Tetra-O-4-methyl­phenyl­sulfonyl­penta­erythritol

Li, S.-X.; Zhu, L.; Fun, H.-K.; Chantrapromma, S.

doi:10.1107/S1600536808020643

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Pages o1474-o1475

doi:10.1107/S1600536808020643

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Tetra-O-4-methylphenylsulfonylpentaerythritol

Shu-Xian Li,^a,^b Lin Zhu,^b Hoong-Kun Fun ^c ^* and Suchada Chantrapromma ^d ‡

^aDepartment of Chemistry, Handan College, Handan, Hebei 056005, People's Republic of China, ^bDepartment of Chemistry, Beijing Normal University, Beijing 100875, People's Republic of China, ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^dCrystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand
^*Correspondence e-mail: hkfun@usm.my

(Received 30 June 2008; accepted 4 July 2008; online 12 July 2008)

In the title molecule (systematic name: methanetetrayltetramethylene tetra-p-toluenesulfonate), C₃₃H₃₆O₁₂S₄, the central C atom and the S atoms exhibit distorted tetrahedral configurations. The aromatic rings in opposite arms are nearly parallel to each other, with a dihedral angle of 10.26 (8) or 3.45 (9)°. The molecules are linked into a two-dimensional network parallel to the bc plane by weak C—H⋯O hydrogen bonds, π–π [centroid–centroid distance = 3.5806 (12) Å] and S—O⋯π [O⋯centroid = 3.1455 (15) Å and S—O⋯centroid = 122.41 (7)°] intermolecular interactions. Intramolecular C—H⋯O hydrogen bonds are also present.

Related literature

For bond-length data, see: Allen et al. (1987 ). For a related structure, see: Li et al. (2008 ). For general background and applications of pentaerythritol derivatives, see: Constable et al. (1998 ); Fundueanu et al. (1998 ); Jiang et al. (2002 ); Kim et al. (2000 ); Luo & Chen (2001 ); Mischiati et al. (2001 ); Oike et al. (2001 ).

Experimental

Crystal data

C₃₃H₃₆O₁₂S₄
M_r = 752.86
Monoclinic, P 2₁ /c
a = 13.2983 (2) Å
b = 18.0368 (2) Å
c = 15.4181 (2) Å
β = 110.653 (1)°
V = 3460.50 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 100.0 (1) K
0.47 × 0.41 × 0.16 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.857, T_max = 0.949
45048 measured reflections
10090 independent reflections
7927 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.119
S = 1.04
10090 reflections
446 parameters
H-atom parameters constrained
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2C⋯O4	0.97	2.48	2.849 (2)	102
C3—H3B⋯O6	0.97	2.47	2.905 (2)	107
C3—H3B⋯O7	0.97	2.55	2.876 (2)	100
C3—H3C⋯O9ⁱ	0.97	2.46	3.433 (2)	175
C4—H4A⋯O4	0.97	2.55	2.879 (2)	100
C5—H5B⋯O12	0.97	2.44	2.888 (2)	107
C5—H5C⋯O7	0.97	2.49	2.8396 (19)	101
C7—H7A⋯O2	0.93	2.58	2.937 (2)	103
C8—H8B⋯O11ⁱⁱ	0.93	2.52	3.140 (2)	124
C10—H10A⋯O6ⁱ	0.93	2.41	3.257 (2)	151
C18—H18A⋯O6	0.93	2.59	2.932 (2)	103
C22—H22A⋯O12ⁱⁱⁱ	0.93	2.52	3.154 (2)	126
C25—H25A⋯O8	0.93	2.56	2.924 (2)	104
C28—H28A⋯O12	0.93	2.54	2.905 (2)	104
C29—H29A⋯O8^iv	0.93	2.42	3.334 (2)	165
C31—H31A⋯O12ⁱⁱⁱ	0.93	2.53	3.209 (2)	130
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z+1; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808020643/ci2625sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808020643/ci2625Isup2.hkl

checkCIF report

Comment top

Pentaerythritol is a valuable starting point for building complex molecular and supramolecular structures due to its symmetric four-armed geometry and is widely used in macromolecular chemistry (Oike et al., 2001), medicinal chemistry (Mischiati et al., 2001; Fundueanu et al., 1998), in the construction of dendrimers (Jiang et al., 2002; Constable et al., 1998) and other applications (Kim et al., 2000; Luo & Chen, 2001). To explore the potential of the pentaerythritol unit in supramolecular chemistry, we report herein the synthesis and crystal structure of tetra-O-(4-methylphenylsulfonyl)pentaerythritol, the title compound.

