Enantiomers of a selective gelatinase inhibitor: (R)- and (S)-2-[(4-phen­oxy­phenyl)­sulfonyl­methyl]thiirane

The compound 2-[(4-phen­oxy­phenyl)­sulfonyl­meth­yl]thiirane, C₁₅H₁₄O₃S₂, a selective gelatinase inhibitor, was synthesized and structurally characterized. Two crystals were analyzed, one each for the R and S enantio­mers, and the results were compared with the previously reported structure of the racemate. The enantio­merically pure compounds both crystallize with Z′ = 2 in the space group P2₁, while the racemic mixture crystallizes with Z′ = 1 in the space group P2₁/c, with disorder in the position of the thiirane group. This disorder accommodates both mol­ecules for each of the enantio­merically pure crystals, showing good overlap of the mol­ecules of the pure enanti­omorphs with the components of the centrosymmetric structure.

S1. Introduction

Matrix metalloproteinases (MMPs) are a group of 23 enzymes in humans that are involved in a number of physiological and pathological processes (Gialeli et al., 2011; Sekhon, 2010; Lee et al., 2004; Stamenkovic, 2003; Sternlicht et al. 2001; Nagase et al., 1999; Massova et al., 1998). Two members of this family, MMP-2 and MMP-9, are known as gelatinases A and B, respectively. These two enzymes have emerged as important targets for inhibition, in the light of their involvement in a number of diseases affecting extracellular matrix remodeling, such as cancer metastasis and stroke. Compound (I) is a potent and selective gelatinase inhibitor (Brown et al., 2000). It is active in rodent models for cancer and stroke, and is a useful tool for the elucidation of the functional properties of these enzymes in in vivo models (Hadass et al., 2013; Cui et al., 2012; Gu et al., 2005; Krüger et al., 2005; Bonfil et al., 2006, 2007).

The optically active (R)- and (S)-enanti­omers of (I), starting from commercially available (R)- and (S)-epi­chloro­hydrin (97% ee), were synthesized and both (R)-(II) and (S)-(III) were equally active towards gelatinase inhibition (Lee et al., 2005). In a previous study, we have shown that the optical purity of the compounds (R)-(II) and (S)-(III) was >90%, based on the fact that no trace of the other enanti­omer was dete­cta­ble in the ¹H NMR spectra in the presence of the chiral shift reagent, europium tris­[3-(hepta­fluoro­propyl­hydroxy­methyl­ene)-(+)-camphorate], Eu(hfc)₃. A key reaction, the epoxide ring-opening reaction by 4-phen­oxy­phenyl­thiol­ate, occurred exclusively at atom C3 of epi­chloro­hydrin, not at atom C1, and the stereocenter was not scrambled during this step. In the final thiirane, the epi­chloro­hydrin C atoms become C13, C14 and C15. Throughout the remainder of the synthetic route, involving the formation of the epoxide ring, sulfide oxidation and thiirane ring formation, the stereocenter was intact. Although we can expect (R)-epi­chloro­hydrin to give the R-enanti­omer, (R)-(II), and (S)-epi­chloro­hydrin to give the S-enanti­omer, (S)-(III), their respective absolute stereochemistries need to be established experimentally. To determine the absolute stereochemistry of compounds (R)-(II) and (S)-(III), crystals were grown and their X-ray crystal structures were determined. We have reported the structure of the racemic (I) previously (Lee et al., 2008).

S2. Experimental

S2.1. Synthesis and crystallization

Compounds (R)-(II) and (S)-(III) were synthesized according to the literature procedure developed in our laboratory (Lee et al., 2005). Crystals of suitable size for single-crystal X-ray diffraction analysis were obtained by diffusion of hexanes (or di­ethyl ether) into a CH₂Cl₂ solution at room temperature overnight.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Examination of the structures of (R)-(II) and (S)-(III) suggests the possibility of inversion symmetry relating the two independent molecules of the asymmetric unit. The intensity data show a number of systematic absence violations for a c-glide, and no solution could be obtained for space group P2₁/m. In addition, 8% of the atoms of the structure do not fit the proposed inversion symmetry. These atoms are located at the stereocenter.

From the synthesis, the stereochemistry of the parent epi­chloro­hydrin was expected to be retained. This was one purpose of the study and was confirmed by comparison of the intensities of Friedel pairs of reflections and a Bayesian analysis of the Friedel pairs. For (R)-(II), the Flack x parameter is 0.055 (9) (Parsons et al., 2013) and the Hooft y parameter is 0.053 (11) (Hooft et al., 2008). (S)-(III) yields a Flack x parameter of 0.02 (2) and a Hooft y parameter of 0.010 (12). For both structures these analyses are in agreement and strongly indicate the correct absolute stereochemistry. Further support for this hypothesis is provided by the |E²-1| statistics for both compounds (0.835 and 0.826, respectively). While these |E²-1| values deviate from the expected value of 0.736 for an acentric space group, they tend towards this value. Based on these analyses, the space group P2₁ was retained.

H atoms were included in geometrically calculated positions and refined with C—H = 0.95 Å for aromatic C—H, 0.99 Å for methyl­ene C—H and 1.00 Å for methyne C—H, and with U_iso(H) = 1.2U_eq(C).

S3. Results and discussion

X-ray analysis of (R)-(II) and (S)-(III) reveals that their respective stereochemistries were (R) and (S), as anti­cipated. The unit-cell dimensions for (I), (R)-(II) and (S)-(III) are all identical. Clearly, (R)-(II) and (S)-(III) are related by inversion (stereoisomers), but they are not perfectly superimposed upon inversion. Compound (I) crystallizes in space group P2₁/c, with disorder in the orientation of the thiirane at the stereocenter located at C14 (Lee et al., 2008). In the chosen asymmetric unit for (I), the S-enanti­omer is present with a site occupancy of 0.701 (7); the R-enanti­omer is present as disorder at a site occupancy of 0.299 (7). Upon inversion, the primary component becomes the R-enanti­omer. It would be equally valid to use a reference asymmetric unit in which the R-enanti­omer was the majority component. In (R)-(II) and (S)-(III), the space group is P2₁. Two independent molecules (molecule 1, indicated with a suffix A on the atom labels, and molecule 2, with a suffix B) (Fig. 1), are present in the unit cell: Z' = 2 and Z = 4. The two molecules within the asymmetric unit are not superimposable, differing in the orientation of the sulfonyl­methyl­thiirane group and the terminal phenyl group (Fig. 2).

The sulfonyl­methyl­thiirane groups are oriented in different directions within the two independent molecules in both (R)-(II) and (S)-(III), demonstrated by the differing C10—S1—C13—C14 torsion angles (Tables 2 and 3). The terminal phenyl groups are also pivoted and do not overlay each other (Fig. 2; C1—O1—C7—C8 torsion angles, Tables 2 and 3). The overlay of the two independent molecules in each compound reveals that the molecules adopt a pseudo-mirror symmetry, differing primarily in the orientation of the thiirane ring; the pseudo-mirror plane accounts for the orientation of the terminal phenyl group. The thiirane ring breaks the mirror symmetry due to the chiral center at C14. It is a known phenomenon that chiral molecules often adopt pseudo-symmetry in structures with Z' > 1 (Collins et al., 2006).

The orientation of the thiirane ring is such that it allows nesting of atom S2 of one molecule into the center of the middle phenyl ring of the second molecule related by an a-axis translation (Table 4). For (R)-(II), the average contact distance is 3.557 Å, and in (S)-(III) the contact between S2 and the ring centroid is 3.506 Å. The molecules otherwise pack in a herringbone-type fashion (Fig. 3), mimicking the glide plane present in the racemate. Again, this is a common feature of chiral structures with Z' > 1 (Collins et al., 2006).

