research communications
Syntheses and crystal structures of two dinaphtho[2,1-d:1′,2′-f][1,3]dithiepine atropisomers
aBDG Synthesis, PO Box 38627, Wellington Mail Centre 5045, Wellington, New Zealand, bFerrier Research Institute, Victoria University of Wellington, PO Box 33436, Lower Hutt 5046, New Zealand, and cDepartment of Chemistry, University of Otago, PO Box 56, Dunedin 9054, New Zealand
*Correspondence e-mail: john.mcadam@otago.ac.nz
The closely related title compounds, 1-(dinaphtho[2,1-d:1′,2′-f][1,3]dithiepin-4-yl)-2,2-dimethylpropan-1-ol, C26H24OS2, 1 and 2-(dinaphtho[2,1-d:1′,2′-f][1,3]dithiepin-4-yl)-3,3-dimethylbutan-2-ol, C27H26OS2, 2, both comprise an atropisomeric binaphthyl dithioacetal unit substituted at the methylene carbon atom with a chiral neopentyl alcohol grouping. The overall stereochemistry of the racemate in each case is defined as aS,R and aR,S. In 1, the hydroxyl group generates inversion dimers via pairwise intermolecular O—H⋯S hydrogen bonds whereas in 2, the O—H⋯S link is intramolecular. Weak C—H⋯π interactions link the molecules into extended arrays in both structures.
1. Chemical context
Stereoselective synthetic methodology continues to be a major research focus underpinning many areas of chemical and biological sciences. One design strategy is the utilization of atropisomerism. This exploits the et al., 2022; Wencel-Delord et al., 2015; Cheng et al., 2021). Dinaphtho[2,1-d:1′,2′-f][1,3]dithiepine (3) provides access to an organosulfur-stabilized carbanion. This undergoes nucleophilic addition to prochiral electrophiles producing separable diastereomeric products with varying degrees of (Delogu et al., 1991). Delogu and co-workers, however, report significantly improved from nucleophilic attack upon substrates in which the chiral auxiliary (dinaphthothiepine) is pre-attached to a (benzaldehyde) stereogenic centre. This work reports the synthesis of the prochiral ketone 5 from a pivaldehyde sourced diastereoisomer mix, and its reduction and methylation reactions that occur with high diastereomeric excess. Single-crystal X-ray structures of 1-(dinaphtho[2,1-d:1′,2′-f][1,3]dithiepin-4-yl)-2,2-dimethylpropan-1-ol, 1, and 2-(dinaphtho[2,1-d:1′,2′-f][1,3]dithiepin-4-yl)-3,3-dimethylbutan-2-ol, 2, confirm the relative stereochemistry of the major isomers.
that results from about single bonds, a particular feature of biaryl compounds (Cen2. Structural commentary
The structural core of compounds 1 and 2 is a 1,1′-linked binaphthalene system. This is functionalized at the 2,2′ positions with a disulfaneylmethane unit, generating a seven-membered ring with pseudo-C2 symmetry locking the binaphthalene into R and S atropisomers. The individual naphthalene ring systems in 1 are predictably flat, with r.m.s. deviations from the ten-atom mean plane of 0.019 and 0.022 Å for C101–C110 and C201–C210 respectively. The C102—C101—C201—C202 torsion angle is −62.5 (3)° and the dihedral angle between naphthalene ring mean planes is 65.91 (4)°. Capping the stereogenic auxiliary is a chiral (at atom C2) neopentyl alcohol group (Fig. 1), giving aS,R and aR,S pairs.
The synthesis of compound 2 (Fig. 2) places a methyl group on the chiral C2 atom in place of the hydrogen atom of 1. This juxtaposition generates a racemate pair with similar conformation and metrics to 1 (Fig. 3): r.m.s. deviations from the naphthalene mean planes are 0.05 and 0.04 Å and the C102—C101—C201—C202 torsion angle is −63.95 (19)°, however the dihedral angle between naphthalene rings is larger at 72.35 (3)°. The alcohol group is positioned such to form an intramolecular hydrogen bond to one of the bridge sulfur atoms (O2—H2O⋯S1 = 2.52 Å).
3. Supramolecular features
In the crystal of 1, inversion dimers form through pairwise classical O2—H2⋯S2 hydrogen bonds (Table 1), which generate R22(10) ring motifs (Fig. 4). C—H⋯π interactions between adjacent naphthalene rings link molecules in the a-axis direction (C106—H106⋯Cg3 = 2.87 Å, where Cg3 is the C201–C204/C210/C209 ring centroid). This is supported by a short contact C105—H105⋯S1 of 2.90 Å (Fig. 5). For 2, in which the alcohol hydrogen atom is engaged in an intramolecular hydrogen bond with sulfur (Table 2), the most important intermolecular interactions are a pair of C—H⋯π interactions that propagate in the b-axis direction: C203—H203⋯Cg2 (2.60 Å) forms a screw diad (Fig. 6), and C103—H103⋯Cg4 (2.93 Å)(Cg2 and Cg4 are the centroids of the C105–C110 and C205–C210 rings, respectively) forms zigzag chains via a glide reflection in the bc plane (Fig. 7).
4. Database survey
A search of the Cambridge Structural Database (version 5.41, November 2019 with updates to March 2020; Groom et al., 2016) suggests the dinaphthodithiepine structure is unprecedented, although a dinaphthodithiepine S-oxide has been reported (refcode JITTEL; Delogu et al., 1991). The analogous dinaphthodioxepine fragment, however, is more common, with more than ten examples reported including the close relative of 1, 4-(1-methoxy-1-phenylethyl)dinaphtho[2,1-d:1′,2′-f][1,3]dioxepine (KUBYEL; Maglioli et al., 1992), and the simple, but chirally resolved (R)-dinaphthodioxepine CAJCEY (Zhang et al., 2015).
5. Synthesis and crystallization
Compounds 1 and 2 were synthesized in three steps (Fig. 8) from dithiepin 3 prepared from a Lewis-acid-catalysed condensation of binaphthothiol with dimethoxymethane (Delogu et al., 1991). Diastereoisomer mix (4): dithioacetal 3 in THF was cooled to 173 K under Ar. n-BuLi (1.6 M in hexanes, 1.2 equiv.) was added dropwise and the suspension stirred for 5 min. Pivaldehyde (1.2 equiv.) was similarly added and the reaction stirred for a further 10 min. The mixture was quenched with saturated NH4Cl and extracted with Et2O. The ethereal extract was washed, dried (MgSO4) and concentrated in vacuo then chromatographed (SiO2/CH2Cl2), giving a white solid, a 5:2 mixture of the two possible of 4 (81%, 44% d.e.). Further with a CH2Cl2/hexane solvent allowed separation into major (1) and minor (4m) [4m, m.p. 424 K, 1H NMR (200 MHz, CDCl3) δ (ppm): 1.02 (9H, s, t-Bu), 1.90 (1H, d, J = 6.0 Hz, OH), 4.01 (1H, dd, J = 6.0, 3.0 Hz, CHOH), 5.18 (1H, d, J = 3.0 Hz, S—CH—S), 7.07–7.28 (4H, m, Ar), 7.42–7.53 (2H, m, Ar), 7.80–8.00 (6H, m, Ar).]