In the title molecule (Fig. 1), atoms C1, S1, S2, S3 and S4 exhibit the usual distorted tetrahedral configuration. The aromatic rings in opposite arms of the molecule are nearly parallel to each other; the dihedral angles between the C6–C11 (A) and C20–C25 (B) benzene rings is 10.26 (8)° and that between the C13–C18 (C) and C27–C32 (D) benzene rings is 3.45 (9)°. The dihedral angle between the adjacent benzene rings are: A/C 49.67 (9)°, A/D 52.93 (9)°, B/C 53.20 (9)° and B/D 56.15 (9)°. The O1/O7/C1/C2/C4 plane (r.m.s. deviation 0.039 Å) forms dihedral angles of 81.59 (5)° and 84.85 (5)°, respectively, with the rings A and B. The benzene rings C and D form dihedral angles of 59.75 (5)° and 62.82 (5)°, respectively, with the O4/O10/C1/C3/C5 plane. The conformations of the four 4-methylphenylsulfonyl groups with respect to the pentaerythritol unit (C1–C5/O1/O4/O7/O10) can be indicated by torsion angles S1—O1—C2—C1 = -175.72 (10)°, S2—O4—C3—C1 = 154.00 (10)°, S3—O7—C4—C1 = -179.78 (10)° and S4—O10—C5—C1 = 154.75 (10)°. Bond lengths and angles in the title molecule are in normal ranges (Allen et al., 1987) and comparable to those in a related structure (Li et al., 2008).

In the crystal packing (Fig. 2), the molecules are linked into a two-dimensional network parallel to the bc plane by weak C—H···O hydrogen bonds (Table 1). In addition, π-π interactions are observed between C13-C18 (centroid Cg1) and C27-C32 (centroid Cg2) benzene rings at (x, y, z) and (1+x, y, z), respectively, with centroid-centroid distance of 3.5806 (12) Å. Also, an S—O···π intermolecular interaction is observed [O3···Cg2ⁱ = 3.1455 (15) Å and S1—O3···Cg2ⁱ = 122.41 (7)°; the symmetry code is given in Table 1].

Related literature top

For bond-length data, see: Allen et al. (1987). For a related structure, see: Li et al. (2008). For general background and applications of pentaerythritol derivatives, see: Constable et al. (1998); Fundueanu et al. (1998); Jiang et al. (2002); Kim et al. (2000); Luo & Chen (2001); Mischiati et al. (2001); Oike et al. (2001).

Experimental top

The title compound was synthesized by dissolving pentaerythritol (1.36 g, 10.0 mmol) in dry pyridine (80 ml) and tosyl chloride (9.5 g, 50.0 mmol) was then added. The reaction mixture was stirred for 24 h at room temperature, after which it was poured into ice-water (250 ml) containing 1 M HCl and extracted with CH₂Cl₂ (80 × 3 ml). The organic layer was washed with water (60 × 2 ml), dried with MgSO₄ and concentrated. The solid residue was recrystallized from ethanol to afford the desired compound as a white solid (6.42 g, yield: 90%). Block-shaped colourless single crystals of the title compound suitable for X-ray structure determination were recrystallized from ethanol by slow evaporation of the solvent in the open air at room temperature (m.p. 423 K).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 40% probability displacement ellipsoids and the atomic numbering.
	Fig. 2. The crystal packing of the title compound, viewed down the b axis. Hydrogen bonds are shown as dashed lines.

methanetetrayltetramethylene tetra-p-toluenesulfonate top

Crystal data top

C₃₃H₃₆O₁₂S₄	F(000) = 1576
M_r = 752.86	D_x = 1.445 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 423 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.2983 (2) Å	Cell parameters from 10090 reflections
b = 18.0368 (2) Å	θ = 1.8–30.0°
c = 15.4181 (2) Å	µ = 0.34 mm⁻¹
β = 110.653 (1)°	T = 100 K
V = 3460.50 (8) Å³	Block, colourless
Z = 4	0.47 × 0.41 × 0.16 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	10090 independent reflections
Radiation source: fine-focus sealed tube	7927 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 8.33 pixels mm^-1	θ_max = 30.0°, θ_min = 1.8°
ω scans	h = −18→17
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −25→25
T_min = 0.857, T_max = 0.949	l = −21→21
45048 measured reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0595P)² + 1.2746P] where P = (F_o² + 2F_c²)/3
10090 reflections	(Δ/σ)_max = 0.001
446 parameters	Δρ_max = 0.66 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₃₃H₃₆O₁₂S₄	V = 3460.50 (8) Å³
M_r = 752.86	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.2983 (2) Å	µ = 0.34 mm⁻¹
b = 18.0368 (2) Å	T = 100 K
c = 15.4181 (2) Å	0.47 × 0.41 × 0.16 mm
β = 110.653 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	10090 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	7927 reflections with I > 2σ(I)
T_min = 0.857, T_max = 0.949	R_int = 0.039
45048 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.04	Δρ_max = 0.66 e Å⁻³
10090 reflections	Δρ_min = −0.42 e Å⁻³
446 parameters

Special details top

Experimental. The low-temparture data was collected with the Oxford Cryosystem Cobra low-temperature attachment.