Comparison of the structures of (R)-(II) and (S)-(III) with the parent racemate (I) shows significant overlap of all three structures (Fig. 4). The disorder present in racemate (I) is a result of the two orientations of the independent molecules in both (R)-(II) and (S)-(III) (Figs. 2 and 4). Since (R)-(II) and (S)-(III) are related by inversion and adopt a unit cell with parameters close to that of racemate (I), it appears that the two orientations of the phenyl and thiirane rings found in the enanti­opure compounds (R)-(II) and (S)-(III) are retained to some degree in the racemate upon crystallization. While the percentages vary, this provides the rationalization for the disorder observed in (I).

In summary, we report the structures of the two enanti­omerically pure thiirane compounds that comprise the structure of the previously reported 2-(4-phen­oxy­phenyl­sulfonyl­methyl)­thiirane, and discuss their role in the observed disorder in the racemate.

Related literature

For related literature, see: Bonfil et al. (2006, 2007); Brown et al. (2000); Collins et al. (2006); Cui et al. (2012); Gialeli et al. (2011); Gu et al. (2005); Hadass et al. (2013); Hooft et al. (2008); Krüger et al. (2005); Lee et al. (2004, 2005, 2008); Massova et al. (1998); Nagase et al. (1999); Parsons et al. (2013); Sekhon (2010); Stamenkovic (2003); Sternlicht et al. (2001).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2007). Cell refinement: APEX2 and SAINT (Bruker, 2007) for R-II; SAINT (Bruker, 2014) for S-III. Data reduction: SAINT (Bruker, 2007) and XPREP (Sheldrick, 2008) for R-II; SAINT (Bruker, 2014) for S-III. For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2014); molecular graphics: CrystalMaker (Palmer, 2008), Mercury (Macrae et al., 2008), pyMOL (Schrödinger, 2011) and POVRay (Cason, 2003); software used to prepare material for publication: XCIF (Sheldrick, 2008), enCIFer (Allen et al., 2004) and publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of (R)-(II), showing the atom-numbering scheme and the interaction between atom S2 and the ring centroid. Displacement ellipsoids are drawn at the 50% probability level. The structure of (S)-(III) is identical, except for the opposite chirality at C14.
	Fig. 2. Overlays of the independent molecules in (a) (R)-(II) and (b) (S)-(III). Fit made at C7 to C12. Molecule A is shown in red, molecule B in light green.
	Fig. 3. A packing diagram of (R)-(II). Molecule B is shown in gray.
	Fig. 4. An overlay of (I) (red), (R)-(II) (green and light green) and (S)-(III) (blue and light blue), demonstrating the disorder. Disorder in (I) is indicated by red stars. (R)-(II)A (green) and (S)-(III)B (light blue) are the mirror images of the reference unit of (I). Note the high degree of structural overlap.

(R-II) (R)-2-(4-Phenoxyphenylsulfonylmethyl)thiirane

Crystal data

C15H14O3S2	F(000) = 640
Mr = 306.38	Dx = 1.448 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
a = 5.3891 (3) Å	Cell parameters from 3913 reflections
b = 28.3231 (13) Å	θ = 3.1–67.3°
c = 9.2503 (4) Å	µ = 3.48 mm^−1
β = 95.434 (3)°	T = 100 K
V = 1405.58 (12) Å^3	Needle, clear colourless
Z = 4	0.23 × 0.01 × 0.01 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	4353 independent reflections
Radiation source: fine-focus sealed tube, Siemens KFFCU2K-90	3926 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
Detector resolution: 8.33 pixels mm^-1	θmax = 69.3°, θmin = 3.1°
ϕ and ω scans	h = −6→4
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −33→33
Tmin = 0.50, Tmax = 0.97	l = −11→10
11717 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0625P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
4353 reflections	Δρmax = 0.43 e Å^−3
361 parameters	Δρmin = −0.23 e Å^−3
1 restraint	Absolute structure: Flack x parameter determined using 1610 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.055 (9)