4-Pivaloyldinaphtho[2,1-d:1′,2′-f][1,3]dithiepine (5): to a stirred solution of alcohol 4 in CH2Cl2 was added CaCO3 and powdered 4 Å molecular sieves. PCC (3.3 equiv.) was added and the reaction mix stirred (30 min, Ar, RT). The solvent was concentrated in vacuo and filtered through SiO2 to give the ketone as a white solid, m.p. 445–446 K (88% yield). 1H NMR (200 MHz, CDCl3) δ (ppm): 1.30 (9H, s, t-Bu), 5.73 (1H, s, S—CH—S), 7.15 (1H, d, J = 8.4 Hz, Ar), 7.18–7.31 (3H, m, Ar), 7.46–7.56 (2H, m, Ar), 7.64 (1H, d, J = 8.4 Hz, Ar), 7.83 (1H, d, J = 8.4 Hz, Ar), 7.95–8.03 (4H, m, Ar). 13C NMR (50 MHz) δ (ppm): 27.2 (Me), 44.3 (CMe3), 64.6 (S–CH—S), 126.3, 126.6, 126.8 (Ar CH), 126.9 (Ar C), 127.5, 127.6 (Ar CH), 127.7 (Ar C), 128.3, 128.4, 129.1, 129.2 (Ar CH), 130.4 (Ar C), 132.2 (Ar CH), 131.5 (Ar C), 133.1 (Ar CH), 134.1, 134.5, 142.8, 143.0 (Ar C), 206.2 (C=O).
1-(Dinaphtho[2,1-d:1′,2′-f][1,3]dithiepin-4-yl)-2,2-dimethylpropan-1-ol (1): a solution of ketone 5 in THF was cooled to 272 K under Ar. LiAlH4 (2 equiv.) was added in one portion and the suspension stirred for 30 min. The reaction mixture was quenched by addition of H2O and extracted with Et2O. The ethereal extract was washed, dried (MgSO4) and concentrated in vacuo, then chromatographed (SiO2/CH2Cl2) to give 1 as a white solid, m.p. 426 K (91%, >95% d.e.). Crystals for X-ray diffraction were obtained from slow evaporation of an EtOH/H2O solvent mix. 1H NMR (300 MHz, CDCl3) δ (ppm): 1.01 (9H, s, t-Bu), 2.70 (1H, d, J = 6.3 Hz, OH), 3.29 (1H, dd, J = 6.3, 3.3 Hz, CHOH), 5.16 (1H, d, J = 3.3 Hz, S—CH—S), 7.10–7.15 (2H, m, Ar), 7.18–7.26 (2H, m, Ar), 7.44–7.51 (2H, m, Ar), 7.80–7.87 (2H, m, Ar), 7.90–7.98 (4H, m, Ar). 13C NMR (75 MHz) δ (ppm): 26.7 (Me), 36.1 (CMe3), 70.1 (COH), 80.2 (S—CH—S), 126.5, 126.7, 127.6, 127.7, 128.3 (Ar CH), 128.8 (Ar C), 129.0, 129.2 (Ar CH), 131.5 (Ar C), 132.2 (Ar CH), 132.3 (Ar C), 133.0 (Ar CH), 133.9, 134.0, 141.7, 142.6 (Ar C).
2-(Dinaphtho[2,1-d:1′,2′-f][1,3]dithiepin-4-yl)-3,3-dimethylbutan-2-ol (2): a solution of ketone 5 in THF was cooled to 193 K under Ar. MeLi (1.0 M in Et2O, 5 equiv.) was added and the solution stirred 30 min. The reaction mixture was quenched by addition of EtOD then H2O and extracted with Et2O. The ethereal extract was washed, dried (MgSO4) and concentrated in vacuo, then chromatographed on SiO2 (1:1 CH2Cl2/hexane) to give 2 as a white solid, m.p. 448–449 K (81%, >95% d.e.). Crystals for X-ray diffraction were obtained from slow evaporation of an EtOH/H2O mix. 1H NMR (200 MHz, CDCl3) δ (ppm): 1.10 (9H, s, t-Bu), 1.16 (3H, s, CMeOH), 3.09 (1H, s, OH), 5.18 (1H, s, S—CH—S), 7.08–7.30 (4H, m, Ar), 7.43–7.52 (2H, m, Ar), 7.83 (1H, d, J = 8.4 Hz, Ar), 7.85 (1H, d, J = 8.4 Hz, Ar), 7.92–7.99 (4H, m, Ar). 13C NMR (50 MHz) δ (ppm): 20.0 (Me), 26.8 (CMe3), 38.6 (CMe3), 76.1 (COH), 79.4 (S—CH—S), 126.1, 126.2, 126.4, 127.4, 127.9, 128.0, 128.5 (Ar CH), 129.0 (Ar C), 129.1, 131.8 (Ar CH), 131.9, 132.0, 132.1 (Ar C), 132.8 (Ar CH), 133.5, 133.7, 141.8, 142.6 (Ar C).
6. Refinement
Crystal data, data collection and structure . All H atoms were refined using a riding model with d(C—H) = 0.95 Å, Uiso = 1.2Ueq (C) for aromatic H, 1.00 Å, Uiso = 1.2Ueq (C) for CH, 0.98 Å, Uiso = 1.5Ueq (C) for methyl H atoms and d(O—H) = 0.84 Å, Uiso = 1.5Ueq (O) for OH.