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

	x	y	z	U_iso*/U_eq
S1	0.04280 (3)	0.38393 (2)	0.37155 (3)	0.01965 (9)
S2	0.41959 (4)	0.31806 (2)	0.71340 (3)	0.02583 (10)
S3	0.16570 (3)	0.37598 (2)	0.89436 (3)	0.02097 (9)
S4	−0.18947 (4)	0.29379 (2)	0.54246 (3)	0.02429 (10)
O1	0.06272 (10)	0.34535 (6)	0.46843 (7)	0.0207 (2)
O2	−0.01854 (10)	0.45006 (6)	0.36647 (8)	0.0249 (2)
O3	0.00233 (10)	0.32556 (7)	0.30634 (8)	0.0267 (3)
O4	0.30102 (10)	0.34530 (6)	0.65781 (9)	0.0256 (3)
O5	0.48315 (12)	0.38305 (7)	0.72159 (10)	0.0347 (3)
O6	0.41903 (11)	0.28056 (7)	0.79505 (9)	0.0323 (3)
O7	0.14708 (10)	0.33953 (6)	0.79639 (7)	0.0213 (2)
O8	0.24146 (10)	0.43489 (6)	0.90850 (8)	0.0256 (3)
O9	0.18879 (11)	0.31437 (6)	0.95619 (8)	0.0280 (3)
O10	−0.07710 (10)	0.33045 (6)	0.60052 (8)	0.0237 (2)
O11	−0.26269 (11)	0.35436 (7)	0.52419 (10)	0.0334 (3)
O12	−0.17766 (11)	0.25301 (7)	0.46728 (8)	0.0302 (3)
C1	0.11235 (13)	0.34044 (8)	0.63322 (10)	0.0189 (3)
C2	0.08925 (14)	0.39261 (8)	0.55016 (11)	0.0205 (3)
H2B	0.0296	0.4252	0.5457	0.025*
H2C	0.1518	0.4227	0.5563	0.025*
C3	0.21256 (13)	0.29377 (8)	0.64564 (12)	0.0213 (3)
H3B	0.2282	0.2619	0.6995	0.026*
H3C	0.2015	0.2629	0.5915	0.026*
C4	0.12796 (14)	0.38928 (8)	0.71795 (11)	0.0203 (3)
H4A	0.1888	0.4222	0.7284	0.024*
H4B	0.0643	0.4191	0.7090	0.024*
C5	0.01947 (13)	0.28597 (8)	0.61833 (11)	0.0207 (3)
H5B	0.0121	0.2538	0.5660	0.025*
H5C	0.0322	0.2555	0.6730	0.025*
C6	0.17148 (13)	0.40800 (8)	0.37554 (10)	0.0193 (3)
C7	0.20491 (14)	0.48153 (9)	0.38533 (12)	0.0246 (3)
H7A	0.1592	0.5190	0.3905	0.030*
C8	0.30696 (15)	0.49811 (9)	0.38722 (13)	0.0284 (4)
H8B	0.3296	0.5473	0.3936	0.034*
C9	0.37690 (14)	0.44311 (10)	0.37979 (12)	0.0265 (3)
C10	0.34113 (15)	0.36985 (9)	0.36990 (12)	0.0274 (4)
H10A	0.3868	0.3324	0.3647	0.033*
C11	0.23934 (15)	0.35158 (9)	0.36764 (12)	0.0249 (3)
H11B	0.2165	0.3025	0.3610	0.030*
C12	0.48782 (16)	0.46125 (12)	0.38123 (15)	0.0365 (4)
H12B	0.5096	0.5085	0.4104	0.055*
H12C	0.4874	0.4630	0.3189	0.055*
H12D	0.5372	0.4238	0.4154	0.055*
C13	0.44820 (14)	0.25381 (9)	0.64082 (12)	0.0250 (3)
C14	0.48460 (15)	0.27930 (10)	0.57213 (12)	0.0279 (4)
H14A	0.4921	0.3298	0.5641	0.033*
C15	0.50952 (15)	0.22807 (10)	0.51580 (13)	0.0296 (4)
H15A	0.5344	0.2447	0.4699	0.035*
C16	0.49800 (15)	0.15206 (10)	0.52657 (13)	0.0290 (4)
C17	0.46100 (15)	0.12852 (10)	0.59613 (14)	0.0306 (4)
H17A	0.4530	0.0780	0.6042	0.037*
C18	0.43601 (14)	0.17829 (9)	0.65301 (13)	0.0266 (3)
H18A	0.4113	0.1617	0.6990	0.032*
C19	0.52492 (17)	0.09697 (12)	0.46446 (14)	0.0370 (4)
H19A	0.5668	0.0573	0.5013	0.056*
H19B	0.5654	0.1212	0.4320	0.056*
H19C	0.4597	0.0773	0.4205	0.056*
C20	0.04014 (14)	0.41323 (8)	0.88336 (11)	0.0211 (3)
C21	−0.04285 (15)	0.36589 (9)	0.88235 (12)	0.0262 (4)
H21A	−0.0325	0.3148	0.8863	0.031*
C22	−0.14120 (15)	0.39600 (10)	0.87544 (12)	0.0275 (4)
H22A	−0.1969	0.3646	0.8750	0.033*
C23	−0.15853 (15)	0.47227 (10)	0.86912 (12)	0.0257 (3)
C24	−0.07485 (16)	0.51828 (10)	0.86920 (13)	0.0295 (4)
H24A	−0.0855	0.5693	0.8647	0.035*
C25	0.02422 (15)	0.48965 (9)	0.87594 (12)	0.0267 (4)
H25A	0.0795	0.5211	0.8755	0.032*
C26	−0.26526 (16)	0.50341 (11)	0.86390 (14)	0.0345 (4)
H26A	−0.2727	0.5529	0.8395	0.052*
H26B	−0.2694	0.5043	0.9248	0.052*
H26C	−0.3219	0.4729	0.8240	0.052*
C27	−0.21526 (13)	0.23237 (9)	0.61915 (12)	0.0229 (3)
C28	−0.21199 (14)	0.15680 (9)	0.60537 (12)	0.0250 (3)
H28A	−0.1927	0.1383	0.5571	0.030*
C29	−0.23782 (15)	0.10914 (10)	0.66464 (13)	0.0289 (4)
H29A	−0.2360	0.0582	0.6556	0.035*
C30	−0.26628 (15)	0.13558 (11)	0.73704 (13)	0.0294 (4)
C31	−0.26943 (15)	0.21215 (11)	0.74919 (13)	0.0304 (4)
H31A	−0.2891	0.2307	0.7972	0.037*
C32	−0.24395 (15)	0.26053 (10)	0.69117 (12)	0.0278 (4)
H32A	−0.2459	0.3114	0.7000	0.033*
