Phenyl 4,6-di-O-acetyl-2,3-dide­oxy-1-thio-α-d-erythro-hex-2-enopyran­oside

Kinfe, H.H.; Mebrahtu, F.M.; Muller, A.

doi:10.1107/S1600536811040165

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages o2840-o2841

doi:10.1107/S1600536811040165

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Phenyl 4,6-di-O-acetyl-2,3-dideoxy-1-thio-α-D-erythro-hex-2-enopyranoside

Henok H. Kinfe,^a ^* Fanuel M. Mebrahtu ^a and Alfred Muller ^a ^*

^aResearch Center for Synthesis and Catalysis, Department of Chemistry, University of Johannesburg (APK Campus), PO Box 524, Auckland Park, Johannesburg 2006, South Africa
^*Correspondence e-mail: hhkinfe@uj.ac.za, mullera@uj.ac.za

(Received 16 September 2011; accepted 29 September 2011; online 5 October 2011)

The pyranosyl ring in the title compound, C₁₆H₁₈O₅S, adopts an envelope conformation, with the acetyl groups in equatorial positions. In the crystal, weak C—H⋯O interactions link the molecules into chains.

Related literature

For details of the Ferrier arrangement, see: Ferrier & Prasad (1969 ). For the synthesis of pseudoglycals utilizing the Ferrier arrangement, see: López et al. (1995 ); Yadav et al. (2001 ). For applications of pseudoglycals, see: Domon et al. (2005 ); Danishefsky & Bilodeau (1996 ); Griffith & Danishefsky (1991 ); Halcomb et al. (1995 ); Bracherro et al. (1998 ); Dorgan & Jackson (1996 ); Chambers et al. (2005 ); Minuth & Boysen (2009 ). For background to the synthetic methodology of glycosides, see: Kinfe et al. (2011 ). For the preparation of the acid catalyst NaHSO₄-SiO₂, see: Breton (1997 ). For ring puckering analysis see, Cremer & Pople (1975 ). For a description of the Csambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₁₆H₁₈O₅S
M_r = 322.36
Monoclinic, P 2₁
a = 5.2330 (4) Å
b = 13.470 (1) Å
c = 11.1760 (9) Å
β = 97.291 (2)°
V = 781.41 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 100 K
0.42 × 0.37 × 0.27 mm

Data collection

Bruker APEXII DUO 4K KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.910, T_max = 0.941
10609 measured reflections
3839 independent reflections
3771 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.066
S = 1.06
3839 reflections
201 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ), 1824 Friedel pairs
Flack parameter: 0.04 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13B⋯O5ⁱ	0.98	2.44	3.3506 (15)	154
Symmetry code: (i) x-1, y, z.

Data collection: APEX2 (Bruker, 2011 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811040165/fj2451sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811040165/fj2451Isup2.hkl

checkCIF report

Comment top

Glycals, 1,2-unsaturated pyranoses, undergo acid catalyzed allylic rearrangement in the presence of alcohols to provide 2,3-unsaturated glycosides (pseudoglycals) (see Ferrier & Prasad, 1969). This reaction is referred as the Ferrier rearrangement reaction. Since the reaction proceeds via an oxycarbonium intermediate, thiols, halides and other nucleophiles can be employed besides alcohols to produce corresponding glycosides (see López et al., 1995; Yadav et al., 2001). The pseudoglycal products from the Ferrier rearrangement reaction have been used as chiral building blocks in the synthesis of antibiotics (see Domon et al., 2005), oligosaccharides (see Danishefsky & Bilodeau, 1996; Griffith & Danishefsky, 1991; Halcomb et al., 1995), nucleosides (see Bracherro et al., 1998), glycopeptides (see Dorgan & Jackson, 1996; Chambers et al., 2005) and also as chiral ligands in asymmetric synthesis (see Minuth & Boysen, 2009). Among other thioglycosides, phenyl 2,3-unsaturated thioglycosides have been extensively employed in organic synthesis such as in the elegant total synthesis of allosamidin (chitinase inhibitor), esperamicin and Calicheamicin (see Danishefsky & Bilodeau, 1996; Griffith & Danishefsky, 1991; Halcomb et al., 1995). Due to the importance of this type of thioglycosides, herein we report the structural analysis of phenyl 2,3-unsaturated thioglycoside I.

The title compound (see Fig. 1, scheme 1) crystallizes in the P2₁ (Z=2) space group resulting in molecules lying on general positions in the unit cell. All bond lengths are within their normal ranges (Allen, 2002) with the acetyl groups all in equatorial positions. The pyran ring is in an envelope conformation with ring puckering parameters of q₂ = 0.4212 (12) Å, q₃ = 0.2974 (12) Å, Q = 0.5156 (11) Å and ϕ₂ = 321.05 (17)° (see Cremer & Pople, 1975). Weak C—H···O/S interactions (see Table 1) stabilize the crystal structure.