details are summarized in Table 3
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Supporting information
https://doi.org/10.1107/S2056989023000476/hb8049sup1.cif
contains datablocks 1, 2, global. DOI:Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989023000476/hb80491sup2.hkl
Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989023000476/hb80492sup3.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989023000476/hb80491sup4.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989023000476/hb80492sup5.cml
For both structures, data collection: SMART (Bruker, 1998); cell
SAINT (Bruker, 1998). Data reduction: SAINT (Bruker, 19980) for (1); SAINT (Bruker, 1998) for (2). For both structures, program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2019/2 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2019/2 (Sheldrick, 2015b) and publCIF (Westrip 2010).C26H24OS2 | Z = 2 |
Mr = 416.57 | F(000) = 440 |
Triclinic, P1 | Dx = 1.294 Mg m−3 |
a = 9.322 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.064 (4) Å | Cell parameters from 4367 reflections |
c = 11.207 (4) Å | θ = 2.9–26.4° |
α = 81.607 (4)° | µ = 0.26 mm−1 |
β = 84.444 (5)° | T = 163 K |
γ = 69.411 (4)° | Block, colourless |
V = 1069.2 (6) Å3 |
Bruker SMART CCD diffractometer | 3838 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.021 |
ω scans | θmax = 26.4°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −11→11 |
Tmin = 0.768, Tmax = 1.000 | k = −13→13 |
13453 measured reflections | l = −10→13 |
4290 independent reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.135 | w = 1/[σ2(Fo2) + (0.074P)2 + 0.8428P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
4290 reflections | Δρmax = 1.16 e Å−3 |
266 parameters | Δρmin = −0.36 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.33969 (6) | 0.51235 (5) | 0.66880 (4) | 0.02624 (15) | |
S2 | 0.42915 (6) | 0.38952 (5) | 0.92483 (5) | 0.03187 (16) | |
O2 | 0.3503 (2) | 0.70274 (19) | 0.83735 (18) | 0.0523 (5) | |
H2O | 0.436483 | 0.656981 | 0.863736 | 0.079* | |
C101 | 0.6401 (2) | 0.35435 (19) | 0.69959 (17) | 0.0224 (4) | |
C102 | 0.5416 (2) | 0.47915 (19) | 0.66592 (17) | 0.0233 (4) | |
C103 | 0.5973 (2) | 0.5826 (2) | 0.62546 (19) | 0.0276 (4) | |
H103 | 0.527808 | 0.667316 | 0.601632 | 0.033* | |
C104 | 0.7515 (3) | 0.5601 (2) | 0.6209 (2) | 0.0294 (4) | |
H104 | 0.788381 | 0.629548 | 0.592874 | 0.035* | |
C105 | 1.0173 (2) | 0.4115 (2) | 0.6538 (2) | 0.0301 (5) | |
H105 | 1.054619 | 0.480523 | 0.624993 | 0.036* | |
C106 | 1.1189 (2) | 0.2914 (2) | 0.6913 (2) | 0.0311 (5) | |
H106 | 1.225710 | 0.277176 | 0.687807 | 0.037* | |
C107 | 1.0640 (2) | 0.1884 (2) | 0.7353 (2) | 0.0306 (5) | |
H107 | 1.134365 | 0.105357 | 0.762955 | 0.037* | |
C108 | 0.9104 (2) | 0.2071 (2) | 0.73834 (19) | 0.0268 (4) | |
H108 | 0.875883 | 0.136539 | 0.767596 | 0.032* | |
C109 | 0.8016 (2) | 0.33038 (19) | 0.69854 (17) | 0.0232 (4) | |
C110 | 0.8571 (2) | 0.4352 (2) | 0.65708 (18) | 0.0256 (4) | |
C201 | 0.5782 (2) | 0.24680 (19) | 0.74177 (18) | 0.0234 (4) | |
C202 | 0.4836 (2) | 0.2524 (2) | 0.84438 (18) | 0.0256 (4) | |
C203 | 0.4292 (2) | 0.1488 (2) | 0.8892 (2) | 0.0317 (5) | |
H203 | 0.364920 | 0.154364 | 0.960880 | 0.038* | |
C204 | 0.4684 (3) | 0.0413 (2) | 0.8304 (2) | 0.0329 (5) | |
H204 | 0.433658 | −0.028498 | 0.862557 | 0.039* | |
C205 | 0.5972 (3) | −0.0763 (2) | 0.6582 (2) | 0.0389 (6) | |
H205 | 0.562432 | −0.146393 | 0.689069 | 0.047* | |
C206 | 0.6824 (3) | −0.0812 (2) | 0.5528 (2) | 0.0444 (6) | |
H206 | 0.706735 | −0.154604 | 0.510160 | 0.053* | |
C207 | 0.7352 (3) | 0.0215 (2) | 0.5060 (2) | 0.0396 (5) | |
H207 | 0.794904 | 0.016518 | 0.432010 | 0.048* | |
C208 | 0.7019 (3) | 0.1285 (2) | 0.5654 (2) | 0.0301 (4) | |
H208 | 0.737903 | 0.197228 | 0.532074 | 0.036* | |
C209 | 0.6144 (2) | 0.13735 (19) | 0.67589 (18) | 0.0249 (4) | |
C210 | 0.5597 (2) | 0.0330 (2) | 0.7226 (2) | 0.0293 (5) | |
C1 | 0.2830 (3) | 0.5109 (2) | 0.8279 (2) | 0.0352 (5) | |
H1 | 0.189445 | 0.485240 | 0.839490 | 0.042* | |
C2 | 0.2412 (3) | 0.6405 (2) | 0.8794 (2) | 0.0418 (6) | |
H2 | 0.248695 | 0.619635 | 0.968939 | 0.050* | |
C3 | 0.0772 (3) | 0.7391 (2) | 0.8560 (2) | 0.0416 (6) | |