Special details

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

Refinement. Examination of the structure suggests the possibility of inversion symmetry relating the two independent molecules of the asymmetric unit. The intensity data show a number of systematic absence violations for P2₁/c and no solution could be obtained for P2₁/m. In addition, 8% of the atoms of the structure do not fit the proposed inversion symmetry. Based on these analyses, the space group P2₁ was retained.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1A	0.70704 (19)	0.56561 (4)	−0.13832 (11)	0.0173 (3)
S2A	0.8468 (2)	0.43844 (4)	0.13205 (13)	0.0270 (3)
O1A	0.9356 (6)	0.71950 (13)	0.2825 (3)	0.0238 (8)
O2A	0.4423 (6)	0.55669 (13)	−0.1384 (3)	0.0230 (7)
O3A	0.8054 (6)	0.57784 (12)	−0.2718 (3)	0.0233 (7)
C1A	1.0894 (9)	0.75743 (17)	0.2500 (5)	0.0199 (10)
C2A	1.3181 (9)	0.76229 (19)	0.3292 (5)	0.0246 (11)
H2A	1.3778	0.7389	0.3973	0.029*
C3A	1.4589 (10)	0.8023 (2)	0.3069 (6)	0.0305 (13)
H3A	1.6161	0.8064	0.3613	0.037*
C4A	1.3749 (11)	0.8358 (2)	0.2082 (6)	0.0320 (13)
H4A	1.4723	0.8631	0.1945	0.038*
C5A	1.1445 (10)	0.82964 (19)	0.1273 (6)	0.0290 (12)
H5A	1.0870	0.8526	0.0571	0.035*
C6A	1.0002 (9)	0.7904 (2)	0.1487 (5)	0.0250 (10)
H6A	0.8427	0.7863	0.0948	0.030*
C7A	0.8926 (9)	0.68441 (17)	0.1816 (5)	0.0180 (10)
C8A	1.0465 (9)	0.67601 (18)	0.0714 (5)	0.0187 (10)
H8A	1.1875	0.6955	0.0622	0.022*
C9A	0.9928 (8)	0.63910 (17)	−0.0247 (5)	0.0188 (10)
H9A	1.0968	0.6330	−0.0999	0.023*
C10A	0.7846 (8)	0.61091 (17)	−0.0099 (5)	0.0179 (9)
C11A	0.6323 (8)	0.61891 (17)	0.1010 (5)	0.0192 (10)
H11A	0.4922	0.5992	0.1109	0.023*
C12A	0.6864 (8)	0.65558 (19)	0.1962 (5)	0.0203 (10)
H12A	0.5833	0.6613	0.2722	0.024*
C13A	0.8710 (8)	0.51414 (16)	−0.0693 (5)	0.0191 (9)
H13A	0.8433	0.4880	−0.1401	0.023*
H13B	1.0520	0.5209	−0.0562	0.023*
C14A	0.7824 (8)	0.49931 (16)	0.0749 (5)	0.0212 (9)
H14A	0.8042	0.5235	0.1539	0.025*
C15A	0.5567 (9)	0.46964 (19)	0.0749 (6)	0.0280 (12)
H15A	0.4705	0.4611	−0.0208	0.034*
H15B	0.4431	0.4763	0.1505	0.034*
S1B	0.3123 (2)	0.45368 (4)	0.60609 (13)	0.0214 (3)
S2B	0.1707 (2)	0.58472 (5)	0.35736 (13)	0.0290 (3)
O1B	0.0601 (6)	0.29480 (13)	0.2112 (3)	0.0263 (8)
O2B	0.5729 (6)	0.46423 (12)	0.6017 (4)	0.0276 (8)
O3B	0.2197 (6)	0.44597 (13)	0.7444 (4)	0.0288 (8)
C1B	−0.0977 (9)	0.25807 (18)	0.2458 (5)	0.0223 (11)
C2B	−0.3246 (9)	0.25306 (18)	0.1644 (5)	0.0248 (11)
H2B	−0.3771	0.2756	0.0917	0.030*
C3B	−0.4750 (10)	0.2148 (2)	0.1900 (6)	0.0294 (12)
H3B	−0.6310	0.2109	0.1343	0.035*
C4B	−0.3982 (11)	0.1822 (2)	0.2963 (6)	0.0334 (14)
H4B	−0.5024	0.1562	0.3136	0.040*
C5B	−0.1714 (11)	0.1873 (2)	0.3778 (6)	0.0323 (13)
H5B	−0.1193	0.1646	0.4501	0.039*
C6B	−0.0176 (9)	0.2261 (2)	0.3531 (5)	0.0265 (11)
H6B	0.1380	0.2302	0.4091	0.032*
C7B	0.1147 (9)	0.32956 (18)	0.3115 (5)	0.0216 (11)
C8B	−0.0297 (9)	0.33920 (19)	0.4247 (5)	0.0190 (10)
H8B	−0.1702	0.3201	0.4388	0.023*
C9B	0.0321 (8)	0.37667 (17)	0.5166 (5)	0.0188 (10)
H9B	−0.0670	0.3838	0.5934	0.023*
C10B	0.2416 (9)	0.40400 (18)	0.4956 (5)	0.0195 (10)
C11B	0.3848 (9)	0.39436 (17)	0.3826 (5)	0.0222 (10)
H11B	0.5260	0.4134	0.3691	0.027*
C12B	0.3236 (9)	0.35762 (18)	0.2906 (5)	0.0210 (10)
H12B	0.4216	0.3510	0.2129	0.025*
C13B	0.1288 (8)	0.49897 (19)	0.5035 (6)	0.0303 (11)
H13C	0.1035	0.4894	0.4002	0.036*
H13D	−0.0371	0.5012	0.5406	0.036*
C14B	0.2505 (9)	0.54610 (17)	0.5137 (5)	0.0272 (11)
H14B	0.2608	0.5616	0.6112	0.033*
C15B	0.4595 (9)	0.5555 (2)	0.4257 (5)	0.0297 (12)
H15C	0.5165	0.5290	0.3675	0.036*
H15D	0.5959	0.5758	0.4696	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1A	0.0147 (6)	0.0172 (6)	0.0199 (6)	−0.0006 (4)	0.0009 (4)	0.0001 (5)
S2A	0.0318 (7)	0.0210 (7)	0.0284 (6)	0.0023 (5)	0.0026 (5)	0.0042 (5)
O1A	0.027 (2)	0.025 (2)	0.0201 (16)	−0.0105 (14)	0.0060 (14)	−0.0037 (14)
O2A	0.0154 (17)	0.026 (2)	0.0266 (16)	−0.0020 (13)	−0.0015 (12)	−0.0030 (14)
O3A	0.0256 (19)	0.025 (2)	0.0196 (16)	−0.0009 (12)	0.0009 (13)	−0.0007 (13)
C1A	0.021 (3)	0.019 (3)	0.021 (2)	−0.0018 (18)	0.0084 (19)	−0.006 (2)
C2A	0.023 (3)	0.027 (3)	0.024 (2)	0.002 (2)	0.006 (2)	−0.006 (2)
C3A	0.026 (3)	0.035 (3)	0.031 (3)	−0.008 (2)	0.009 (2)	−0.014 (3)
C4A	0.040 (3)	0.027 (3)	0.032 (3)	−0.012 (2)	0.019 (3)	−0.012 (2)
C5A	0.039 (3)	0.023 (3)	0.027 (3)	0.002 (2)	0.012 (2)	0.000 (2)
C6A	0.024 (3)	0.027 (3)	0.024 (2)	0.001 (2)	0.0050 (18)	−0.004 (2)
C7A	0.017 (3)	0.016 (3)	0.020 (2)	0.0004 (17)	−0.0027 (17)	0.000 (2)
C8A	0.016 (3)	0.019 (3)	0.020 (2)	−0.0006 (18)	−0.0005 (18)	0.002 (2)
C9A	0.016 (2)	0.022 (3)	0.018 (2)	0.0016 (17)	0.0022 (17)	0.0017 (19)
C10A	0.016 (2)	0.017 (2)	0.020 (2)	0.0036 (17)	0.0006 (18)	0.0026 (19)
C11A	0.014 (2)	0.019 (3)	0.025 (2)	−0.0020 (17)	−0.0002 (17)	0.0020 (19)
C12A	0.014 (2)	0.028 (3)	0.020 (2)	−0.0003 (18)	0.0066 (18)	0.002 (2)
C13A	0.019 (2)	0.011 (2)	0.027 (2)	0.0018 (15)	0.0019 (18)	0.0013 (19)
C14A	0.023 (2)	0.017 (2)	0.024 (2)	0.0029 (17)	0.0001 (17)	−0.0003 (19)
C15A	0.024 (3)	0.032 (3)	0.029 (3)	0.001 (2)	0.005 (2)	0.009 (2)
S1B	0.0159 (6)	0.0169 (6)	0.0314 (6)	−0.0008 (4)	0.0015 (4)	−0.0006 (5)
S2B	0.0311 (7)	0.0280 (7)	0.0271 (6)	0.0009 (5)	−0.0022 (5)	0.0046 (5)
O1B	0.025 (2)	0.033 (2)	0.0208 (16)	−0.0076 (14)	0.0047 (13)	−0.0036 (15)
O2B	0.0169 (18)	0.022 (2)	0.0436 (19)	0.0001 (12)	−0.0010 (14)	−0.0052 (15)
O3B	0.029 (2)	0.026 (2)	0.0305 (18)	−0.0023 (14)	0.0012 (14)	−0.0060 (15)
C1B	0.022 (3)	0.021 (3)	0.025 (2)	−0.0044 (18)	0.009 (2)	−0.007 (2)
C2B	0.024 (3)	0.027 (3)	0.024 (3)	0.001 (2)	0.006 (2)	−0.007 (2)
C3B	0.020 (3)	0.037 (3)	0.032 (3)	−0.007 (2)	0.008 (2)	−0.012 (3)
C4B	0.038 (3)	0.028 (3)	0.037 (3)	−0.012 (2)	0.021 (3)	−0.015 (3)
C5B	0.046 (4)	0.023 (3)	0.030 (3)	−0.002 (2)	0.013 (2)	−0.002 (2)
C6B	0.026 (3)	0.031 (3)	0.023 (2)	0.000 (2)	0.005 (2)	−0.004 (2)
C7B	0.020 (3)	0.022 (3)	0.022 (2)	0.0006 (19)	−0.0033 (19)	0.004 (2)
C8B	0.012 (2)	0.026 (3)	0.019 (2)	−0.0016 (17)	0.0007 (18)	0.003 (2)
C9B	0.013 (2)	0.021 (3)	0.023 (2)	0.0006 (17)	0.0052 (17)	0.0038 (19)
C10B	0.014 (2)	0.021 (3)	0.023 (2)	0.0006 (17)	−0.0019 (18)	0.0007 (19)
C11B	0.015 (2)	0.020 (3)	0.032 (3)	0.0003 (18)	0.0052 (19)	0.009 (2)
C12B	0.017 (3)	0.024 (3)	0.022 (2)	0.0032 (18)	0.0053 (18)	0.004 (2)
C13B	0.017 (3)	0.023 (3)	0.050 (3)	0.0018 (19)	0.000 (2)	0.006 (2)
C14B	0.030 (3)	0.026 (3)	0.024 (2)	−0.0013 (18)	−0.0053 (19)	0.008 (2)
C15B	0.021 (3)	0.036 (3)	0.033 (3)	−0.005 (2)	0.003 (2)	0.013 (2)