Related literature top

For details of the Ferrier arrangement, see: Ferrier & Prasad (1969). For the synthesis of pseudoglycals utilizing the Ferrier arrangement, see: López et al. (1995); Yadav et al. (2001). For applications of pseudoglycals, see: Domon et al. (2005); Danishefsky & Bilodeau (1996); Griffith & Danishefsky (1991); Halcomb et al. (1995); Bracherro et al. (1998); Dorgan & Jackson (1996); Chambers et al. (2005); Minuth & Boysen (2009). For background to the synthetic methodology of glycosides, see: Kinfe et al. (2011). For the preparation of the acid catalyst NaHSO₄-SiO₂, see: Breton (1997). For ring puckering analysis see, Cremer & Pople (1975). For a description of the Csambridge Structural Database, see: Allen (2002).

Experimental top

To a solution of a tri-O-acetyl-D-glucal (100 mg, 0.36 mmol) in CH₃CN (1 ml) NaHSO₄-SiO₂ (2.5 mg, 3.0 mmol NaHSO₄/g) was added (see Breton, 1997). The resulting mixture was stirred at 80 °C for 5 min. After adding silica gel to the reaction mixture at room temperature, the solvent was evaporated in vacuo without heating until a free-flowing solid was obtained. The resulting solid was column chromatographed using 1:9 ethyl acetate:hexane eluent to afford α:β (4:1) mixture of 2,3-unsaturated glycosides in 96% yield as a white solid (see Kinfe et al., 2011). Recrystalization from a mixture of DCM and hexane afforded the title thioglycoside I in 60% yield as white crystals. Analytical data: ¹H NMR (CDCl₃, 300 MHz): δ 7.51 (d, J = 7.2 Hz, 2H), 7.29–7.17 (m, 3H), 6.03 (d, J = 10.2 Hz, 1H), 5.83 (d, J = 10.8 Hz, 1H), 5.73 (s, 1H), 5.35 (d, J = 9.6 Hz, 1H), 4.60–4.13 (m, 3H), 2.07 (s, 3H), 2.03 (s, 3H); ¹³C NMR (CDCl₃, 75 MHz): δ 170.7, 170.2, 134.7, 131.7, 128.9, 128.5, 127.6, 83.6, 67.2, 65.0, 63.0, 20.9, 20.7.

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. View of (I). Displacement ellipsoids are drawn at a 50% probability level.

Phenyl 4,6-di-O-acetyl-2,3-dideoxy-1-thio-α-D-erythro-hex-2-enopyranoside top

Crystal data top

C₁₆H₁₈O₅S	F(000) = 340
M_r = 322.36	D_x = 1.37 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 7987 reflections
a = 5.2330 (4) Å	θ = 3.0–28.3°
b = 13.470 (1) Å	µ = 0.23 mm⁻¹
c = 11.1760 (9) Å	T = 100 K
β = 97.291 (2)°	Prism, colourless
V = 781.41 (10) Å³	0.42 × 0.37 × 0.27 mm
Z = 2

Data collection top

Bruker APEXII DUO 4K KappaCCD diffractometer	3839 independent reflections
Graphite monochromator	3771 reflections with I > 2σ(I)
Detector resolution: 8.4 pixels mm^-1	R_int = 0.020
ϕ and ω scans	θ_max = 28.4°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −6→6
T_min = 0.910, T_max = 0.941	k = −17→17
10609 measured reflections	l = −14→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.025	H-atom parameters constrained
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0412P)² + 0.0965P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
3839 reflections	Δρ_max = 0.31 e Å⁻³
201 parameters	Δρ_min = −0.20 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1824 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (4)

Crystal data top

C₁₆H₁₈O₅S	V = 781.41 (10) Å³
M_r = 322.36	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 5.2330 (4) Å	µ = 0.23 mm⁻¹
b = 13.470 (1) Å	T = 100 K
c = 11.1760 (9) Å	0.42 × 0.37 × 0.27 mm
β = 97.291 (2)°

Data collection top

Bruker APEXII DUO 4K KappaCCD diffractometer	3839 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	3771 reflections with I > 2σ(I)
T_min = 0.910, T_max = 0.941	R_int = 0.020
10609 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	H-atom parameters constrained
wR(F²) = 0.066	Δρ_max = 0.31 e Å⁻³
S = 1.06	Δρ_min = −0.20 e Å⁻³
3839 reflections	Absolute structure: Flack (1983), 1824 Friedel pairs
201 parameters	Absolute structure parameter: 0.04 (4)
1 restraint

Special details top

Experimental. The intensity data was collected on a Bruker APEX Duo 4 K KappaCCD diffractometer using an exposure time of 10 s/frame. A total of 1490 frames were collected with a frame width of 0.5° covering up to θ = 28.36° with 99.8% completeness accomplished.