C4 | 0.0518 (3) | 0.7846 (3) | 0.7226 (3) | 0.0542 (7) | |
H4A | 0.141715 | 0.803457 | 0.683974 | 0.081* | |
H4B | −0.039111 | 0.863395 | 0.713553 | 0.081* | |
H4C | 0.036433 | 0.716157 | 0.684337 | 0.081* | |
C5 | 0.0606 (5) | 0.8572 (3) | 0.9196 (3) | 0.0774 (12) | |
H5A | 0.076028 | 0.829663 | 1.006016 | 0.116* | |
H5B | −0.042288 | 0.921700 | 0.908727 | 0.116* | |
H5C | 0.137525 | 0.895767 | 0.884872 | 0.116* | |
C6 | −0.0428 (5) | 0.6797 (4) | 0.9093 (5) | 0.0960 (16) | |
H6A | −0.020465 | 0.642462 | 0.993122 | 0.144* | |
H6B | −0.040525 | 0.611050 | 0.862058 | 0.144* | |
H6C | −0.144613 | 0.747157 | 0.906937 | 0.144* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0222 (3) | 0.0305 (3) | 0.0242 (3) | −0.0072 (2) | −0.00247 (18) | −0.00161 (19) |
S2 | 0.0381 (3) | 0.0304 (3) | 0.0227 (3) | −0.0063 (2) | −0.0030 (2) | −0.0022 (2) |
O2 | 0.0655 (13) | 0.0478 (11) | 0.0519 (11) | −0.0269 (10) | −0.0113 (10) | −0.0072 (9) |
C101 | 0.0255 (10) | 0.0240 (9) | 0.0205 (9) | −0.0117 (8) | −0.0009 (7) | −0.0034 (7) |
C102 | 0.0243 (9) | 0.0248 (10) | 0.0219 (9) | −0.0093 (8) | −0.0032 (7) | −0.0025 (7) |
C103 | 0.0310 (11) | 0.0215 (9) | 0.0286 (10) | −0.0077 (8) | −0.0038 (8) | −0.0002 (8) |
C104 | 0.0338 (11) | 0.0245 (10) | 0.0332 (11) | −0.0153 (9) | −0.0016 (9) | 0.0003 (8) |
C105 | 0.0305 (11) | 0.0337 (11) | 0.0322 (11) | −0.0190 (9) | −0.0010 (8) | −0.0030 (9) |
C106 | 0.0229 (10) | 0.0404 (12) | 0.0330 (11) | −0.0142 (9) | −0.0021 (8) | −0.0054 (9) |
C107 | 0.0269 (10) | 0.0299 (11) | 0.0325 (11) | −0.0068 (9) | −0.0043 (8) | −0.0019 (9) |
C108 | 0.0272 (10) | 0.0248 (10) | 0.0286 (10) | −0.0099 (8) | −0.0029 (8) | −0.0009 (8) |
C109 | 0.0256 (10) | 0.0236 (9) | 0.0226 (9) | −0.0109 (8) | −0.0018 (7) | −0.0026 (7) |
C110 | 0.0285 (10) | 0.0271 (10) | 0.0248 (10) | −0.0141 (8) | −0.0015 (8) | −0.0028 (8) |
C201 | 0.0217 (9) | 0.0209 (9) | 0.0277 (10) | −0.0082 (7) | −0.0055 (8) | 0.0014 (7) |
C202 | 0.0257 (10) | 0.0254 (10) | 0.0249 (10) | −0.0081 (8) | −0.0048 (8) | 0.0004 (8) |
C203 | 0.0276 (11) | 0.0344 (11) | 0.0310 (11) | −0.0126 (9) | −0.0024 (8) | 0.0079 (9) |
C204 | 0.0313 (11) | 0.0293 (11) | 0.0401 (12) | −0.0166 (9) | −0.0091 (9) | 0.0100 (9) |
C205 | 0.0515 (14) | 0.0229 (11) | 0.0468 (14) | −0.0168 (10) | −0.0180 (11) | 0.0024 (9) |
C206 | 0.0649 (17) | 0.0241 (11) | 0.0440 (14) | −0.0108 (11) | −0.0134 (12) | −0.0080 (10) |
C207 | 0.0503 (14) | 0.0320 (12) | 0.0343 (12) | −0.0094 (11) | −0.0039 (10) | −0.0071 (9) |
C208 | 0.0337 (11) | 0.0262 (10) | 0.0305 (11) | −0.0103 (9) | −0.0041 (9) | −0.0021 (8) |
C209 | 0.0247 (10) | 0.0225 (9) | 0.0286 (10) | −0.0094 (8) | −0.0070 (8) | 0.0005 (8) |
C210 | 0.0317 (11) | 0.0233 (10) | 0.0343 (11) | −0.0111 (8) | −0.0125 (9) | 0.0042 (8) |
C1 | 0.0378 (12) | 0.0341 (12) | 0.0260 (11) | −0.0048 (10) | 0.0001 (9) | 0.0007 (9) |
C2 | 0.0597 (16) | 0.0358 (13) | 0.0271 (11) | −0.0129 (11) | −0.0022 (10) | −0.0038 (9) |
C3 | 0.0484 (14) | 0.0281 (11) | 0.0383 (13) | −0.0040 (10) | 0.0106 (11) | −0.0036 (9) |
C4 | 0.0498 (16) | 0.0470 (15) | 0.0469 (15) | 0.0086 (13) | −0.0090 (12) | −0.0055 (12) |
C5 | 0.127 (3) | 0.0404 (16) | 0.0465 (17) | −0.0064 (18) | 0.0000 (19) | −0.0079 (13) |
C6 | 0.065 (2) | 0.065 (2) | 0.136 (4) | −0.0105 (19) | 0.047 (2) | −0.006 (2) |
S1—C102 | 1.784 (2) | C204—C210 | 1.404 (3) |
S1—C1 | 1.809 (2) | C204—H204 | 0.9500 |
S2—C202 | 1.772 (2) | C205—C206 | 1.355 (4) |
S2—C1 | 1.848 (2) | C205—C210 | 1.419 (3) |
O2—C2 | 1.426 (3) | C205—H205 | 0.9500 |
O2—H2O | 0.8400 | C206—C207 | 1.406 (4) |
C101—C102 | 1.384 (3) | C206—H206 | 0.9500 |
C101—C109 | 1.433 (3) | C207—C208 | 1.368 (3) |
C101—C201 | 1.496 (3) | C207—H207 | 0.9500 |
C102—C103 | 1.417 (3) | C208—C209 | 1.411 (3) |
C103—C104 | 1.367 (3) | C208—H208 | 0.9500 |
C103—H103 | 0.9500 | C209—C210 | 1.433 (3) |
C104—C110 | 1.414 (3) | C1—C2 | 1.532 (3) |
C104—H104 | 0.9500 | C1—H1 | 1.0000 |
C105—C106 | 1.366 (3) | C2—C3 | 1.555 (4) |
C105—C110 | 1.421 (3) | C2—H2 | 1.0000 |
C105—H105 | 0.9500 | C3—C4 | 1.520 (4) |
C106—C107 | 1.414 (3) | C3—C6 | 1.521 (5) |
C106—H106 | 0.9500 | C3—C5 | 1.533 (4) |
C107—C108 | 1.371 (3) | C4—H4A | 0.9800 |
