
C13—C12—C11	119.7 (3)	C43—C44—S8	119.4 (3)
C13—C12—H12	120.2	C45—C44—S8	121.5 (3)
C11—C12—H12	120.2	C40—C45—C44	120.8 (3)
C12—C13—C8	119.3 (3)	C40—C45—O12	119.5 (3)
C12—C13—S8	119.0 (3)	C44—C45—O12	119.6 (3)
C8—C13—S8	121.7 (3)	C47—C46—C51	121.1 (4)
C15—C14—C19	118.9 (4)	C47—C46—S7	119.6 (3)
C15—C14—H14	120.5	C51—C46—S7	119.4 (3)
C19—C14—H14	120.5	C48—C47—C46	119.2 (4)
C14—C15—C16	121.1 (4)	C48—C47—H47	120.4
C14—C15—H15	119.4	C46—C47—H47	120.4
C16—C15—H15	119.4	C47—C48—C49	121.2 (4)
C17—C16—C15	118.0 (4)	C47—C48—H48	119.4
C17—C16—C20	122.0 (5)	C49—C48—H48	119.4
C15—C16—C20	120.0 (5)	C50—C49—C48	118.4 (4)
C18—C17—C16	122.3 (4)	C50—C49—C52	120.6 (4)
C18—C17—H17	118.8	C48—C49—C52	121.0 (4)
C16—C17—H17	118.8	C51—C50—C49	121.9 (4)
C17—C18—C19	118.7 (4)	C51—C50—H50	119.0
C17—C18—H18	120.7	C49—C50—H50	119.0
C19—C18—H18	120.7	C50—C51—C46	118.3 (4)
C14—C19—C18	120.9 (4)	C50—C51—H51	120.9
C14—C19—S3	119.3 (3)	C46—C51—H51	120.9
C18—C19—S3	119.7 (3)	C49—C52—H52A	109.5
C16—C20—H20A	109.5	C49—C52—H52B	109.5
C16—C20—H20B	109.5	H52A—C52—H52B	109.5
H20A—C20—H20B	109.5	C49—C52—H52C	109.5
C16—C20—H20C	109.5	H52A—C52—H52C	109.5
H20A—C20—H20C	109.5	H52B—C52—H52C	109.5
H20B—C20—H20C	109.5	Cl2—C53—Cl1	113.0 (3)
C22—C21—C26	121.0 (3)	Cl2—C53—H53A	109.0
C22—C21—O11	119.5 (3)	Cl1—C53—H53A	109.0
C26—C21—O11	119.4 (3)	Cl2—C53—H53B	109.0
C23—C22—C21	119.0 (3)	Cl1—C53—H53B	109.0
C23—C22—S2	119.2 (3)	H53A—C53—H53B	107.8
C21—C22—S2	121.8 (3)	C8—O9—S1	118.8 (2)
C24—C23—C22	119.6 (3)	C32—O10—S5	117.8 (2)
C24—C23—H23	120.2	C21—O11—S3	119.2 (2)
C22—C23—H23	120.2	C45—O12—S7	119.2 (2)
C23—C24—C25	121.7 (3)	O1—S1—O2	120.9 (2)
C23—C24—Br4	119.2 (3)	O1—S1—O9	107.33 (15)
C25—C24—Br4	119.0 (3)	O2—S1—O9	106.71 (17)
C26—C25—C24	119.0 (3)	O1—S1—C6	111.5 (2)
C26—C25—H25	120.5	O2—S1—C6	107.20 (19)
C24—C25—H25	120.5	O9—S1—C6	101.25 (15)
C25—C26—C21	119.6 (3)	C9—S2—C22	99.98 (16)
C25—C26—S4	118.6 (3)	O5—S3—O6	120.6 (2)
C21—C26—S4	121.8 (3)	O5—S3—O11	107.63 (15)
C28—C27—C32	119.7 (3)	O6—S3—O11	106.77 (17)
C28—C27—S4	118.6 (3)	O5—S3—C19	111.19 (18)
C32—C27—S4	121.7 (3)	O6—S3—C19	107.50 (18)
C29—C28—C27	118.9 (3)	O11—S3—C19	101.35 (15)
C29—C28—H28	120.5	C27—S4—C26	97.10 (15)
C27—C28—H28	120.5	O4—S5—O3	121.12 (18)
C30—C29—C28	121.9 (3)	O4—S5—O10	106.07 (15)
C30—C29—Br2	119.5 (3)	O3—S5—O10	106.85 (14)
C28—C29—Br2	118.5 (3)	O4—S5—C33	107.62 (17)
C29—C30—C31	119.6 (3)	O3—S5—C33	111.79 (19)
C29—C30—H30	120.2	O10—S5—C33	101.43 (15)
C31—C30—H30	120.2	C31—S6—C40	99.90 (17)
C32—C31—C30	119.0 (3)	O7—S7—O8	120.84 (18)
C32—C31—S6	121.9 (3)	O7—S7—O12	107.23 (14)
C30—C31—S6	119.1 (3)	O8—S7—O12	106.70 (15)
C31—C32—C27	120.8 (3)	O7—S7—C46	111.01 (18)
C31—C32—O10	119.2 (3)	O8—S7—C46	108.04 (17)
C27—C32—O10	119.9 (3)	O12—S7—C46	101.15 (15)
C34—C33—C38	120.6 (4)	C13—S8—C44	98.43 (16)

