Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614021214/fa3348sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614021214/fa3348R-IIsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614021214/fa3348S-IIIsup3.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614021214/fa3348R-IIsup4.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614021214/fa3348S-IIIsup5.cml |
CCDC references: 1025708; 1025709
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).
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.
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 Uiso(H) = 1.2Ueq(C).
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.
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).
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) Å3 | Needle, clear colourless |
Z = 4 | 0.23 × 0.01 × 0.01 mm |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0625P)2] where P = (Fo2 + 2Fc2)/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) |
C15H14O3S2 | V = 1405.58 (12) Å3 |
Mr = 306.38 | Z = 4 |
Monoclinic, P21 | Cu Kα radiation |
a = 5.3891 (3) Å | µ = 3.48 mm−1 |
b = 28.3231 (13) Å | T = 100 K |
c = 9.2503 (4) Å | 0.23 × 0.01 × 0.01 mm |
β = 95.434 (3)° |
Bruker SMART APEX CCD area-detector diffractometer | 4353 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | 3926 reflections with I > 2σ(I) |
Tmin = 0.50, Tmax = 0.97 | Rint = 0.035 |
11717 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.097 | Δρmax = 0.43 e Å−3 |
S = 1.07 | Δρmin = −0.23 e Å−3 |
4353 reflections | Absolute structure: Flack x parameter determined using 1610 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013). |
361 parameters | Absolute structure parameter: 0.055 (9) |
1 restraint |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
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) Å3 | Needle, clear colourless |
Z = 4 | 0.22 × 0.07 × 0.01 mm |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.143 | w = 1/[σ2(Fo2) + (0.0721P)2 + 3.2676P] where P = (Fo2 + 2Fc2)/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) |
C15H14O3S2 | V = 1406.17 (12) Å3 |
Mr = 306.38 | Z = 4 |
Monoclinic, P21 | Cu Kα radiation |
a = 5.3887 (3) Å | µ = 3.47 mm−1 |
b = 28.3506 (12) Å | T = 100 K |
c = 9.2463 (4) Å | 0.22 × 0.07 × 0.01 mm |
β = 95.463 (3)° |
Bruker SMART APEX CCD area-detector diffractometer | 4473 independent reflections |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2012) | 3968 reflections with I > 2σ(I) |
Tmin = 0.789, Tmax = 0.971 | Rint = 0.053 |
25587 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.143 | Δρmax = 0.66 e Å−3 |
S = 1.02 | Δρmin = −0.44 e Å−3 |
4473 reflections | Absolute structure: Flack x parameter determined using 1669 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
361 parameters | Absolute structure parameter: 0.02 (2) |
1 restraint |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
Experimental details
(R-II) | (S-III) | |
Crystal data | ||
Chemical formula | C15H14O3S2 | C15H14O3S2 |
Mr | 306.38 | 306.38 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21 |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 5.3891 (3), 28.3231 (13), 9.2503 (4) | 5.3887 (3), 28.3506 (12), 9.2463 (4) |
β (°) | 95.434 (3) | 95.463 (3) |
V (Å3) | 1405.58 (12) | 1406.17 (12) |
Z | 4 | 4 |
Radiation type | Cu Kα | Cu Kα |
µ (mm−1) | 3.48 | 3.47 |
Crystal size (mm) | 0.23 × 0.01 × 0.01 | 0.22 × 0.07 × 0.01 |
Data collection | ||
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2007) | Multi-scan (TWINABS; Sheldrick, 2012) |
Tmin, Tmax | 0.50, 0.97 | 0.789, 0.971 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11717, 4353, 3926 | 25587, 4473, 3968 |
Rint | 0.035 | 0.053 |
(sin θ/λ)max (Å−1) | 0.607 | 0.604 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.097, 1.07 | 0.054, 0.143, 1.02 |
No. of reflections | 4353 | 4473 |
No. of parameters | 361 | 361 |
No. of restraints | 1 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.23 | 0.66, −0.44 |
Absolute structure | Flack x parameter determined using 1610 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013). | Flack x parameter determined using 1669 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Absolute structure parameter | 0.055 (9) | 0.02 (2) |
Computer programs: APEX2 (Bruker, 2007), APEX2 and SAINT (Bruker, 2007), SAINT (Bruker, 2014), SAINT (Bruker, 2007) and XPREP (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2014), CrystalMaker (Palmer, 2008), Mercury (Macrae et al., 2008), pyMOL (Schrödinger, 2011) and POVRay (Cason, 2003), XCIF (Sheldrick, 2008), enCIFer (Allen et al., 2004) and publCIF (Westrip, 2010).
C1A—O1A—C7A—C8A | 20.5 (7) | C1B—O1B—C7B—C8B | −20.4 (7) |
C10A—S1A—C13A—C14A | 62.8 (4) | C10B—S1B—C13B—C14B | −146.2 (4) |
C1A—O1A—C7A—C8A | −18.8 (12) | C1B—O1B—C7B—C8B | 21.0 (12) |
C10A—S1A—C13A—C14A | −62.9 (6) | C10B—S1B—C13B—C14B | 145.3 (6) |
(R)-(II) | (S)-(III) | |
S2A···CgB | 3.571i | 3.576ii |
S2B···CgA | 3.543ii | 3.436i |
CgA/B denotes the centroid of the C7–C12 phenyl ring of molecule A or B. Symmetry codes: (i) 1 + x, y, z; (ii) 1 - x, y, z. |