C107—H107 | 0.9500 | C4—H4B | 0.9800 |
C108—C109 | 1.423 (3) | C4—H4C | 0.9800 |
C108—H108 | 0.9500 | C5—H5A | 0.9800 |
C109—C110 | 1.430 (3) | C5—H5B | 0.9800 |
C201—C202 | 1.375 (3) | C5—H5C | 0.9800 |
C201—C209 | 1.432 (3) | C6—H6A | 0.9800 |
C202—C203 | 1.420 (3) | C6—H6B | 0.9800 |
C203—C204 | 1.364 (3) | C6—H6C | 0.9800 |
C203—H203 | 0.9500 | ||
C102—S1—C1 | 103.57 (10) | C207—C206—H206 | 119.7 |
C202—S2—C1 | 101.51 (10) | C208—C207—C206 | 121.0 (2) |
C2—O2—H2O | 109.5 | C208—C207—H207 | 119.5 |
C102—C101—C109 | 119.27 (18) | C206—C207—H207 | 119.5 |
C102—C101—C201 | 120.37 (18) | C207—C208—C209 | 120.4 (2) |
C109—C101—C201 | 120.31 (17) | C207—C208—H208 | 119.8 |
C101—C102—C103 | 121.48 (19) | C209—C208—H208 | 119.8 |
C101—C102—S1 | 120.23 (15) | C208—C209—C201 | 122.31 (18) |
C103—C102—S1 | 118.26 (15) | C208—C209—C210 | 118.36 (19) |
C104—C103—C102 | 119.70 (19) | C201—C209—C210 | 119.33 (19) |
C104—C103—H103 | 120.1 | C204—C210—C205 | 121.1 (2) |
C102—C103—H103 | 120.1 | C204—C210—C209 | 119.5 (2) |
C103—C104—C110 | 121.20 (19) | C205—C210—C209 | 119.4 (2) |
C103—C104—H104 | 119.4 | C2—C1—S1 | 116.18 (16) |
C110—C104—H104 | 119.4 | C2—C1—S2 | 106.60 (16) |
C106—C105—C110 | 121.38 (19) | S1—C1—S2 | 113.04 (12) |
C106—C105—H105 | 119.3 | C2—C1—H1 | 106.8 |
C110—C105—H105 | 119.3 | S1—C1—H1 | 106.8 |
C105—C106—C107 | 119.6 (2) | S2—C1—H1 | 106.8 |
C105—C106—H106 | 120.2 | O2—C2—C1 | 110.7 (2) |
C107—C106—H106 | 120.2 | O2—C2—C3 | 108.9 (2) |
C108—C107—C106 | 120.7 (2) | C1—C2—C3 | 116.1 (2) |
C108—C107—H107 | 119.7 | O2—C2—H2 | 106.9 |
C106—C107—H107 | 119.7 | C1—C2—H2 | 106.9 |
C107—C108—C109 | 121.21 (19) | C3—C2—H2 | 106.9 |
C107—C108—H108 | 119.4 | C4—C3—C6 | 109.3 (3) |
C109—C108—H108 | 119.4 | C4—C3—C5 | 108.4 (2) |
C108—C109—C110 | 117.97 (18) | C6—C3—C5 | 109.5 (3) |
C108—C109—C101 | 123.16 (18) | C4—C3—C2 | 112.7 (2) |
C110—C109—C101 | 118.87 (18) | C6—C3—C2 | 110.3 (2) |
C104—C110—C105 | 121.46 (18) | C5—C3—C2 | 106.5 (3) |
C104—C110—C109 | 119.42 (19) | C3—C4—H4A | 109.5 |
C105—C110—C109 | 119.13 (19) | C3—C4—H4B | 109.5 |
C202—C201—C209 | 118.82 (18) | H4A—C4—H4B | 109.5 |
C202—C201—C101 | 120.21 (18) | C3—C4—H4C | 109.5 |
C209—C201—C101 | 120.97 (18) | H4A—C4—H4C | 109.5 |
C201—C202—C203 | 121.20 (19) | H4B—C4—H4C | 109.5 |
C201—C202—S2 | 120.23 (16) | C3—C5—H5A | 109.5 |
C203—C202—S2 | 118.56 (16) | C3—C5—H5B | 109.5 |
C204—C203—C202 | 120.6 (2) | H5A—C5—H5B | 109.5 |
C204—C203—H203 | 119.7 | C3—C5—H5C | 109.5 |
C202—C203—H203 | 119.7 | H5A—C5—H5C | 109.5 |
C203—C204—C210 | 120.46 (19) | H5B—C5—H5C | 109.5 |
C203—C204—H204 | 119.8 | C3—C6—H6A | 109.5 |
C210—C204—H204 | 119.8 | C3—C6—H6B | 109.5 |
C206—C205—C210 | 120.3 (2) | H6A—C6—H6B | 109.5 |
C206—C205—H205 | 119.9 | C3—C6—H6C | 109.5 |
C210—C205—H205 | 119.9 | H6A—C6—H6C | 109.5 |
C205—C206—C207 | 120.6 (2) | H6B—C6—H6C | 109.5 |
C205—C206—H206 | 119.7 | ||
C109—C101—C102—C103 | 2.8 (3) | C1—S2—C202—C203 | −104.56 (18) |
C201—C101—C102—C103 | −179.89 (18) | C201—C202—C203—C204 | −0.7 (3) |
C109—C101—C102—S1 | −178.94 (14) | S2—C202—C203—C204 | −179.89 (16) |
C201—C101—C102—S1 | −1.6 (3) | C202—C203—C204—C210 | −1.8 (3) |
C1—S1—C102—C101 | 75.24 (18) | C210—C205—C206—C207 | 0.2 (4) |
C1—S1—C102—C103 | −106.41 (17) | C205—C206—C207—C208 | 0.0 (4) |
C101—C102—C103—C104 | −0.9 (3) | C206—C207—C208—C209 | 0.5 (4) |
S1—C102—C103—C104 | −179.27 (16) | C207—C208—C209—C201 | 179.4 (2) |
C102—C103—C104—C110 | −0.7 (3) | C207—C208—C209—C210 | −1.1 (3) |
C110—C105—C106—C107 | −0.5 (3) | C202—C201—C209—C208 | 175.57 (19) |
C105—C106—C107—C108 | 1.4 (3) | C101—C201—C209—C208 | −3.7 (3) |
C106—C107—C108—C109 | −0.5 (3) | C202—C201—C209—C210 | −4.0 (3) |
C107—C108—C109—C110 | −1.1 (3) | C101—C201—C209—C210 | 176.66 (17) |
C107—C108—C109—C101 | 179.71 (19) | C203—C204—C210—C205 | −177.9 (2) |
C102—C101—C109—C108 | 176.21 (18) | C203—C204—C210—C209 | 1.3 (3) |
C201—C101—C109—C108 | −1.1 (3) | C206—C205—C210—C204 | 178.4 (2) |
C102—C101—C109—C110 | −3.0 (3) | C206—C205—C210—C209 | −0.8 (3) |
C201—C101—C109—C110 | 179.67 (17) | C208—C209—C210—C204 | −178.01 (19) |
C103—C104—C110—C105 | −179.3 (2) | C201—C209—C210—C204 | 1.6 (3) |