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	0.97008 (5)	0.73210 (2)	0.55390 (2)	0.01758 (7)
O1	1.10976 (16)	0.64668 (6)	0.77149 (7)	0.01499 (16)
O2	0.67619 (16)	0.67526 (6)	0.89081 (8)	0.01858 (18)
O3	0.43919 (18)	0.61581 (8)	1.02918 (8)	0.0242 (2)
O4	0.82603 (16)	0.40209 (6)	0.72849 (8)	0.01964 (18)
O5	1.07925 (17)	0.28011 (7)	0.81406 (9)	0.02305 (19)
C1	1.1974 (2)	0.65826 (9)	0.65814 (10)	0.0151 (2)
H1	1.3636	0.6957	0.6713	0.018*
C2	1.2504 (2)	0.56087 (10)	0.60152 (11)	0.0181 (2)
H2	1.3308	0.5601	0.5299	0.022*
C3	1.1873 (2)	0.47589 (9)	0.64935 (12)	0.0193 (2)
H3	1.2388	0.4154	0.6158	0.023*
C4	1.0364 (2)	0.47220 (9)	0.75525 (12)	0.0167 (2)
H4	1.1499	0.4524	0.8302	0.02*
C5	0.9137 (2)	0.57276 (9)	0.77150 (10)	0.0153 (2)
H5	0.7744	0.5852	0.7033	0.018*
C6	1.0169 (2)	0.84785 (9)	0.63084 (11)	0.0169 (2)
C7	1.2088 (3)	0.91243 (10)	0.60335 (13)	0.0234 (3)
H7	1.313	0.8954	0.5427	0.028*
C8	1.2472 (3)	1.00164 (11)	0.66480 (14)	0.0282 (3)
H8	1.3785	1.0457	0.6463	0.034*
C9	1.0957 (3)	1.02695 (10)	0.75292 (14)	0.0264 (3)
H9	1.123	1.0882	0.7948	0.032*
C10	0.9041 (3)	0.96298 (11)	0.77997 (13)	0.0274 (3)
H10	0.7995	0.9805	0.8402	0.033*
C11	0.8644 (2)	0.87300 (10)	0.71901 (13)	0.0228 (3)
H11	0.7333	0.829	0.7378	0.027*
C12	0.8777 (2)	0.30606 (9)	0.76035 (11)	0.0163 (2)
C13	0.6527 (2)	0.24055 (10)	0.71904 (11)	0.0195 (2)
H13A	0.6456	0.2284	0.6322	0.029*
H13B	0.4933	0.2731	0.7354	0.029*
H13C	0.6719	0.1772	0.7624	0.029*
C14	0.8047 (2)	0.58030 (9)	0.88967 (11)	0.0196 (2)
H14A	0.681	0.5257	0.897	0.024*
H14B	0.9446	0.5758	0.958	0.024*
C15	0.4963 (2)	0.68315 (10)	0.96714 (11)	0.0192 (2)
C16	0.3881 (3)	0.78618 (10)	0.96492 (12)	0.0234 (3)
H16A	0.2147	0.7843	0.9892	0.035*
H16B	0.3795	0.8133	0.8831	0.035*
H16C	0.4993	0.8283	1.021	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02171 (13)	0.01391 (12)	0.01645 (12)	0.00008 (11)	−0.00018 (9)	−0.00028 (11)
O1	0.0158 (4)	0.0132 (4)	0.0160 (4)	−0.0031 (3)	0.0023 (3)	−0.0005 (3)
O2	0.0180 (4)	0.0171 (4)	0.0219 (4)	0.0008 (3)	0.0073 (3)	0.0004 (3)
O3	0.0226 (4)	0.0306 (5)	0.0202 (4)	0.0000 (4)	0.0058 (3)	0.0053 (4)
O4	0.0152 (4)	0.0108 (4)	0.0315 (5)	−0.0018 (3)	−0.0023 (3)	0.0026 (3)
O5	0.0170 (4)	0.0158 (4)	0.0359 (5)	0.0016 (3)	0.0017 (4)	0.0043 (4)
C1	0.0144 (5)	0.0133 (5)	0.0176 (5)	0.0004 (4)	0.0019 (4)	−0.0003 (4)
C2	0.0163 (5)	0.0162 (5)	0.0224 (6)	0.0024 (4)	0.0045 (4)	−0.0037 (5)
C3	0.0150 (5)	0.0155 (6)	0.0272 (6)	0.0016 (4)	0.0017 (5)	−0.0048 (5)
C4	0.0138 (5)	0.0110 (5)	0.0246 (6)	−0.0011 (4)	−0.0002 (4)	0.0007 (4)
C5	0.0133 (5)	0.0129 (5)	0.0193 (5)	−0.0018 (4)	0.0009 (4)	0.0004 (4)
C6	0.0195 (5)	0.0122 (5)	0.0179 (5)	0.0013 (4)	−0.0019 (4)	0.0008 (4)
C7	0.0238 (6)	0.0216 (7)	0.0251 (6)	−0.0026 (5)	0.0036 (5)	0.0000 (5)
C8	0.0287 (7)	0.0194 (6)	0.0356 (8)	−0.0069 (5)	0.0003 (6)	−0.0004 (5)
C9	0.0284 (7)	0.0155 (6)	0.0324 (7)	0.0036 (5)	−0.0072 (5)	−0.0040 (5)
C10	0.0278 (7)	0.0223 (6)	0.0320 (7)	0.0045 (5)	0.0039 (5)	−0.0075 (5)
C11	0.0222 (6)	0.0174 (6)	0.0291 (7)	0.0003 (5)	0.0041 (5)	−0.0014 (5)
C12	0.0170 (5)	0.0125 (5)	0.0207 (5)	0.0004 (4)	0.0078 (4)	−0.0001 (4)
C13	0.0176 (5)	0.0154 (5)	0.0260 (5)	−0.0024 (5)	0.0047 (4)	−0.0003 (5)
C14	0.0187 (5)	0.0159 (6)	0.0252 (6)	0.0006 (4)	0.0064 (4)	0.0041 (5)
C15	0.0145 (5)	0.0276 (6)	0.0151 (5)	−0.0006 (5)	0.0007 (4)	−0.0026 (5)
C16	0.0234 (6)	0.0262 (7)	0.0210 (6)	0.0021 (5)	0.0044 (5)	−0.0042 (5)