Geometric parameters (Å, º)

S1A—O3A	1.432 (3)	S1B—O3B	1.433 (4)
S1A—O2A	1.449 (3)	S1B—O2B	1.440 (4)
S1A—C10A	1.771 (5)	S1B—C10B	1.760 (5)
S1A—C13A	1.791 (5)	S1B—C13B	1.829 (5)
S2A—C14A	1.827 (5)	S2B—C15B	1.822 (5)
S2A—C15A	1.830 (5)	S2B—C14B	1.832 (5)
O1A—C7A	1.368 (6)	O1B—C7B	1.366 (6)
O1A—C1A	1.407 (6)	O1B—C1B	1.400 (6)
C1A—C6A	1.378 (8)	C1B—C2B	1.382 (8)
C1A—C2A	1.380 (7)	C1B—C6B	1.382 (8)
C2A—C3A	1.390 (8)	C2B—C3B	1.388 (8)
C2A—H2A	0.9500	C2B—H2B	0.9500
C3A—C4A	1.363 (9)	C3B—C4B	1.382 (9)
C3A—H3A	0.9500	C3B—H3B	0.9500
C4A—C5A	1.399 (8)	C4B—C5B	1.381 (9)
C4A—H4A	0.9500	C4B—H4B	0.9500
C5A—C6A	1.381 (8)	C5B—C6B	1.408 (8)
C5A—H5A	0.9500	C5B—H5B	0.9500
C6A—H6A	0.9500	C6B—H6B	0.9500
C7A—C8A	1.394 (7)	C7B—C8B	1.389 (7)
C7A—C12A	1.396 (7)	C7B—C12B	1.406 (7)
C8A—C9A	1.385 (7)	C8B—C9B	1.380 (8)
C8A—H8A	0.9500	C8B—H8B	0.9500
C9A—C10A	1.394 (7)	C9B—C10B	1.398 (7)
C9A—H9A	0.9500	C9B—H9B	0.9500
C10A—C11A	1.392 (6)	C10B—C11B	1.384 (7)
C11A—C12A	1.375 (7)	C11B—C12B	1.365 (8)
C11A—H11A	0.9500	C11B—H11B	0.9500
C12A—H12A	0.9500	C12B—H12B	0.9500
C13A—C14A	1.518 (6)	C13B—C14B	1.486 (7)
C13A—H13A	0.9900	C13B—H13C	0.9900
C13A—H13B	0.9900	C13B—H13D	0.9900
C14A—C15A	1.479 (7)	C14B—C15B	1.475 (6)
C14A—H14A	1.0000	C14B—H14B	1.0000
C15A—H15A	0.9900	C15B—H15C	0.9900
C15A—H15B	0.9900	C15B—H15D	0.9900
O3A—S1A—O2A	119.12 (19)	O3B—S1B—O2B	118.7 (2)
O3A—S1A—C10A	108.7 (2)	O3B—S1B—C10B	108.8 (2)
O2A—S1A—C10A	107.2 (2)	O2B—S1B—C10B	107.9 (2)
O3A—S1A—C13A	107.1 (2)	O3B—S1B—C13B	110.7 (2)
O2A—S1A—C13A	108.1 (2)	O2B—S1B—C13B	108.7 (2)
C10A—S1A—C13A	105.9 (2)	C10B—S1B—C13B	100.5 (2)
C14A—S2A—C15A	47.7 (2)	C15B—S2B—C14B	47.6 (2)
C7A—O1A—C1A	118.3 (3)	C7B—O1B—C1B	118.5 (4)
C6A—C1A—C2A	122.0 (5)	C2B—C1B—C6B	121.6 (5)
C6A—C1A—O1A	119.3 (4)	C2B—C1B—O1B	118.5 (4)
C2A—C1A—O1A	118.5 (4)	C6B—C1B—O1B	119.7 (5)
C1A—C2A—C3A	118.4 (5)	C1B—C2B—C3B	119.2 (5)
C1A—C2A—H2A	120.8	C1B—C2B—H2B	120.4
C3A—C2A—H2A	120.8	C3B—C2B—H2B	120.4
C4A—C3A—C2A	121.0 (5)	C4B—C3B—C2B	120.2 (5)
C4A—C3A—H3A	119.5	C4B—C3B—H3B	119.9
C2A—C3A—H3A	119.5	C2B—C3B—H3B	119.9
C3A—C4A—C5A	119.6 (5)	C5B—C4B—C3B	120.6 (5)
C3A—C4A—H4A	120.2	C5B—C4B—H4B	119.7
C5A—C4A—H4A	120.2	C3B—C4B—H4B	119.7
C6A—C5A—C4A	120.5 (5)	C4B—C5B—C6B	119.8 (5)
C6A—C5A—H5A	119.8	C4B—C5B—H5B	120.1
C4A—C5A—H5A	119.8	C6B—C5B—H5B	120.1
C1A—C6A—C5A	118.6 (5)	C1B—C6B—C5B	118.6 (5)
C1A—C6A—H6A	120.7	C1B—C6B—H6B	120.7
C5A—C6A—H6A	120.7	C5B—C6B—H6B	120.7
O1A—C7A—C8A	123.3 (4)	O1B—C7B—C8B	123.6 (5)
O1A—C7A—C12A	116.3 (4)	O1B—C7B—C12B	116.0 (4)
C8A—C7A—C12A	120.4 (4)	C8B—C7B—C12B	120.3 (5)
C9A—C8A—C7A	119.7 (4)	C9B—C8B—C7B	119.7 (4)
C9A—C8A—H8A	120.2	C9B—C8B—H8B	120.1
C7A—C8A—H8A	120.2	C7B—C8B—H8B	120.1
C8A—C9A—C10A	119.4 (4)	C8B—C9B—C10B	119.4 (4)
C8A—C9A—H9A	120.3	C8B—C9B—H9B	120.3
C10A—C9A—H9A	120.3	C10B—C9B—H9B	120.3
C11A—C10A—C9A	121.0 (4)	C11B—C10B—C9B	120.8 (5)
C11A—C10A—S1A	119.6 (4)	C11B—C10B—S1B	119.4 (4)
C9A—C10A—S1A	119.3 (3)	C9B—C10B—S1B	119.7 (4)
C12A—C11A—C10A	119.4 (4)	C12B—C11B—C10B	120.1 (4)
C12A—C11A—H11A	120.3	C12B—C11B—H11B	119.9
C10A—C11A—H11A	120.3	C10B—C11B—H11B	119.9
C11A—C12A—C7A	120.1 (4)	C11B—C12B—C7B	119.6 (4)
C11A—C12A—H12A	119.9	C11B—C12B—H12B	120.2
C7A—C12A—H12A	119.9	C7B—C12B—H12B	120.2
C14A—C13A—S1A	110.7 (3)	C14B—C13B—S1B	112.5 (4)
C14A—C13A—H13A	109.5	C14B—C13B—H13C	109.1
S1A—C13A—H13A	109.5	S1B—C13B—H13C	109.1
C14A—C13A—H13B	109.5	C14B—C13B—H13D	109.1
S1A—C13A—H13B	109.5	S1B—C13B—H13D	109.1
H13A—C13A—H13B	108.1	H13C—C13B—H13D	107.8
C15A—C14A—C13A	119.0 (4)	C15B—C14B—C13B	118.9 (5)
C15A—C14A—S2A	66.3 (3)	C15B—C14B—S2B	65.9 (3)
C13A—C14A—S2A	116.7 (3)	C13B—C14B—S2B	114.6 (4)
C15A—C14A—H14A	115.3	C15B—C14B—H14B	116.0
C13A—C14A—H14A	115.3	C13B—C14B—H14B	116.0
S2A—C14A—H14A	115.3	S2B—C14B—H14B	116.0
C14A—C15A—S2A	66.0 (3)	C14B—C15B—S2B	66.5 (3)
C14A—C15A—H15A	117.1	C14B—C15B—H15C	117.1
S2A—C15A—H15A	117.1	S2B—C15B—H15C	117.1
C14A—C15A—H15B	117.1	C14B—C15B—H15D	117.1
S2A—C15A—H15B	117.1	S2B—C15B—H15D	117.1
H15A—C15A—H15B	114.1	H15C—C15B—H15D	114.1
C7A—O1A—C1A—C6A	72.7 (6)	C7B—O1B—C1B—C2B	116.1 (5)
C7A—O1A—C1A—C2A	−112.3 (5)	C7B—O1B—C1B—C6B	−68.1 (6)
C6A—C1A—C2A—C3A	1.1 (7)	C6B—C1B—C2B—C3B	−0.6 (7)
O1A—C1A—C2A—C3A	−173.7 (4)	O1B—C1B—C2B—C3B	175.1 (4)
C1A—C2A—C3A—C4A	−0.7 (7)	C1B—C2B—C3B—C4B	0.3 (7)
C2A—C3A—C4A—C5A	−0.5 (8)	C2B—C3B—C4B—C5B	−0.3 (8)
C3A—C4A—C5A—C6A	1.2 (8)	C3B—C4B—C5B—C6B	0.5 (8)
C2A—C1A—C6A—C5A	−0.5 (7)	C2B—C1B—C6B—C5B	0.8 (7)
O1A—C1A—C6A—C5A	174.4 (4)	O1B—C1B—C6B—C5B	−174.9 (4)
C4A—C5A—C6A—C1A	−0.7 (7)	C4B—C5B—C6B—C1B	−0.7 (7)
C1A—O1A—C7A—C8A	20.5 (7)	C1B—O1B—C7B—C8B	−20.4 (7)
C1A—O1A—C7A—C12A	−161.4 (4)	C1B—O1B—C7B—C12B	162.6 (4)
O1A—C7A—C8A—C9A	178.6 (4)	O1B—C7B—C8B—C9B	−176.5 (4)
C12A—C7A—C8A—C9A	0.6 (7)	C12B—C7B—C8B—C9B	0.3 (7)
C7A—C8A—C9A—C10A	0.2 (7)	C7B—C8B—C9B—C10B	−0.9 (7)
C8A—C9A—C10A—C11A	−0.9 (7)	C8B—C9B—C10B—C11B	1.1 (7)
C8A—C9A—C10A—S1A	176.8 (4)	C8B—C9B—C10B—S1B	176.7 (4)
O3A—S1A—C10A—C11A	152.5 (4)	O3B—S1B—C10B—C11B	−155.8 (4)
O2A—S1A—C10A—C11A	22.5 (4)	O2B—S1B—C10B—C11B	−25.8 (5)
C13A—S1A—C10A—C11A	−92.8 (4)	C13B—S1B—C10B—C11B	88.0 (4)
O3A—S1A—C10A—C9A	−25.3 (4)	O3B—S1B—C10B—C9B	28.6 (5)
O2A—S1A—C10A—C9A	−155.2 (4)	O2B—S1B—C10B—C9B	158.6 (4)
C13A—S1A—C10A—C9A	89.5 (4)	C13B—S1B—C10B—C9B	−87.7 (4)
C9A—C10A—C11A—C12A	0.9 (7)	C9B—C10B—C11B—C12B	−0.5 (7)
S1A—C10A—C11A—C12A	−176.9 (4)	S1B—C10B—C11B—C12B	−176.1 (4)
C10A—C11A—C12A—C7A	−0.1 (7)	C10B—C11B—C12B—C7B	−0.2 (8)
O1A—C7A—C12A—C11A	−178.8 (4)	O1B—C7B—C12B—C11B	177.3 (4)
C8A—C7A—C12A—C11A	−0.6 (7)	C8B—C7B—C12B—C11B	0.3 (8)
O3A—S1A—C13A—C14A	178.6 (3)	O3B—S1B—C13B—C14B	98.9 (4)
O2A—S1A—C13A—C14A	−51.9 (4)	O2B—S1B—C13B—C14B	−33.1 (5)
C10A—S1A—C13A—C14A	62.8 (4)	C10B—S1B—C13B—C14B	−146.2 (4)
S1A—C13A—C14A—C15A	83.9 (4)	S1B—C13B—C14B—C15B	77.5 (5)
S1A—C13A—C14A—S2A	160.2 (2)	S1B—C13B—C14B—S2B	152.4 (3)
C15A—S2A—C14A—C13A	−111.8 (4)	C15B—S2B—C14B—C13B	−112.1 (5)
C13A—C14A—C15A—S2A	108.5 (4)	C13B—C14B—C15B—S2B	105.9 (4)