C103—C104—C110—C109 | 0.4 (3) | C208—C209—C210—C205 | 1.2 (3) |
C106—C105—C110—C104 | 178.6 (2) | C201—C209—C210—C205 | −179.20 (18) |
C106—C105—C110—C109 | −1.1 (3) | C102—S1—C1—C2 | 88.26 (19) |
C108—C109—C110—C104 | −177.79 (19) | C102—S1—C1—S2 | −35.46 (16) |
C101—C109—C110—C104 | 1.4 (3) | C202—S2—C1—C2 | −172.79 (16) |
C108—C109—C110—C105 | 1.9 (3) | C202—S2—C1—S1 | −43.95 (16) |
C101—C109—C110—C105 | −178.90 (18) | S1—C1—C2—O2 | −44.5 (3) |
C102—C101—C201—C202 | −62.5 (3) | S2—C1—C2—O2 | 82.5 (2) |
C109—C101—C201—C202 | 114.9 (2) | S1—C1—C2—C3 | 80.3 (2) |
C102—C101—C201—C209 | 116.8 (2) | S2—C1—C2—C3 | −152.75 (18) |
C109—C101—C201—C209 | −65.8 (2) | O2—C2—C3—C4 | 62.2 (3) |
C209—C201—C202—C203 | 3.6 (3) | C1—C2—C3—C4 | −63.5 (3) |
C101—C201—C202—C203 | −177.04 (18) | O2—C2—C3—C6 | −175.2 (3) |
C209—C201—C202—S2 | −177.24 (14) | C1—C2—C3—C6 | 59.0 (3) |
C101—C201—C202—S2 | 2.1 (3) | O2—C2—C3—C5 | −56.4 (3) |
C1—S2—C202—C201 | 76.29 (18) | C1—C2—C3—C5 | 177.8 (2) |
Cg3 is the centroid of the C201–C204/C210/C209 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···S2i | 0.84 | 2.69 | 3.341 (2) | 136 |
C105—H105···S1ii | 0.95 | 2.90 | 3.580 (2) | 130 |
C106—H106···Cg3ii | 0.95 | 2.87 | 3.719 (3) | 150 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x+1, y, z. |
C27H26OS2 | Dx = 1.277 Mg m−3 |
Mr = 430.60 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 6104 reflections |
a = 17.565 (5) Å | θ = 2.9–26.3° |
b = 11.103 (3) Å | µ = 0.25 mm−1 |
c = 22.977 (7) Å | T = 163 K |
V = 4481 (2) Å3 | Block, colourless |
Z = 8 | 0.55 × 0.45 × 0.12 mm |
F(000) = 1824 |
Bruker SMART CCD diffractometer | 3668 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.038 |
ω scans | θmax = 26.4°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −21→21 |
Tmin = 0.822, Tmax = 1.000 | k = −13→7 |
48381 measured reflections | l = −28→28 |
4501 independent reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.0489P)2 + 0.9358P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
4501 reflections | Δρmax = 0.28 e Å−3 |
276 parameters | Δρmin = −0.24 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.73428 (2) | 0.32278 (3) | 0.25341 (2) | 0.02829 (11) | |
S2 | 0.57569 (2) | 0.35112 (3) | 0.30806 (2) | 0.02663 (10) | |
O2 | 0.77271 (6) | 0.20287 (13) | 0.36637 (5) | 0.0479 (3) | |
H2 | 0.792870 | 0.197942 | 0.333304 | 0.072* | |
C101 | 0.61144 (8) | 0.32916 (12) | 0.17891 (6) | 0.0239 (3) | |
C102 | 0.67252 (8) | 0.26247 (12) | 0.19914 (6) | 0.0259 (3) | |
C103 | 0.68946 (9) | 0.14850 (13) | 0.17479 (7) | 0.0319 (3) | |
H103 | 0.732573 | 0.104691 | 0.188011 | 0.038* | |
C104 | 0.64385 (9) | 0.10128 (13) | 0.13222 (6) | 0.0341 (4) | |
H104 | 0.657238 | 0.026560 | 0.114873 | 0.041* | |
C105 | 0.52481 (10) | 0.10881 (15) | 0.07366 (6) | 0.0380 (4) | |
H105 | 0.535790 | 0.031949 | 0.057546 | 0.046* | |
C106 | 0.45920 (11) | 0.16638 (16) | 0.05810 (7) | 0.0425 (4) | |
H106 | 0.424837 | 0.129142 | 0.031728 | 0.051* | |
C107 | 0.44247 (10) | 0.28053 (16) | 0.08105 (7) | 0.0396 (4) | |
H107 | 0.396725 | 0.320332 | 0.070249 | 0.048* | |
C108 | 0.49224 (9) | 0.33496 (13) | 0.11920 (6) | 0.0312 (3) | |
H108 | 0.480660 | 0.412796 | 0.133911 | 0.037* | |
C109 | 0.56037 (8) | 0.27724 (12) | 0.13696 (6) | 0.0264 (3) | |
C110 | 0.57705 (9) | 0.16155 (13) | 0.11349 (6) | 0.0302 (3) | |
C201 | 0.59921 (8) | 0.45406 (12) | 0.20081 (6) | 0.0232 (3) | |
C202 | 0.58292 (8) | 0.47451 (12) | 0.25909 (6) | 0.0237 (3) | |
C203 | 0.57257 (8) | 0.59249 (13) | 0.28098 (6) | 0.0259 (3) | |
H203 | 0.560058 | 0.604415 | 0.320791 | 0.031* | |
C204 | 0.58057 (8) | 0.68877 (13) | 0.24491 (6) | 0.0266 (3) | |
H204 | 0.572416 | 0.767657 | 0.259657 | 0.032* | |
C205 | 0.61547 (9) | 0.77265 (13) | 0.14852 (6) | 0.0302 (3) | |
H205 | 0.608553 | 0.852015 | 0.163038 | 0.036* | |
C206 | 0.63931 (9) | 0.75659 (14) | 0.09223 (7) | 0.0350 (4) | |
H206 | 0.649514 | 0.824584 | 0.068372 | 0.042* | |
C207 | 0.64870 (9) | 0.63969 (14) | 0.06970 (6) | 0.0351 (4) | |
H207 | 0.665319 | 0.628986 | 0.030693 | 0.042* | |
C208 | 0.63402 (9) | 0.54164 (13) | 0.10370 (6) | 0.0295 (3) | |
H208 | 0.639712 | 0.463207 | 0.087764 | 0.035* | |