C33	−0.29291 (18)	0.08257 (13)	0.80129 (15)	0.0412 (5)
H33A	−0.3346	0.0421	0.7661	0.062*
H33B	−0.3335	0.1080	0.8328	0.062*
H33C	−0.2276	0.0637	0.8460	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0232 (2)	0.02041 (17)	0.01541 (17)	0.00089 (14)	0.00691 (15)	−0.00004 (13)
S2	0.0271 (2)	0.0254 (2)	0.0251 (2)	−0.00384 (16)	0.00944 (17)	−0.00123 (16)
S3	0.0284 (2)	0.01908 (17)	0.01522 (18)	0.00331 (14)	0.00744 (16)	0.00123 (13)
S4	0.0255 (2)	0.02166 (18)	0.0239 (2)	0.00318 (15)	0.00649 (17)	−0.00113 (15)
O1	0.0300 (6)	0.0187 (5)	0.0152 (5)	−0.0004 (4)	0.0103 (5)	−0.0008 (4)
O2	0.0259 (6)	0.0246 (5)	0.0243 (6)	0.0052 (5)	0.0090 (5)	0.0024 (5)
O3	0.0298 (7)	0.0288 (6)	0.0193 (6)	−0.0038 (5)	0.0060 (5)	−0.0053 (5)
O4	0.0273 (6)	0.0218 (5)	0.0310 (6)	0.0007 (5)	0.0143 (5)	0.0025 (5)
O5	0.0381 (8)	0.0302 (6)	0.0361 (7)	−0.0115 (5)	0.0133 (6)	−0.0044 (5)
O6	0.0386 (8)	0.0343 (7)	0.0228 (6)	−0.0049 (6)	0.0093 (6)	0.0004 (5)
O7	0.0321 (7)	0.0177 (5)	0.0151 (5)	0.0052 (4)	0.0097 (5)	0.0022 (4)
O8	0.0265 (6)	0.0254 (6)	0.0227 (6)	0.0006 (5)	0.0057 (5)	−0.0001 (5)
O9	0.0401 (8)	0.0243 (6)	0.0180 (6)	0.0057 (5)	0.0085 (5)	0.0053 (4)
O10	0.0224 (6)	0.0204 (5)	0.0289 (6)	0.0013 (4)	0.0099 (5)	−0.0037 (5)
O11	0.0310 (7)	0.0252 (6)	0.0390 (8)	0.0076 (5)	0.0063 (6)	0.0022 (5)
O12	0.0381 (8)	0.0297 (6)	0.0213 (6)	0.0014 (5)	0.0088 (5)	−0.0021 (5)
C1	0.0248 (8)	0.0175 (6)	0.0161 (7)	0.0020 (6)	0.0091 (6)	0.0007 (5)
C2	0.0287 (9)	0.0184 (6)	0.0165 (7)	0.0010 (6)	0.0107 (6)	−0.0016 (5)
C3	0.0241 (8)	0.0197 (7)	0.0225 (8)	0.0012 (6)	0.0110 (7)	−0.0009 (6)
C4	0.0294 (9)	0.0172 (6)	0.0158 (7)	0.0033 (6)	0.0099 (6)	0.0020 (5)
C5	0.0245 (8)	0.0182 (6)	0.0212 (7)	0.0027 (6)	0.0103 (7)	0.0015 (6)
C6	0.0240 (8)	0.0199 (7)	0.0154 (7)	0.0012 (6)	0.0088 (6)	0.0012 (5)
C7	0.0283 (9)	0.0188 (7)	0.0278 (8)	0.0016 (6)	0.0112 (7)	−0.0021 (6)
C8	0.0286 (9)	0.0227 (7)	0.0356 (10)	−0.0018 (6)	0.0133 (8)	−0.0006 (7)
C9	0.0257 (9)	0.0316 (8)	0.0244 (8)	0.0025 (7)	0.0115 (7)	0.0035 (7)
C10	0.0327 (10)	0.0254 (8)	0.0293 (9)	0.0092 (7)	0.0175 (8)	0.0048 (7)
C11	0.0348 (10)	0.0178 (7)	0.0263 (8)	0.0033 (6)	0.0159 (7)	0.0018 (6)
C12	0.0290 (10)	0.0412 (10)	0.0443 (12)	0.0038 (8)	0.0190 (9)	0.0072 (9)
C13	0.0197 (8)	0.0280 (8)	0.0260 (8)	0.0004 (6)	0.0066 (7)	−0.0001 (7)
C14	0.0246 (9)	0.0318 (8)	0.0254 (8)	0.0006 (7)	0.0066 (7)	0.0050 (7)
C15	0.0270 (9)	0.0374 (9)	0.0237 (8)	0.0020 (7)	0.0083 (7)	0.0040 (7)
C16	0.0222 (9)	0.0348 (9)	0.0281 (9)	0.0030 (7)	0.0064 (7)	−0.0026 (7)
C17	0.0265 (9)	0.0282 (8)	0.0381 (10)	0.0001 (7)	0.0125 (8)	−0.0001 (7)
C18	0.0221 (8)	0.0274 (8)	0.0317 (9)	−0.0013 (6)	0.0111 (7)	0.0012 (7)
C19	0.0365 (11)	0.0414 (10)	0.0337 (10)	0.0048 (8)	0.0130 (9)	−0.0035 (8)
C20	0.0285 (9)	0.0197 (7)	0.0169 (7)	0.0023 (6)	0.0105 (6)	0.0002 (6)
C21	0.0354 (10)	0.0204 (7)	0.0254 (8)	−0.0007 (6)	0.0140 (7)	0.0004 (6)
C22	0.0319 (10)	0.0280 (8)	0.0252 (8)	−0.0043 (7)	0.0130 (7)	−0.0007 (7)
C23	0.0311 (9)	0.0290 (8)	0.0191 (8)	0.0028 (7)	0.0116 (7)	−0.0006 (6)
C24	0.0381 (10)	0.0216 (7)	0.0336 (9)	0.0063 (7)	0.0185 (8)	0.0012 (7)
C25	0.0331 (10)	0.0205 (7)	0.0295 (9)	−0.0013 (6)	0.0149 (8)	0.0004 (6)
C26	0.0344 (11)	0.0411 (10)	0.0322 (10)	0.0068 (8)	0.0168 (8)	−0.0009 (8)
C27	0.0178 (8)	0.0248 (7)	0.0242 (8)	0.0014 (6)	0.0051 (6)	−0.0021 (6)
C28	0.0228 (8)	0.0244 (8)	0.0300 (9)	0.0010 (6)	0.0120 (7)	−0.0043 (6)
C29	0.0254 (9)	0.0257 (8)	0.0373 (10)	−0.0005 (6)	0.0133 (8)	−0.0007 (7)
C30	0.0204 (9)	0.0401 (10)	0.0284 (9)	−0.0018 (7)	0.0093 (7)	0.0017 (7)
C31	0.0254 (9)	0.0430 (10)	0.0236 (8)	0.0032 (7)	0.0097 (7)	−0.0056 (7)
C32	0.0272 (9)	0.0296 (8)	0.0238 (8)	0.0034 (7)	0.0056 (7)	−0.0064 (7)
C33	0.0358 (11)	0.0524 (12)	0.0406 (12)	−0.0050 (9)	0.0198 (9)	0.0083 (10)