(S-III) (S)-2-(4-Phenoxyphenylsulfonylmethyl)thiirane

Crystal data

C15H14O3S2	F(000) = 640
Mr = 306.38	Dx = 1.447 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
a = 5.3887 (3) Å	Cell parameters from 5268 reflections
b = 28.3506 (12) Å	θ = 4.8–68.0°
c = 9.2463 (4) Å	µ = 3.47 mm^−1
β = 95.463 (3)°	T = 100 K
V = 1406.17 (12) Å^3	Needle, clear colourless
Z = 4	0.22 × 0.07 × 0.01 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	4473 independent reflections
Radiation source: fine-focus sealed tube, Siemens KFFCU2K-90	3968 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
Detector resolution: 8.33 pixels mm^-1	θmax = 68.5°, θmin = 3.1°
ϕ and ω scans	h = −6→6
Absorption correction: multi-scan (TWINABS; Sheldrick, 2012)	k = −33→33
Tmin = 0.789, Tmax = 0.971	l = −11→11
25587 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.054	H-atom parameters constrained
wR(F^2) = 0.143	w = 1/[σ^2(Fo^2) + (0.0721P)^2 + 3.2676P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.002
4473 reflections	Δρmax = 0.66 e Å^−3
361 parameters	Δρmin = −0.44 e Å^−3
1 restraint	Absolute structure: Flack x parameter determined using 1669 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (2)