C209 | 0.61029 (8) | 0.55475 (12) | 0.16274 (6) | 0.0236 (3) | |
C210 | 0.60099 (8) | 0.67326 (12) | 0.18533 (6) | 0.0242 (3) | |
C1 | 0.67673 (8) | 0.32372 (13) | 0.32134 (6) | 0.0260 (3) | |
H1 | 0.695201 | 0.394259 | 0.344427 | 0.031* | |
C2 | 0.69130 (9) | 0.21063 (13) | 0.36018 (6) | 0.0311 (3) | |
C22 | 0.66153 (11) | 0.09668 (14) | 0.33065 (7) | 0.0441 (4) | |
H22A | 0.668752 | 0.027603 | 0.356614 | 0.066* | |
H22B | 0.689526 | 0.083149 | 0.294336 | 0.066* | |
H22C | 0.607217 | 0.106213 | 0.322042 | 0.066* | |
C3 | 0.66090 (9) | 0.22442 (14) | 0.42475 (6) | 0.0341 (4) | |
C4 | 0.70379 (12) | 0.1358 (2) | 0.46484 (8) | 0.0589 (6) | |
H4A | 0.694488 | 0.053034 | 0.451776 | 0.088* | |
H4B | 0.685593 | 0.145161 | 0.504909 | 0.088* | |
H4C | 0.758489 | 0.152811 | 0.463292 | 0.088* | |
C5 | 0.57532 (10) | 0.19676 (16) | 0.43056 (8) | 0.0440 (4) | |
H5A | 0.565400 | 0.114255 | 0.417450 | 0.066* | |
H5B | 0.546176 | 0.253339 | 0.406580 | 0.066* | |
H5C | 0.559937 | 0.205096 | 0.471365 | 0.066* | |
C6 | 0.67636 (12) | 0.35085 (16) | 0.44817 (7) | 0.0494 (5) | |
H6A | 0.730208 | 0.370831 | 0.442579 | 0.074* | |
H6B | 0.664061 | 0.353651 | 0.489751 | 0.074* | |
H6C | 0.644719 | 0.409185 | 0.427202 | 0.074* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.02315 (19) | 0.0351 (2) | 0.02660 (19) | −0.00032 (14) | 0.00222 (14) | 0.00127 (15) |
S2 | 0.02381 (19) | 0.0310 (2) | 0.02514 (18) | 0.00074 (14) | 0.00317 (14) | 0.00552 (14) |
O2 | 0.0308 (6) | 0.0716 (9) | 0.0413 (7) | 0.0141 (6) | 0.0026 (5) | 0.0183 (6) |
C101 | 0.0277 (7) | 0.0227 (7) | 0.0211 (7) | −0.0025 (6) | 0.0044 (5) | 0.0002 (5) |
C102 | 0.0263 (7) | 0.0260 (7) | 0.0252 (7) | −0.0010 (6) | 0.0048 (6) | 0.0003 (5) |
C103 | 0.0336 (8) | 0.0283 (8) | 0.0338 (8) | 0.0048 (6) | 0.0081 (7) | 0.0012 (6) |
C104 | 0.0469 (9) | 0.0223 (7) | 0.0333 (8) | −0.0022 (7) | 0.0136 (7) | −0.0051 (6) |
C105 | 0.0553 (11) | 0.0351 (8) | 0.0235 (7) | −0.0155 (8) | 0.0077 (7) | −0.0064 (6) |
C106 | 0.0531 (11) | 0.0492 (10) | 0.0251 (8) | −0.0211 (9) | −0.0044 (8) | −0.0023 (7) |
C107 | 0.0408 (9) | 0.0494 (10) | 0.0286 (8) | −0.0089 (8) | −0.0053 (7) | 0.0062 (7) |
C108 | 0.0356 (8) | 0.0328 (8) | 0.0252 (7) | −0.0039 (6) | −0.0007 (6) | 0.0029 (6) |
C109 | 0.0335 (8) | 0.0264 (7) | 0.0193 (7) | −0.0053 (6) | 0.0041 (6) | 0.0013 (5) |
C110 | 0.0408 (9) | 0.0266 (7) | 0.0233 (7) | −0.0086 (6) | 0.0088 (6) | −0.0018 (6) |
C201 | 0.0220 (7) | 0.0244 (7) | 0.0232 (7) | 0.0004 (5) | −0.0013 (5) | −0.0015 (5) |
C202 | 0.0215 (7) | 0.0261 (7) | 0.0234 (7) | 0.0010 (5) | 0.0008 (5) | 0.0021 (5) |
C203 | 0.0254 (7) | 0.0309 (7) | 0.0214 (7) | 0.0035 (6) | 0.0009 (6) | −0.0039 (6) |
C204 | 0.0262 (7) | 0.0251 (7) | 0.0285 (7) | 0.0035 (6) | −0.0002 (6) | −0.0055 (6) |
C205 | 0.0343 (8) | 0.0238 (7) | 0.0324 (8) | 0.0012 (6) | −0.0017 (6) | 0.0004 (6) |
C206 | 0.0454 (9) | 0.0278 (8) | 0.0317 (8) | −0.0019 (7) | 0.0017 (7) | 0.0072 (6) |
C207 | 0.0454 (9) | 0.0382 (9) | 0.0218 (7) | −0.0026 (7) | 0.0040 (7) | 0.0017 (6) |
C208 | 0.0362 (8) | 0.0279 (7) | 0.0244 (7) | −0.0011 (6) | 0.0012 (6) | −0.0031 (6) |
C209 | 0.0236 (7) | 0.0253 (7) | 0.0220 (7) | 0.0003 (5) | −0.0006 (5) | −0.0010 (5) |
C210 | 0.0218 (7) | 0.0251 (7) | 0.0256 (7) | 0.0014 (5) | −0.0018 (6) | −0.0007 (5) |
C1 | 0.0232 (7) | 0.0304 (7) | 0.0243 (7) | 0.0006 (6) | 0.0019 (6) | 0.0009 (6) |
C2 | 0.0288 (8) | 0.0339 (8) | 0.0306 (8) | 0.0052 (6) | 0.0022 (6) | 0.0064 (6) |
C22 | 0.0646 (12) | 0.0270 (8) | 0.0406 (9) | 0.0041 (8) | 0.0093 (8) | 0.0027 (7) |
C3 | 0.0383 (9) | 0.0374 (9) | 0.0266 (8) | 0.0030 (7) | 0.0017 (6) | 0.0085 (6) |
C4 | 0.0635 (13) | 0.0740 (14) | 0.0392 (10) | 0.0173 (11) | 0.0035 (9) | 0.0263 (10) |
C5 | 0.0441 (10) | 0.0500 (10) | 0.0378 (9) | −0.0037 (8) | 0.0113 (8) | 0.0070 (8) |
C6 | 0.0676 (13) | 0.0534 (11) | 0.0272 (8) | −0.0114 (9) | 0.0007 (8) | −0.0017 (7) |
S1—C102 | 1.7832 (15) | C204—H204 | 0.9500 |
S1—C1 | 1.8596 (15) | C205—C206 | 1.371 (2) |
S2—C202 | 1.7773 (14) | C205—C210 | 1.413 (2) |
S2—C1 | 1.8265 (15) | C205—H205 | 0.9500 |
O2—C2 | 1.4396 (19) | C206—C207 | 1.407 (2) |
O2—H2 | 0.8400 | C206—H206 | 0.9500 |
C101—C102 | 1.384 (2) | C207—C208 | 1.364 (2) |