Geometric parameters (Å, º) top

S1—O3	1.4238 (12)	C12—H12C	0.96
S1—O2	1.4315 (12)	C12—H12D	0.96
S1—O1	1.5833 (11)	C13—C14	1.389 (2)
S1—C6	1.7453 (17)	C13—C18	1.392 (2)
S2—O5	1.4244 (13)	C14—C15	1.386 (3)
S2—O6	1.4314 (13)	C14—H14A	0.93
S2—O4	1.5840 (13)	C15—C16	1.396 (3)
S2—C13	1.7435 (18)	C15—H15A	0.93
S3—O9	1.4252 (12)	C16—C17	1.395 (3)
S3—O8	1.4271 (13)	C16—C19	1.508 (3)
S3—O7	1.5848 (11)	C17—C18	1.375 (3)
S3—C20	1.7518 (17)	C17—H17A	0.93
S4—O11	1.4240 (13)	C18—H18A	0.93
S4—O12	1.4274 (13)	C19—H19A	0.96
S4—O10	1.5899 (13)	C19—H19B	0.96
S4—C27	1.7404 (18)	C19—H19C	0.96
O1—C2	1.4578 (18)	C20—C21	1.391 (2)
O4—C3	1.458 (2)	C20—C25	1.393 (2)
O7—C4	1.4546 (18)	C21—C22	1.385 (3)
O10—C5	1.4559 (19)	C21—H21A	0.93
C1—C4	1.528 (2)	C22—C23	1.393 (2)
C1—C3	1.530 (2)	C22—H22A	0.93
C1—C2	1.531 (2)	C23—C24	1.388 (3)
C1—C5	1.531 (2)	C23—C26	1.502 (3)
C2—H2B	0.97	C24—C25	1.384 (3)
C2—H2C	0.97	C24—H24A	0.93
C3—H3B	0.97	C25—H25A	0.93
C3—H3C	0.97	C26—H26A	0.96
C4—H4A	0.97	C26—H26B	0.96
C4—H4B	0.97	C26—H26C	0.96
C5—H5B	0.97	C27—C28	1.383 (2)
C5—H5C	0.97	C27—C32	1.391 (2)
C6—C7	1.390 (2)	C28—C29	1.383 (2)
C6—C11	1.394 (2)	C28—H28A	0.93
C7—C8	1.380 (2)	C29—C30	1.384 (3)
C7—H7A	0.93	C29—H29A	0.93
C8—C9	1.392 (2)	C30—C31	1.396 (3)
C8—H8B	0.93	C30—C33	1.506 (3)
C9—C10	1.395 (2)	C31—C32	1.375 (3)
C9—C12	1.503 (3)	C31—H31A	0.93
C10—C11	1.382 (3)	C32—H32A	0.93
C10—H10A	0.93	C33—H33A	0.96
C11—H11B	0.93	C33—H33B	0.96
C12—H12B	0.96	C33—H33C	0.96