Geometric parameters (Å, º) top

S1—C6	1.7824 (12)	C6—C7	1.3921 (18)
S1—C1	1.8465 (12)	C7—C8	1.386 (2)
O1—C1	1.4096 (13)	C7—H7	0.95
O1—C5	1.4298 (13)	C8—C9	1.383 (2)
O2—C15	1.3522 (14)	C8—H8	0.95
O2—C14	1.4460 (14)	C9—C10	1.384 (2)
O3—C15	1.2024 (16)	C9—H9	0.95
O4—C12	1.3596 (14)	C10—C11	1.3929 (19)
O4—C4	1.4527 (14)	C10—H10	0.95
O5—C12	1.1974 (15)	C11—H11	0.95
C1—C2	1.4975 (17)	C12—C13	1.4967 (17)
C1—H1	1	C13—H13A	0.98
C2—C3	1.3228 (19)	C13—H13B	0.98
C2—H2	0.95	C13—H13C	0.98
C3—C4	1.5046 (18)	C14—H14A	0.99
C3—H3	0.95	C14—H14B	0.99
C4—C5	1.5199 (16)	C15—C16	1.4980 (18)
C4—H4	1	C16—H16A	0.98
C5—C14	1.5069 (16)	C16—H16B	0.98
C5—H5	1	C16—H16C	0.98
C6—C11	1.3864 (18)