C6—C1—C2—C3	−0.1 (6)	C41—C42—C43—C44	−2.5 (6)
C1—C2—C3—C4	−0.8 (7)	Br3—C42—C43—C44	−179.8 (3)
C1—C2—C3—C7	178.1 (4)	C42—C43—C44—C45	0.3 (5)
C2—C3—C4—C5	0.9 (7)	C42—C43—C44—S8	179.0 (3)
C7—C3—C4—C5	−178.0 (4)	C41—C40—C45—C44	−2.1 (5)
C3—C4—C5—C6	−0.1 (6)	S6—C40—C45—C44	179.6 (3)
C4—C5—C6—C1	−0.9 (6)	C41—C40—C45—O12	−179.2 (3)
C4—C5—C6—S1	178.4 (3)	S6—C40—C45—O12	2.5 (4)
C2—C1—C6—C5	1.0 (6)	C43—C44—C45—C40	2.0 (5)
C2—C1—C6—S1	−178.3 (3)	S8—C44—C45—C40	−176.7 (3)
C13—C8—C9—C10	−1.2 (5)	C43—C44—C45—O12	179.1 (3)
O9—C8—C9—C10	−177.1 (3)	S8—C44—C45—O12	0.4 (5)
C13—C8—C9—S2	179.6 (3)	C51—C46—C47—C48	−0.9 (6)
O9—C8—C9—S2	3.6 (4)	S7—C46—C47—C48	178.2 (3)
C8—C9—C10—C11	−0.1 (5)	C46—C47—C48—C49	−0.3 (6)
S2—C9—C10—C11	179.2 (3)	C47—C48—C49—C50	1.0 (6)
C9—C10—C11—C12	0.8 (5)	C47—C48—C49—C52	−179.0 (4)
C9—C10—C11—Br1	176.6 (3)	C48—C49—C50—C51	−0.6 (6)
C10—C11—C12—C13	−0.3 (5)	C52—C49—C50—C51	179.4 (4)
Br1—C11—C12—C13	−176.0 (3)	C49—C50—C51—C46	−0.5 (6)
C11—C12—C13—C8	−1.0 (5)	C47—C46—C51—C50	1.3 (6)
C11—C12—C13—S8	178.2 (3)	S7—C46—C51—C50	−177.8 (3)
C9—C8—C13—C12	1.7 (5)	C9—C8—O9—S1	−99.3 (3)
O9—C8—C13—C12	177.6 (3)	C13—C8—O9—S1	84.7 (4)
C9—C8—C13—S8	−177.4 (3)	C31—C32—O10—S5	−99.5 (3)
O9—C8—C13—S8	−1.5 (4)	C27—C32—O10—S5	83.7 (3)
C19—C14—C15—C16	−2.7 (6)	C22—C21—O11—S3	−97.4 (3)
C14—C15—C16—C17	2.6 (6)	C26—C21—O11—S3	87.3 (3)
C14—C15—C16—C20	−177.3 (4)	C40—C45—O12—S7	−100.4 (3)
C15—C16—C17—C18	−1.1 (6)	C44—C45—O12—S7	82.5 (4)
C20—C16—C17—C18	178.8 (4)	C8—O9—S1—O1	19.2 (3)
C16—C17—C18—C19	−0.3 (6)	C8—O9—S1—O2	−111.8 (3)
C15—C14—C19—C18	1.2 (5)	C8—O9—S1—C6	136.2 (3)
C15—C14—C19—S3	−177.2 (3)	C5—C6—S1—O1	19.2 (4)
C17—C18—C19—C14	0.3 (6)	C1—C6—S1—O1	−161.5 (3)
C17—C18—C19—S3	178.7 (3)	C5—C6—S1—O2	153.7 (3)
C26—C21—C22—C23	−4.1 (5)	C1—C6—S1—O2	−27.0 (4)
O11—C21—C22—C23	−179.3 (3)	C5—C6—S1—O9	−94.7 (3)
C26—C21—C22—S2	177.9 (2)	C1—C6—S1—O9	84.6 (3)
O11—C21—C22—S2	2.7 (4)	C10—C9—S2—C22	109.5 (3)
C21—C22—C23—C24	1.3 (5)	C8—C9—S2—C22	−71.2 (3)
S2—C22—C23—C24	179.4 (3)	C23—C22—S2—C9	109.9 (3)