O3—S1—O2	120.75 (8)	C9—C12—H12C	109.5
O3—S1—O1	103.71 (7)	H12B—C12—H12C	109.5
O2—S1—O1	108.68 (7)	C9—C12—H12D	109.5
O3—S1—C6	109.30 (8)	H12B—C12—H12D	109.5
O2—S1—C6	109.11 (7)	H12C—C12—H12D	109.5
O1—S1—C6	103.91 (7)	C14—C13—C18	121.01 (16)
O5—S2—O6	119.85 (8)	C14—C13—S2	118.89 (13)
O5—S2—O4	103.83 (8)	C18—C13—S2	120.09 (14)
O6—S2—O4	108.03 (8)	C15—C14—C13	118.81 (17)
O5—S2—C13	110.30 (9)	C15—C14—H14A	120.6
O6—S2—C13	108.69 (8)	C13—C14—H14A	120.6
O4—S2—C13	105.06 (8)	C14—C15—C16	121.31 (17)
O9—S3—O8	120.30 (8)	C14—C15—H15A	119.3
O9—S3—O7	103.79 (7)	C16—C15—H15A	119.3
O8—S3—O7	108.60 (7)	C17—C16—C15	118.28 (17)
O9—S3—C20	109.69 (8)	C17—C16—C19	120.99 (17)
O8—S3—C20	109.06 (7)	C15—C16—C19	120.73 (17)
O7—S3—C20	104.11 (7)	C18—C17—C16	121.45 (17)
O11—S4—O12	119.87 (8)	C18—C17—H17A	119.3
O11—S4—O10	103.51 (7)	C16—C17—H17A	119.3
O12—S4—O10	108.71 (7)	C17—C18—C13	119.13 (17)
O11—S4—C27	109.74 (8)	C17—C18—H18A	120.4
O12—S4—C27	109.16 (8)	C13—C18—H18A	120.4
O10—S4—C27	104.68 (7)	C16—C19—H19A	109.5
C2—O1—S1	117.87 (9)	C16—C19—H19B	109.5
C3—O4—S2	118.41 (10)	H19A—C19—H19B	109.5
C4—O7—S3	117.34 (9)	C16—C19—H19C	109.5
C5—O10—S4	117.92 (10)	H19A—C19—H19C	109.5
C4—C1—C3	111.13 (13)	H19B—C19—H19C	109.5
C4—C1—C2	106.71 (12)	C21—C20—C25	120.63 (16)
C3—C1—C2	110.60 (13)	C21—C20—S3	119.40 (12)
C4—C1—C5	110.94 (13)	C25—C20—S3	119.97 (13)
C3—C1—C5	106.66 (12)	C22—C21—C20	118.94 (15)
C2—C1—C5	110.85 (13)	C22—C21—H21A	120.5
O1—C2—C1	106.24 (11)	C20—C21—H21A	120.5
O1—C2—H2B	110.5	C21—C22—C23	121.42 (17)
C1—C2—H2B	110.5	C21—C22—H22A	119.3
O1—C2—H2C	110.5	C23—C22—H22A	119.3
C1—C2—H2C	110.5	C24—C23—C22	118.54 (17)
H2B—C2—H2C	108.7	C24—C23—C26	121.25 (16)
O4—C3—C1	107.03 (12)	C22—C23—C26	120.21 (17)
O4—C3—H3B	110.3	C25—C24—C23	121.23 (16)
C1—C3—H3B	110.3	C25—C24—H24A	119.4
O4—C3—H3C	110.3	C23—C24—H24A	119.4
C1—C3—H3C	110.3	C24—C25—C20	119.23 (17)
H3B—C3—H3C	108.6	C24—C25—H25A	120.4
O7—C4—C1	106.63 (11)	C20—C25—H25A	120.4
O7—C4—H4A	110.4	C23—C26—H26A	109.5
C1—C4—H4A	110.4	C23—C26—H26B	109.5
O7—C4—H4B	110.4	H26A—C26—H26B	109.5
C1—C4—H4B	110.4	C23—C26—H26C	109.5
H4A—C4—H4B	108.6	H26A—C26—H26C	109.5
O10—C5—C1	106.62 (12)	H26B—C26—H26C	109.5
O10—C5—H5B	110.4	C28—C27—C32	120.99 (16)
C1—C5—H5B	110.4	C28—C27—S4	119.91 (13)
O10—C5—H5C	110.4	C32—C27—S4	119.03 (13)
C1—C5—H5C	110.4	C27—C28—C29	118.85 (16)
H5B—C5—H5C	108.6	C27—C28—H28A	120.6
C7—C6—C11	120.93 (16)	C29—C28—H28A	120.6
C7—C6—S1	120.88 (13)	C28—C29—C30	121.41 (16)
C11—C6—S1	118.18 (12)	C28—C29—H29A	119.3
C8—C7—C6	118.92 (15)	C30—C29—H29A	119.3
C8—C7—H7A	120.5	C29—C30—C31	118.61 (17)
C6—C7—H7A	120.5	C29—C30—C33	120.43 (18)
C7—C8—C9	121.64 (16)	C31—C30—C33	120.96 (18)
C7—C8—H8B	119.2	C32—C31—C30	120.96 (17)
C9—C8—H8B	119.2	C32—C31—H31A	119.5
C8—C9—C10	118.19 (16)	C30—C31—H31A	119.5
C8—C9—C12	121.62 (17)	C31—C32—C27	119.18 (16)
C10—C9—C12	120.19 (16)	C31—C32—H32A	120.4
C11—C10—C9	121.47 (16)	C27—C32—H32A	120.4
C11—C10—H10A	119.3	C30—C33—H33A	109.5
C9—C10—H10A	119.3	C30—C33—H33B	109.5
C10—C11—C6	118.85 (15)	H33A—C33—H33B	109.5
C10—C11—H11B	120.6	C30—C33—H33C	109.5
C6—C11—H11B	120.6	H33A—C33—H33C	109.5
C9—C12—H12B	109.5	H33B—C33—H33C	109.5