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1A	0.2929 (4)	0.59141 (6)	0.63875 (18)	0.0157 (4)
S2A	0.1530 (5)	0.71863 (7)	0.3688 (2)	0.0266 (5)
O1A	0.0645 (12)	0.4375 (2)	0.2178 (6)	0.0236 (14)
O2A	0.1926 (11)	0.57904 (19)	0.7715 (5)	0.0225 (13)
O3A	0.5569 (11)	0.6001 (2)	0.6394 (5)	0.0214 (12)
C1A	−0.0901 (17)	0.3997 (3)	0.2493 (8)	0.0200 (18)
C2A	−0.3188 (17)	0.3946 (3)	0.1712 (8)	0.0221 (19)
H2A	−0.3782	0.4180	0.1029	0.027*
C3A	−0.463 (2)	0.3548 (3)	0.1930 (10)	0.034 (2)
H3A	−0.6211	0.3511	0.1393	0.041*
C4A	−0.377 (2)	0.3213 (3)	0.2914 (10)	0.032 (2)
H4A	−0.4741	0.2940	0.3055	0.039*
C5A	−0.144 (2)	0.3274 (3)	0.3721 (9)	0.029 (2)
H5A	−0.0856	0.3043	0.4416	0.035*
C6A	0.0006 (17)	0.3667 (3)	0.3511 (9)	0.0242 (18)
H6A	0.1579	0.3709	0.4052	0.029*
C7A	0.1061 (17)	0.4729 (3)	0.3187 (8)	0.0170 (17)
C8A	−0.0456 (16)	0.4808 (3)	0.4291 (8)	0.0175 (17)
H8A	−0.1850	0.4609	0.4387	0.021*
C9A	0.0062 (17)	0.5179 (3)	0.5262 (8)	0.0194 (18)
H9A	−0.0987	0.5240	0.6010	0.023*
C10A	0.2155 (16)	0.5461 (3)	0.5113 (8)	0.0160 (17)
C11A	0.3675 (17)	0.5383 (3)	0.3992 (8)	0.0190 (17)
H11A	0.5068	0.5581	0.3884	0.023*
C12A	0.3113 (16)	0.5011 (3)	0.3036 (8)	0.0182 (17)
H12A	0.4143	0.4950	0.2278	0.022*
C13A	0.1292 (15)	0.6428 (3)	0.5695 (8)	0.0186 (16)
H13A	−0.0518	0.6361	0.5565	0.022*
H13B	0.1571	0.6689	0.6403	0.022*
C14A	0.2181 (15)	0.6578 (3)	0.4242 (8)	0.0216 (16)
H14A	0.1978	0.6337	0.3449	0.026*
C15A	0.4445 (17)	0.6874 (3)	0.4274 (10)	0.030 (2)
H15A	0.5600	0.6812	0.3525	0.036*
H15B	0.5284	0.6957	0.5240	0.036*
S1B	0.6873 (4)	0.70339 (6)	−0.1052 (2)	0.0212 (5)
S2B	0.8290 (4)	0.57240 (8)	0.1433 (2)	0.0282 (5)
O1B	0.9399 (12)	0.8624 (2)	0.2891 (5)	0.0250 (14)
O2B	0.7782 (12)	0.7110 (2)	−0.2438 (6)	0.0276 (14)
O3B	0.4263 (11)	0.69272 (19)	−0.1006 (6)	0.0253 (13)
C1B	1.0972 (17)	0.8993 (3)	0.2529 (8)	0.0212 (18)
C2B	1.3235 (18)	0.9040 (3)	0.3363 (9)	0.025 (2)
H2B	1.3752	0.8817	0.4099	0.030*
C3B	1.4721 (18)	0.9424 (3)	0.3087 (9)	0.028 (2)
H3B	1.6289	0.9461	0.3637	0.034*
C4B	1.398 (2)	0.9750 (3)	0.2038 (10)	0.032 (2)
H4B	1.5012	1.0012	0.1882	0.038*
C5B	1.173 (2)	0.9698 (3)	0.1215 (10)	0.030 (2)
H5B	1.1230	0.9921	0.0478	0.036*
C6B	1.0176 (18)	0.9311 (3)	0.1468 (9)	0.025 (2)
H6B	0.8612	0.9272	0.0914	0.030*
C7B	0.8843 (17)	0.8275 (3)	0.1882 (9)	0.0202 (18)
C8B	1.0289 (17)	0.8178 (3)	0.0748 (9)	0.0186 (18)
H8B	1.1687	0.8370	0.0601	0.022*
C9B	0.9678 (15)	0.7801 (3)	−0.0161 (9)	0.0179 (17)
H9B	1.0675	0.7725	−0.0922	0.021*
C10B	0.7575 (15)	0.7534 (3)	0.0055 (8)	0.0160 (17)
C11B	0.6141 (16)	0.7631 (3)	0.1174 (8)	0.0192 (17)
H11B	0.4719	0.7442	0.1299	0.023*
C12B	0.6751 (17)	0.7997 (3)	0.2108 (8)	0.0193 (18)
H12B	0.5782	0.8062	0.2891	0.023*
C13B	0.8703 (16)	0.6580 (3)	−0.0042 (9)	0.0278 (19)
H13C	1.0349	0.6555	−0.0429	0.033*
H13D	0.8989	0.6676	0.0989	0.033*
C14B	0.7487 (17)	0.6112 (3)	−0.0125 (9)	0.030 (2)
H14B	0.7371	0.5957	−0.1099	0.036*
C15B	0.5399 (17)	0.6018 (3)	0.0756 (9)	0.028 (2)
H15C	0.4030	0.5817	0.0316	0.034*
H15D	0.4836	0.6283	0.1343	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1A	0.0148 (10)	0.0170 (10)	0.0151 (9)	−0.0003 (7)	0.0000 (7)	0.0009 (7)
S2A	0.0347 (14)	0.0198 (11)	0.0249 (10)	0.0022 (9)	0.0014 (9)	0.0041 (8)
O1A	0.029 (4)	0.024 (3)	0.018 (3)	−0.011 (3)	0.006 (2)	−0.004 (2)
O2A	0.020 (3)	0.027 (3)	0.020 (3)	0.001 (2)	−0.001 (2)	0.000 (2)
O3A	0.020 (3)	0.023 (3)	0.020 (3)	−0.002 (2)	−0.002 (2)	−0.002 (2)
C1A	0.027 (5)	0.017 (4)	0.018 (4)	0.002 (3)	0.012 (4)	−0.006 (3)
C2A	0.019 (5)	0.032 (5)	0.015 (4)	−0.001 (4)	0.004 (3)	−0.007 (3)
C3A	0.033 (6)	0.037 (6)	0.035 (5)	−0.008 (4)	0.010 (4)	−0.016 (4)
C4A	0.051 (7)	0.020 (5)	0.030 (5)	−0.013 (4)	0.022 (5)	−0.010 (4)
C5A	0.047 (7)	0.021 (5)	0.022 (4)	0.003 (4)	0.014 (4)	0.000 (3)
C6A	0.023 (5)	0.027 (5)	0.023 (4)	0.004 (4)	0.004 (3)	−0.004 (3)
C7A	0.020 (5)	0.020 (4)	0.010 (4)	−0.002 (3)	−0.002 (3)	0.001 (3)
C8A	0.013 (5)	0.021 (4)	0.016 (4)	0.000 (3)	−0.008 (3)	0.000 (3)
C9A	0.027 (5)	0.016 (4)	0.015 (4)	0.004 (3)	0.002 (3)	0.004 (3)
C10A	0.020 (5)	0.015 (4)	0.013 (4)	0.001 (3)	0.000 (3)	0.002 (3)
C11A	0.020 (5)	0.015 (4)	0.022 (4)	0.003 (3)	−0.001 (3)	0.001 (3)
C12A	0.015 (5)	0.026 (4)	0.015 (4)	0.001 (3)	0.006 (3)	0.000 (3)
C13A	0.014 (4)	0.017 (4)	0.023 (4)	0.005 (3)	−0.009 (3)	0.001 (3)
C14A	0.027 (5)	0.013 (4)	0.024 (4)	0.003 (3)	−0.005 (3)	−0.002 (3)
C15A	0.020 (6)	0.042 (5)	0.028 (4)	0.002 (4)	0.006 (4)	0.008 (4)
S1B	0.0190 (12)	0.0173 (10)	0.0272 (10)	−0.0007 (8)	0.0010 (8)	0.0002 (8)
S2B	0.0314 (14)	0.0272 (12)	0.0251 (11)	0.0018 (9)	−0.0014 (9)	0.0039 (8)
O1B	0.033 (4)	0.029 (3)	0.013 (3)	−0.008 (3)	0.005 (2)	−0.002 (2)
O2B	0.030 (4)	0.027 (3)	0.026 (3)	−0.005 (3)	0.002 (3)	−0.008 (2)
O3B	0.012 (3)	0.024 (3)	0.039 (3)	−0.002 (2)	−0.004 (2)	−0.001 (2)
C1B	0.019 (5)	0.021 (4)	0.025 (4)	−0.006 (3)	0.008 (3)	−0.007 (3)
C2B	0.023 (5)	0.028 (5)	0.022 (4)	0.005 (4)	0.001 (4)	−0.006 (3)
C3B	0.019 (5)	0.036 (5)	0.030 (5)	−0.010 (4)	0.002 (4)	−0.011 (4)
C4B	0.035 (6)	0.031 (5)	0.032 (5)	−0.011 (4)	0.018 (5)	−0.012 (4)
C5B	0.046 (7)	0.020 (5)	0.028 (5)	−0.002 (4)	0.012 (4)	−0.001 (4)
C6B	0.030 (6)	0.026 (5)	0.020 (4)	−0.004 (4)	0.006 (4)	−0.004 (3)
C7B	0.020 (5)	0.019 (4)	0.021 (4)	−0.001 (3)	−0.004 (3)	0.004 (3)
C8B	0.015 (5)	0.022 (4)	0.020 (4)	−0.002 (3)	0.005 (3)	0.006 (3)
C9B	0.009 (4)	0.022 (4)	0.023 (4)	−0.001 (3)	0.003 (3)	0.006 (3)
C10B	0.007 (4)	0.024 (4)	0.017 (4)	0.001 (3)	0.000 (3)	0.000 (3)
C11B	0.014 (5)	0.020 (4)	0.023 (4)	0.000 (3)	−0.001 (3)	0.006 (3)
C12B	0.020 (5)	0.023 (4)	0.016 (4)	−0.001 (3)	0.004 (3)	0.004 (3)
C13B	0.020 (5)	0.027 (5)	0.035 (5)	−0.001 (4)	−0.003 (4)	0.009 (4)
C14B	0.035 (6)	0.031 (5)	0.021 (4)	0.002 (4)	−0.006 (3)	0.007 (3)
C15B	0.022 (5)	0.033 (5)	0.031 (5)	−0.008 (4)	0.003 (4)	0.013 (4)