C22—C23—C24—C25	1.5 (6)	C21—C22—S2—C9	−72.1 (3)
C22—C23—C24—Br4	178.7 (3)	C21—O11—S3—O5	18.4 (3)
C23—C24—C25—C26	−1.6 (6)	C21—O11—S3—O6	−112.4 (3)
Br4—C24—C25—C26	−178.8 (3)	C21—O11—S3—C19	135.2 (3)
C24—C25—C26—C21	−1.2 (5)	C14—C19—S3—O5	10.2 (3)
C24—C25—C26—S4	179.5 (3)	C18—C19—S3—O5	−168.2 (3)
C22—C21—C26—C25	4.0 (5)	C14—C19—S3—O6	144.2 (3)
O11—C21—C26—C25	179.2 (3)	C18—C19—S3—O6	−34.2 (4)
C22—C21—C26—S4	−176.7 (3)	C14—C19—S3—O11	−103.9 (3)
O11—C21—C26—S4	−1.4 (4)	C18—C19—S3—O11	77.7 (3)
C32—C27—C28—C29	−0.3 (5)	C28—C27—S4—C26	−110.9 (3)
S4—C27—C28—C29	−179.4 (3)	C32—C27—S4—C26	69.9 (3)
C27—C28—C29—C30	−1.5 (5)	C25—C26—S4—C27	−111.9 (3)
C27—C28—C29—Br2	−178.2 (3)	C21—C26—S4—C27	68.8 (3)
C28—C29—C30—C31	0.6 (6)	C32—O10—S5—O4	−118.6 (2)
Br2—C29—C30—C31	177.3 (3)	C32—O10—S5—O3	11.9 (3)
C29—C30—C31—C32	2.1 (5)	C32—O10—S5—C33	129.1 (2)
C29—C30—C31—S6	179.8 (3)	C34—C33—S5—O4	−28.7 (4)
C30—C31—C32—C27	−3.8 (5)	C38—C33—S5—O4	150.4 (3)
S6—C31—C32—C27	178.5 (3)	C34—C33—S5—O3	−164.0 (3)
C30—C31—C32—O10	179.4 (3)	C38—C33—S5—O3	15.1 (4)
S6—C31—C32—O10	1.7 (4)	C34—C33—S5—O10	82.5 (3)
C28—C27—C32—C31	3.0 (5)	C38—C33—S5—O10	−98.4 (3)
S4—C27—C32—C31	−177.9 (3)	C32—C31—S6—C40	−71.4 (3)
C28—C27—C32—O10	179.7 (3)	C30—C31—S6—C40	110.9 (3)
S4—C27—C32—O10	−1.2 (4)	C41—C40—S6—C31	110.3 (3)
C38—C33—C34—C35	1.6 (6)	C45—C40—S6—C31	−71.5 (3)
S5—C33—C34—C35	−179.3 (3)	C45—O12—S7—O7	13.5 (3)
C33—C34—C35—C36	−0.5 (7)	C45—O12—S7—O8	−117.3 (3)
C34—C35—C36—C37	−1.1 (7)	C45—O12—S7—C46	129.9 (3)
C34—C35—C36—C39	179.2 (4)	C47—C46—S7—O7	−162.0 (3)
C35—C36—C37—C38	1.7 (7)	C51—C46—S7—O7	17.1 (4)
C39—C36—C37—C38	−178.6 (4)	C47—C46—S7—O8	−27.4 (3)
C34—C33—C38—C37	−1.0 (6)	C51—C46—S7—O8	151.7 (3)
S5—C33—C38—C37	179.9 (3)	C47—C46—S7—O12	84.5 (3)
C36—C37—C38—C33	−0.6 (6)	C51—C46—S7—O12	−96.4 (3)
C45—C40—C41—C42	−0.1 (5)	C12—C13—S8—C44	−110.6 (3)
S6—C40—C41—C42	178.2 (3)	C8—C13—S8—C44	68.6 (3)
C40—C41—C42—C43	2.4 (6)	C43—C44—S8—C13	−112.0 (3)
C40—C41—C42—Br3	179.7 (3)	C45—C44—S8—C13	66.6 (3)