O3—S1—O1—C2	−170.85 (11)	O4—S2—C13—C14	83.71 (15)
O2—S1—O1—C2	−41.20 (13)	O5—S2—C13—C18	151.46 (14)
C6—S1—O1—C2	74.89 (12)	O6—S2—C13—C18	18.19 (17)
O5—S2—O4—C3	−173.46 (11)	O4—S2—C13—C18	−97.23 (15)
O6—S2—O4—C3	−45.20 (13)	C18—C13—C14—C15	−0.4 (3)
C13—S2—O4—C3	70.68 (13)	S2—C13—C14—C15	178.62 (14)
O9—S3—O7—C4	−176.31 (12)	C13—C14—C15—C16	0.4 (3)
O8—S3—O7—C4	−47.20 (13)	C14—C15—C16—C17	−0.3 (3)
C20—S3—O7—C4	68.89 (13)	C14—C15—C16—C19	179.71 (18)
O11—S4—O10—C5	−170.33 (11)	C15—C16—C17—C18	0.1 (3)
O12—S4—O10—C5	−41.85 (13)	C19—C16—C17—C18	−179.86 (18)
C27—S4—O10—C5	74.70 (12)	C16—C17—C18—C13	−0.1 (3)
S1—O1—C2—C1	−175.72 (10)	C14—C13—C18—C17	0.3 (3)
C4—C1—C2—O1	−173.83 (13)	S2—C13—C18—C17	−178.76 (14)
C3—C1—C2—O1	65.17 (16)	O9—S3—C20—C21	−37.17 (15)
C5—C1—C2—O1	−52.92 (16)	O8—S3—C20—C21	−170.84 (13)
S2—O4—C3—C1	154.00 (10)	O7—S3—C20—C21	73.38 (14)
C4—C1—C3—O4	−60.20 (16)	O9—S3—C20—C25	142.69 (14)
C2—C1—C3—O4	58.14 (16)	O8—S3—C20—C25	9.02 (16)
C5—C1—C3—O4	178.76 (12)	O7—S3—C20—C25	−106.76 (14)
S3—O7—C4—C1	−179.78 (10)	C25—C20—C21—C22	−1.1 (3)
C3—C1—C4—O7	−60.81 (16)	S3—C20—C21—C22	178.76 (13)
C2—C1—C4—O7	178.53 (13)	C20—C21—C22—C23	0.3 (3)
C5—C1—C4—O7	57.68 (16)	C21—C22—C23—C24	0.5 (3)
S4—O10—C5—C1	154.75 (10)	C21—C22—C23—C26	−178.59 (17)
C4—C1—C5—O10	62.45 (15)	C22—C23—C24—C25	−0.4 (3)
C3—C1—C5—O10	−176.39 (12)	C26—C23—C24—C25	178.66 (16)
C2—C1—C5—O10	−55.93 (15)	C23—C24—C25—C20	−0.4 (3)
O3—S1—C6—C7	142.11 (13)	C21—C20—C25—C24	1.2 (3)
O2—S1—C6—C7	8.11 (16)	S3—C20—C25—C24	−178.69 (13)
O1—S1—C6—C7	−107.68 (14)	O11—S4—C27—C28	138.81 (14)
O3—S1—C6—C11	−37.20 (15)	O12—S4—C27—C28	5.58 (17)
O2—S1—C6—C11	−171.20 (12)	O10—S4—C27—C28	−110.67 (14)
O1—S1—C6—C11	73.01 (14)	O11—S4—C27—C32	−38.17 (16)
C11—C6—C7—C8	−0.1 (2)	O12—S4—C27—C32	−171.40 (14)
S1—C6—C7—C8	−179.35 (13)	O10—S4—C27—C32	72.35 (15)
C6—C7—C8—C9	−0.1 (3)	C32—C27—C28—C29	0.0 (3)
C7—C8—C9—C10	0.2 (3)	S4—C27—C28—C29	−176.92 (14)
C7—C8—C9—C12	179.59 (17)	C27—C28—C29—C30	−0.2 (3)
C8—C9—C10—C11	−0.1 (3)	C28—C29—C30—C31	0.5 (3)
C12—C9—C10—C11	−179.50 (17)	C28—C29—C30—C33	−179.33 (18)
C9—C10—C11—C6	0.0 (3)	C29—C30—C31—C32	−0.6 (3)
C7—C6—C11—C10	0.2 (2)	C33—C30—C31—C32	179.26 (18)
S1—C6—C11—C10	179.46 (13)	C30—C31—C32—C27	0.4 (3)
O5—S2—C13—C14	−27.60 (17)	C28—C27—C32—C31	−0.1 (3)
O6—S2—C13—C14	−160.86 (14)	S4—C27—C32—C31	176.88 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2C···O4	0.97	2.48	2.849 (2)	102
C3—H3B···O6	0.97	2.47	2.905 (2)	107
C3—H3B···O7	0.97	2.55	2.876 (2)	100
C3—H3C···O9ⁱ	0.97	2.46	3.433 (2)	175
C4—H4A···O4	0.97	2.55	2.879 (2)	100
C5—H5B···O12	0.97	2.44	2.888 (2)	107
C5—H5C···O7	0.97	2.49	2.8396 (19)	101
C7—H7A···O2	0.93	2.58	2.937 (2)	103
C8—H8B···O11ⁱⁱ	0.93	2.52	3.140 (2)	124
C10—H10A···O6ⁱ	0.93	2.41	3.257 (2)	151
C18—H18A···O6	0.93	2.59	2.932 (2)	103
C22—H22A···O12ⁱⁱⁱ	0.93	2.52	3.154 (2)	126
C25—H25A···O8	0.93	2.56	2.924 (2)	104
C28—H28A···O12	0.93	2.54	2.905 (2)	104
C29—H29A···O8^iv	0.93	2.42	3.334 (2)	165
C31—H31A···O12ⁱⁱⁱ	0.93	2.53	3.209 (2)	130