Geometric parameters (Å, º)

S1A—O2A	1.431 (5)	S1B—O2B	1.431 (6)
S1A—O3A	1.443 (6)	S1B—O3B	1.443 (6)
S1A—C10A	1.766 (8)	S1B—C10B	1.769 (8)
S1A—C13A	1.791 (7)	S1B—C13B	1.824 (9)
S2A—C14A	1.824 (7)	S2B—C15B	1.825 (10)
S2A—C15A	1.839 (10)	S2B—C14B	1.832 (8)
O1A—C7A	1.374 (10)	O1B—C7B	1.375 (10)
O1A—C1A	1.404 (10)	O1B—C1B	1.406 (10)
C1A—C2A	1.376 (13)	C1B—C6B	1.371 (13)
C1A—C6A	1.383 (12)	C1B—C2B	1.386 (13)
C2A—C3A	1.395 (13)	C2B—C3B	1.390 (13)
C2A—H2A	0.9500	C2B—H2B	0.9500
C3A—C4A	1.366 (15)	C3B—C4B	1.372 (15)
C3A—H3A	0.9500	C3B—H3B	0.9500
C4A—C5A	1.409 (16)	C4B—C5B	1.373 (15)
C4A—H4A	0.9500	C4B—H4B	0.9500
C5A—C6A	1.384 (13)	C5B—C6B	1.414 (13)
C5A—H5A	0.9500	C5B—H5B	0.9500
C6A—H6A	0.9500	C6B—H6B	0.9500
C7A—C12A	1.382 (12)	C7B—C8B	1.392 (12)
C7A—C8A	1.386 (12)	C7B—C12B	1.407 (12)
C8A—C9A	1.393 (11)	C8B—C9B	1.380 (12)
C8A—H8A	0.9500	C8B—H8B	0.9500
C9A—C10A	1.400 (12)	C9B—C10B	1.393 (11)
C9A—H9A	0.9500	C9B—H9B	0.9500
C10A—C11A	1.399 (11)	C10B—C11B	1.376 (11)
C11A—C12A	1.392 (12)	C11B—C12B	1.370 (12)
C11A—H11A	0.9500	C11B—H11B	0.9500
C12A—H12A	0.9500	C12B—H12B	0.9500
C13A—C14A	1.528 (10)	C13B—C14B	1.477 (12)
C13A—H13A	0.9900	C13B—H13C	0.9900
C13A—H13B	0.9900	C13B—H13D	0.9900
C14A—C15A	1.480 (12)	C14B—C15B	1.475 (11)
C14A—H14A	1.0000	C14B—H14B	1.0000
C15A—H15A	0.9900	C15B—H15C	0.9900
C15A—H15B	0.9900	C15B—H15D	0.9900
O2A—S1A—O3A	119.4 (3)	O2B—S1B—O3B	118.4 (4)
O2A—S1A—C10A	108.0 (3)	O2B—S1B—C10B	109.0 (4)
O3A—S1A—C10A	107.3 (4)	O3B—S1B—C10B	107.8 (4)
O2A—S1A—C13A	107.0 (4)	O2B—S1B—C13B	110.5 (4)
O3A—S1A—C13A	108.3 (4)	O3B—S1B—C13B	108.5 (4)
C10A—S1A—C13A	106.1 (4)	C10B—S1B—C13B	101.2 (4)
C14A—S2A—C15A	47.7 (4)	C15B—S2B—C14B	47.6 (4)
C7A—O1A—C1A	118.5 (6)	C7B—O1B—C1B	118.1 (6)
C2A—C1A—C6A	121.8 (8)	C6B—C1B—C2B	122.3 (8)
C2A—C1A—O1A	119.4 (7)	C6B—C1B—O1B	120.3 (8)
C6A—C1A—O1A	118.6 (8)	C2B—C1B—O1B	117.2 (7)
C1A—C2A—C3A	119.6 (8)	C1B—C2B—C3B	117.7 (8)
C1A—C2A—H2A	120.2	C1B—C2B—H2B	121.2
C3A—C2A—H2A	120.2	C3B—C2B—H2B	121.2
C4A—C3A—C2A	120.0 (10)	C4B—C3B—C2B	121.5 (10)
C4A—C3A—H3A	120.0	C4B—C3B—H3B	119.2
C2A—C3A—H3A	120.0	C2B—C3B—H3B	119.2
C3A—C4A—C5A	119.7 (8)	C3B—C4B—C5B	120.2 (9)
C3A—C4A—H4A	120.1	C3B—C4B—H4B	119.9
C5A—C4A—H4A	120.1	C5B—C4B—H4B	119.9
C6A—C5A—C4A	120.7 (9)	C4B—C5B—C6B	119.7 (9)
C6A—C5A—H5A	119.7	C4B—C5B—H5B	120.1
C4A—C5A—H5A	119.7	C6B—C5B—H5B	120.1
C1A—C6A—C5A	118.2 (9)	C1B—C6B—C5B	118.6 (9)
C1A—C6A—H6A	120.9	C1B—C6B—H6B	120.7
C5A—C6A—H6A	120.9	C5B—C6B—H6B	120.7
O1A—C7A—C12A	115.7 (7)	O1B—C7B—C8B	123.5 (8)
O1A—C7A—C8A	123.3 (7)	O1B—C7B—C12B	115.4 (7)
C12A—C7A—C8A	121.0 (7)	C8B—C7B—C12B	121.0 (8)
C7A—C8A—C9A	120.0 (8)	C9B—C8B—C7B	119.5 (8)
C7A—C8A—H8A	120.0	C9B—C8B—H8B	120.2
C9A—C8A—H8A	120.0	C7B—C8B—H8B	120.2
C8A—C9A—C10A	118.8 (7)	C8B—C9B—C10B	118.9 (7)
C8A—C9A—H9A	120.6	C8B—C9B—H9B	120.5
C10A—C9A—H9A	120.6	C10B—C9B—H9B	120.5
C11A—C10A—C9A	121.1 (7)	C11B—C10B—C9B	121.5 (8)
C11A—C10A—S1A	119.4 (6)	C11B—C10B—S1B	119.3 (6)
C9A—C10A—S1A	119.4 (6)	C9B—C10B—S1B	119.0 (6)