C6—S1—C1	97.40 (5)	C9—C8—H8	119.8
C1—O1—C5	113.11 (8)	C7—C8—H8	119.8
C15—O2—C14	115.90 (9)	C8—C9—C10	119.91 (13)
C12—O4—C4	116.37 (9)	C8—C9—H9	120
O1—C1—C2	112.43 (9)	C10—C9—H9	120
O1—C1—S1	111.69 (8)	C9—C10—C11	120.14 (13)
C2—C1—S1	110.14 (8)	C9—C10—H10	119.9
O1—C1—H1	107.4	C11—C10—H10	119.9
C2—C1—H1	107.4	C6—C11—C10	119.78 (12)
S1—C1—H1	107.4	C6—C11—H11	120.1
C3—C2—C1	121.21 (11)	C10—C11—H11	120.1
C3—C2—H2	119.4	O5—C12—O4	122.84 (11)
C1—C2—H2	119.4	O5—C12—C13	126.21 (11)
C2—C3—C4	121.95 (11)	O4—C12—C13	110.94 (10)
C2—C3—H3	119	C12—C13—H13A	109.5
C4—C3—H3	119	C12—C13—H13B	109.5
O4—C4—C3	108.61 (10)	H13A—C13—H13B	109.5
O4—C4—C5	106.45 (9)	C12—C13—H13C	109.5
C3—C4—C5	109.66 (10)	H13A—C13—H13C	109.5
O4—C4—H4	110.7	H13B—C13—H13C	109.5
C3—C4—H4	110.7	O2—C14—C5	107.18 (9)
C5—C4—H4	110.7	O2—C14—H14A	110.3
O1—C5—C14	107.73 (9)	C5—C14—H14A	110.3
O1—C5—C4	107.84 (9)	O2—C14—H14B	110.3
C14—C5—C4	112.17 (10)	C5—C14—H14B	110.3
O1—C5—H5	109.7	H14A—C14—H14B	108.5
C14—C5—H5	109.7	O3—C15—O2	123.27 (12)
C4—C5—H5	109.7	O3—C15—C16	125.96 (11)
C11—C6—C7	120.04 (12)	O2—C15—C16	110.75 (11)
C11—C6—S1	120.02 (9)	C15—C16—H16A	109.5
C7—C6—S1	119.93 (10)	C15—C16—H16B	109.5
C8—C7—C6	119.72 (13)	H16A—C16—H16B	109.5
C8—C7—H7	120.1	C15—C16—H16C	109.5
C6—C7—H7	120.1	H16A—C16—H16C	109.5
C9—C8—C7	120.41 (13)	H16B—C16—H16C	109.5

C5—O1—C1—C2	−46.21 (12)	C1—S1—C6—C11	−90.11 (10)
C5—O1—C1—S1	78.20 (10)	C1—S1—C6—C7	89.10 (11)
C6—S1—C1—O1	68.09 (9)	C11—C6—C7—C8	0.25 (19)
C6—S1—C1—C2	−166.23 (8)	S1—C6—C7—C8	−178.96 (11)
O1—C1—C2—C3	7.92 (16)	C6—C7—C8—C9	−0.2 (2)
S1—C1—C2—C3	−117.34 (12)	C7—C8—C9—C10	−0.1 (2)
C1—C2—C3—C4	6.16 (19)	C8—C9—C10—C11	0.3 (2)
C12—O4—C4—C3	89.25 (12)	C7—C6—C11—C10	−0.06 (19)
C12—O4—C4—C5	−152.74 (10)	S1—C6—C11—C10	179.15 (10)
C2—C3—C4—O4	131.42 (12)	C9—C10—C11—C6	−0.2 (2)
C2—C3—C4—C5	15.47 (16)	C4—O4—C12—O5	4.37 (17)
C1—O1—C5—C14	−170.14 (9)	C4—O4—C12—C13	−175.44 (10)
C1—O1—C5—C4	68.59 (11)	C15—O2—C14—C5	158.61 (10)
O4—C4—C5—O1	−167.47 (9)	O1—C5—C14—O2	65.92 (11)
C3—C4—C5—O1	−50.15 (12)	C4—C5—C14—O2	−175.56 (9)
O4—C4—C5—C14	74.07 (12)	C14—O2—C15—O3	−1.62 (17)
C3—C4—C5—C14	−168.62 (10)	C14—O2—C15—C16	176.90 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···S1	1	2.86	3.2848 (12)	106
C13—H13B···O5ⁱ	0.98	2.44	3.3506 (15)	154

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₈O₅S
M_r	322.36
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	5.2330 (4), 13.470 (1), 11.1760 (9)
β (°)	97.291 (2)
V (Å³)	781.41 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.42 × 0.37 × 0.27

Data collection
Diffractometer	Bruker APEXII DUO 4K KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.910, 0.941
No. of measured, independent and observed [I > 2σ(I)] reflections	10609, 3839, 3771
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.066, 1.06
No. of reflections	3839
No. of parameters	201
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.20
Absolute structure	Flack (1983), 1824 Friedel pairs
Absolute structure parameter	0.04 (4)

Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2008), SAINT and XPREP (Bruker, 2008), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···S1	1	2.86	3.2848 (12)	106
C13—H13B···O5ⁱ	0.98	2.44	3.3506 (15)	154

Symmetry code: (i) x−1, y, z.

Acknowledgements

Research funds of the University of Johannesburg and the Research Center for Synthesis and Catalysis are gratefully acknowledged. Mr C. Ncube is thanked for the data collection.

References

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