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

Experimental details

Crystal data
Chemical formula	C₃₃H₃₆O₁₂S₄
M_r	752.86
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	13.2983 (2), 18.0368 (2), 15.4181 (2)
β (°)	110.653 (1)
V (Å³)	3460.50 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.47 × 0.41 × 0.16

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.857, 0.949
No. of measured, independent and observed [I > 2σ(I)] reflections	45048, 10090, 7927
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.119, 1.04
No. of reflections	10090
No. of parameters	446
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.42

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2C···O4	0.97	2.48	2.849 (2)	102
C3—H3B···O6	0.97	2.47	2.905 (2)	107
C3—H3B···O7	0.97	2.55	2.876 (2)	100
C3—H3C···O9ⁱ	0.97	2.46	3.433 (2)	175
C4—H4A···O4	0.97	2.55	2.879 (2)	100
C5—H5B···O12	0.97	2.44	2.888 (2)	107
C5—H5C···O7	0.97	2.49	2.8396 (19)	101
C7—H7A···O2	0.93	2.58	2.937 (2)	103
C8—H8B···O11ⁱⁱ	0.93	2.52	3.140 (2)	124
C10—H10A···O6ⁱ	0.93	2.41	3.257 (2)	151
C18—H18A···O6	0.93	2.59	2.932 (2)	103
C22—H22A···O12ⁱⁱⁱ	0.93	2.52	3.154 (2)	126
C25—H25A···O8	0.93	2.56	2.924 (2)	104
C28—H28A···O12	0.93	2.54	2.905 (2)	104
C29—H29A···O8^iv	0.93	2.42	3.334 (2)	165
C31—H31A···O12ⁱⁱⁱ	0.93	2.53	3.209 (2)	130

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

Footnotes

‡Additional correspondence author, e-mail: suchada.c@psu.ac.th.

Acknowledgements

The authors gratefully acknowledge the financial assistance of Beijing Normal University. The authors also thank Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

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