C12A—C11A—C10A	118.9 (8)	C12B—C11B—C10B	120.4 (8)
C12A—C11A—H11A	120.6	C12B—C11B—H11B	119.8
C10A—C11A—H11A	120.6	C10B—C11B—H11B	119.8
C7A—C12A—C11A	120.1 (7)	C11B—C12B—C7B	118.6 (7)
C7A—C12A—H12A	119.9	C11B—C12B—H12B	120.7
C11A—C12A—H12A	119.9	C7B—C12B—H12B	120.7
C14A—C13A—S1A	110.8 (5)	C14B—C13B—S1B	113.0 (6)
C14A—C13A—H13A	109.5	C14B—C13B—H13C	109.0
S1A—C13A—H13A	109.5	S1B—C13B—H13C	109.0
C14A—C13A—H13B	109.5	C14B—C13B—H13D	109.0
S1A—C13A—H13B	109.5	S1B—C13B—H13D	109.0
H13A—C13A—H13B	108.1	H13C—C13B—H13D	107.8
C15A—C14A—C13A	117.8 (7)	C15B—C14B—C13B	119.4 (8)
C15A—C14A—S2A	66.7 (5)	C15B—C14B—S2B	66.0 (5)
C13A—C14A—S2A	116.2 (5)	C13B—C14B—S2B	115.4 (6)
C15A—C14A—H14A	115.7	C15B—C14B—H14B	115.6
C13A—C14A—H14A	115.7	C13B—C14B—H14B	115.6
S2A—C14A—H14A	115.7	S2B—C14B—H14B	115.6
C14A—C15A—S2A	65.7 (5)	C14B—C15B—S2B	66.5 (5)
C14A—C15A—H15A	117.2	C14B—C15B—H15C	117.1
S2A—C15A—H15A	117.2	S2B—C15B—H15C	117.1
C14A—C15A—H15B	117.2	C14B—C15B—H15D	117.1
S2A—C15A—H15B	117.2	S2B—C15B—H15D	117.1
H15A—C15A—H15B	114.2	H15C—C15B—H15D	114.1
C7A—O1A—C1A—C2A	111.4 (8)	C7B—O1B—C1B—C6B	68.2 (10)
C7A—O1A—C1A—C6A	−73.3 (10)	C7B—O1B—C1B—C2B	−116.9 (8)
C6A—C1A—C2A—C3A	−1.0 (11)	C6B—C1B—C2B—C3B	−0.4 (11)
O1A—C1A—C2A—C3A	174.1 (7)	O1B—C1B—C2B—C3B	−175.2 (7)
C1A—C2A—C3A—C4A	0.1 (12)	C1B—C2B—C3B—C4B	0.8 (12)
C2A—C3A—C4A—C5A	0.8 (13)	C2B—C3B—C4B—C5B	−1.1 (13)
C3A—C4A—C5A—C6A	−0.9 (13)	C3B—C4B—C5B—C6B	1.0 (13)
C2A—C1A—C6A—C5A	0.8 (11)	C2B—C1B—C6B—C5B	0.4 (12)
O1A—C1A—C6A—C5A	−174.3 (7)	O1B—C1B—C6B—C5B	175.0 (7)
C4A—C5A—C6A—C1A	0.1 (12)	C4B—C5B—C6B—C1B	−0.7 (12)
C1A—O1A—C7A—C12A	161.5 (8)	C1B—O1B—C7B—C8B	21.0 (12)
C1A—O1A—C7A—C8A	−18.8 (12)	C1B—O1B—C7B—C12B	−162.3 (8)
O1A—C7A—C8A—C9A	−179.0 (7)	O1B—C7B—C8B—C9B	175.9 (7)
C12A—C7A—C8A—C9A	0.7 (12)	C12B—C7B—C8B—C9B	−0.6 (13)
C7A—C8A—C9A—C10A	−1.2 (12)	C7B—C8B—C9B—C10B	1.9 (12)
C8A—C9A—C10A—C11A	1.7 (12)	C8B—C9B—C10B—C11B	−1.7 (12)
C8A—C9A—C10A—S1A	−176.8 (6)	C8B—C9B—C10B—S1B	−177.0 (6)
O2A—S1A—C10A—C11A	−153.4 (6)	O2B—S1B—C10B—C11B	155.2 (7)
O3A—S1A—C10A—C11A	−23.5 (7)	O3B—S1B—C10B—C11B	25.5 (8)
C13A—S1A—C10A—C11A	92.1 (7)	C13B—S1B—C10B—C11B	−88.4 (7)
O2A—S1A—C10A—C9A	25.1 (8)	O2B—S1B—C10B—C9B	−29.4 (8)
O3A—S1A—C10A—C9A	155.1 (6)	O3B—S1B—C10B—C9B	−159.1 (6)
C13A—S1A—C10A—C9A	−89.3 (7)	C13B—S1B—C10B—C9B	87.0 (7)
C9A—C10A—C11A—C12A	−1.6 (12)	C9B—C10B—C11B—C12B	0.2 (13)
S1A—C10A—C11A—C12A	176.9 (6)	S1B—C10B—C11B—C12B	175.5 (6)
O1A—C7A—C12A—C11A	179.1 (7)	C10B—C11B—C12B—C7B	1.0 (12)
C8A—C7A—C12A—C11A	−0.6 (13)	O1B—C7B—C12B—C11B	−177.6 (7)
C10A—C11A—C12A—C7A	1.0 (12)	C8B—C7B—C12B—C11B	−0.8 (13)
O2A—S1A—C13A—C14A	−178.0 (5)	O2B—S1B—C13B—C14B	−99.3 (7)
O3A—S1A—C13A—C14A	52.0 (6)	O3B—S1B—C13B—C14B	32.0 (8)
C10A—S1A—C13A—C14A	−62.9 (6)	C10B—S1B—C13B—C14B	145.3 (6)
S1A—C13A—C14A—C15A	−83.9 (7)	S1B—C13B—C14B—C15B	−76.6 (9)
S1A—C13A—C14A—S2A	−160.1 (4)	S1B—C13B—C14B—S2B	−152.1 (5)
C15A—S2A—C14A—C13A	110.8 (8)	C15B—S2B—C14B—C13B	112.6 (9)
C13A—C14A—C15A—S2A	−108.4 (6)	C13B—C14B—C15B—S2B	−106.7 (8)