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2, Cg3 and Cg4 are the centroids of the C14–C19, C1–C6, C51–C56 and C33–C38 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O8	0.95	2.51	3.303 (5)	141
C53—H53A···O5ⁱ	0.99	2.38	3.175 (5)	137
C53—H53B···O4ⁱⁱ	0.99	2.37	3.249 (5)	147
C17—H17···O2ⁱⁱⁱ	0.95	2.38	3.266 (5)	155
C10—H10···Cg1	0.95	2.75	3.698 (1)	178
C23—H23···Cg2	0.95	2.65	3.602 (1)	176
C30—H30···Cg3	0.95	2.80	3.742 (1)	174
C41—H41···Cg4	0.95	2.85	3.794 (1)	172

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

Experimental details

Crystal data
Chemical formula	C₅₂H₃₆Br₄O₁₂S₈·CH₂Cl₂
M_r	1513.85
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	12.6945 (14), 20.793 (2), 23.190 (3)
β (°)	103.350 (2)
V (Å³)	5955.8 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.13
Crystal size (mm)	0.30 × 0.21 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.453, 0.705
No. of measured, independent and observed [I > 2σ(I)] reflections	30976, 11092, 7807
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.107, 1.06
No. of reflections	11092
No. of parameters	715
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.68

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

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2, Cg3 and Cg4 are the centroids of the C14–C19, C1–C6, C51–C56 and C33–C38 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O8	0.95	2.51	3.303 (5)	141.3
C53—H53A···O5ⁱ	0.99	2.38	3.175 (5)	137.3
C53—H53B···O4ⁱⁱ	0.99	2.37	3.249 (5)	146.9
C17—H17···O2ⁱⁱⁱ	0.95	2.38	3.266 (5)	155.3
C10—H10···Cg1	0.95	2.749	3.698 (1)	177.66
C23—H23···Cg2	0.95	2.654	3.602 (1)	175.84
C30—H30···Cg3	0.95	2.795	3.742 (1)	174.05
C41—H41···Cg4	0.95	2.851	3.794 (1)	172.30

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

Acknowledgements

Financial support from the National Natural Science Foundation of China (No. 20572064) and the Shandong Province Natural Science Foundation (Y2006B30) is gratefully acknowledged.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bondi, A. J. (1964). Chem. Phys. 68, 441–452. CrossRef CAS Google Scholar
Bruker (1999). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Guo, D.-S., Liu, Z.-P., Ma, J.-P. & Huang, R.-Q. (2007). Tetrahedron Lett. 48, 1221–1224. Web of Science CrossRef CAS Google Scholar
Kasyan, O., Swierczynski, D., Drapailo, A., Suwinska, K., Lipkowski, J. & Kalchenko, V. (2003). Tetrahedron Lett. 44, 7167–7170. Web of Science CSD CrossRef CAS Google Scholar
Kumagai, H., Hasegawa, M., Miyanari, S., Sugawa, Y., Sato, Y., Hori, T., Ueda, S., Kamiyama, H. & Miyano, S. (1997). Tetrahedron Lett. 38, 3971–3972. CrossRef CAS Web of Science Google Scholar
Lhoták, P. (2004). Eur. J. Org. Chem. pp. 1675–1692. Google Scholar
Lhoták, P., Himl, M., Stibor, I., Sykora, J. & Cisarová, I. (2001). Tetrahedron Lett. 42, 7107–7110. Google Scholar
Lommerse, J. P. M., Stone, A. J., Taylor, R. & Allen, F. H. (1996). J. Am. Chem. Soc. 118, 3108–3116. CrossRef CAS Web of Science Google Scholar
Metrangolo, P. & Resnati, G. (2001). Chem. Eur. J. 7, 2511–2519. CrossRef PubMed CAS Google Scholar
Morohashi, N., Narumi, F., Iki, N., Hattori, T. & Miyano, S. (2006). Chem. Rev. 106, 5291–5316. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shokova, E. A. & Kovalev, V. V. (2003). Russ. J. Org. Chem. 39, 1–28. Web of Science CrossRef CAS Google Scholar
Tsuzuki, S., Honda, K., Uchimaru, T., Mikami, M. & Tanabe, K. (2000). J. Am. Chem. Soc. 122, 3746–3753. Web of Science CrossRef CAS Google Scholar
Xu, W.-N., Yuan, J.-M., Liu, Y., Ma, J.-P. & Guo, D.-S. (2008). Acta Cryst. C64, o349–o352. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 4| April 2010| Pages o871-o872

doi:10.1107/S1600536810009554

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

5,11,17,23-Tetra­bromo-25,26,27,28-tetra­kis(4-tolyl­sulfon­yl­oxy)-2,8,14,20-tetra­thia­calix[4]arene di­chloro­methane solvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

5,11,17,23-Tetrabromo-25,26,27,28-tetrakis(4-tolylsulfonyloxy)-2,8,14,20-tetrathiacalix[4]arene dichloromethane solvate