C101—C109 | 1.437 (2) | C207—H207 | 0.9500 |
C101—C201 | 1.4908 (19) | C208—C209 | 1.4265 (19) |
C102—C103 | 1.415 (2) | C208—H208 | 0.9500 |
C103—C104 | 1.369 (2) | C209—C210 | 1.4239 (19) |
C103—H103 | 0.9500 | C1—C2 | 1.5616 (19) |
C104—C110 | 1.418 (2) | C1—H1 | 1.0000 |
C104—H104 | 0.9500 | C2—C22 | 1.528 (2) |
C105—C106 | 1.366 (3) | C2—C3 | 1.584 (2) |
C105—C110 | 1.422 (2) | C22—H22A | 0.9800 |
C105—H105 | 0.9500 | C22—H22B | 0.9800 |
C106—C107 | 1.404 (2) | C22—H22C | 0.9800 |
C106—H106 | 0.9500 | C3—C6 | 1.528 (2) |
C107—C108 | 1.378 (2) | C3—C5 | 1.540 (2) |
C107—H107 | 0.9500 | C3—C4 | 1.544 (2) |
C108—C109 | 1.418 (2) | C4—H4A | 0.9800 |
C108—H108 | 0.9500 | C4—H4B | 0.9800 |
C109—C110 | 1.424 (2) | C4—H4C | 0.9800 |
C201—C202 | 1.3881 (19) | C5—H5A | 0.9800 |
C201—C209 | 1.4327 (19) | C5—H5B | 0.9800 |
C202—C203 | 1.4149 (19) | C5—H5C | 0.9800 |
C203—C204 | 1.360 (2) | C6—H6A | 0.9800 |
C203—H203 | 0.9500 | C6—H6B | 0.9800 |
C204—C210 | 1.426 (2) | C6—H6C | 0.9800 |
C102—S1—C1 | 104.97 (7) | C206—C207—H207 | 119.9 |
C202—S2—C1 | 99.47 (6) | C207—C208—C209 | 121.22 (13) |
C2—O2—H2 | 109.5 | C207—C208—H208 | 119.4 |
C102—C101—C109 | 119.64 (13) | C209—C208—H208 | 119.4 |
C102—C101—C201 | 119.74 (13) | C210—C209—C208 | 118.32 (12) |
C109—C101—C201 | 120.62 (13) | C210—C209—C201 | 118.88 (12) |
C101—C102—C103 | 120.57 (14) | C208—C209—C201 | 122.72 (12) |
C101—C102—S1 | 120.37 (11) | C205—C210—C209 | 118.86 (13) |
C103—C102—S1 | 118.97 (11) | C205—C210—C204 | 121.71 (13) |
C104—C103—C102 | 120.13 (15) | C209—C210—C204 | 119.38 (12) |
C104—C103—H103 | 119.9 | C2—C1—S2 | 112.86 (10) |
C102—C103—H103 | 119.9 | C2—C1—S1 | 112.71 (10) |
C103—C104—C110 | 121.37 (14) | S2—C1—S1 | 112.89 (8) |
C103—C104—H104 | 119.3 | C2—C1—H1 | 105.9 |
C110—C104—H104 | 119.3 | S2—C1—H1 | 105.9 |
C106—C105—C110 | 121.35 (15) | S1—C1—H1 | 105.9 |
C106—C105—H105 | 119.3 | O2—C2—C22 | 109.52 (13) |
C110—C105—H105 | 119.3 | O2—C2—C1 | 105.51 (12) |
C105—C106—C107 | 120.06 (15) | C22—C2—C1 | 110.85 (13) |
C105—C106—H106 | 120.0 | O2—C2—C3 | 104.36 (12) |
C107—C106—H106 | 120.0 | C22—C2—C3 | 112.37 (13) |
C108—C107—C106 | 120.15 (16) | C1—C2—C3 | 113.72 (12) |
C108—C107—H107 | 119.9 | C2—C22—H22A | 109.5 |
C106—C107—H107 | 119.9 | C2—C22—H22B | 109.5 |
C107—C108—C109 | 121.37 (15) | H22A—C22—H22B | 109.5 |
C107—C108—H108 | 119.3 | C2—C22—H22C | 109.5 |
C109—C108—H108 | 119.3 | H22A—C22—H22C | 109.5 |
C108—C109—C110 | 118.20 (13) | H22B—C22—H22C | 109.5 |
C108—C109—C101 | 122.59 (13) | C6—C3—C5 | 109.03 (14) |
C110—C109—C101 | 119.17 (14) | C6—C3—C4 | 106.79 (15) |
C104—C110—C105 | 122.35 (14) | C5—C3—C4 | 107.29 (14) |
C104—C110—C109 | 118.76 (14) | C6—C3—C2 | 111.02 (13) |
C105—C110—C109 | 118.85 (15) | C5—C3—C2 | 113.01 (13) |
C202—C201—C209 | 119.30 (12) | C4—C3—C2 | 109.43 (13) |
C202—C201—C101 | 120.49 (12) | C3—C4—H4A | 109.5 |
C209—C201—C101 | 120.02 (12) | C3—C4—H4B | 109.5 |
C201—C202—C203 | 121.39 (12) | H4A—C4—H4B | 109.5 |
C201—C202—S2 | 119.96 (11) | C3—C4—H4C | 109.5 |
C203—C202—S2 | 118.64 (10) | H4A—C4—H4C | 109.5 |
C204—C203—C202 | 119.86 (13) | H4B—C4—H4C | 109.5 |
C204—C203—H203 | 120.1 | C3—C5—H5A | 109.5 |
C202—C203—H203 | 120.1 | C3—C5—H5B | 109.5 |
C203—C204—C210 | 121.08 (13) | H5A—C5—H5B | 109.5 |
C203—C204—H204 | 119.5 | C3—C5—H5C | 109.5 |
C210—C204—H204 | 119.5 | H5A—C5—H5C | 109.5 |
C206—C205—C210 | 121.19 (13) | H5B—C5—H5C | 109.5 |
C206—C205—H205 | 119.4 | C3—C6—H6A | 109.5 |
C210—C205—H205 | 119.4 | C3—C6—H6B | 109.5 |
C205—C206—C207 | 120.19 (14) | H6A—C6—H6B | 109.5 |
C205—C206—H206 | 119.9 | C3—C6—H6C | 109.5 |
C207—C206—H206 | 119.9 | H6A—C6—H6C | 109.5 |
C208—C207—C206 | 120.20 (14) | H6B—C6—H6C | 109.5 |
C208—C207—H207 | 119.9 | ||
C109—C101—C102—C103 | 6.2 (2) | C202—C203—C204—C210 | −1.4 (2) |
C201—C101—C102—C103 | −173.77 (12) | C210—C205—C206—C207 | 1.0 (2) |
C109—C101—C102—S1 | −177.39 (10) | C205—C206—C207—C208 | 0.1 (2) |
C201—C101—C102—S1 | 2.59 (18) | C206—C207—C208—C209 | −1.1 (2) |
C1—S1—C102—C101 | 70.88 (12) | C207—C208—C209—C210 | 1.0 (2) |
C1—S1—C102—C103 | −112.69 (12) | C207—C208—C209—C201 | −175.80 (14) |
C101—C102—C103—C104 | −2.2 (2) | C202—C201—C209—C210 | −2.7 (2) |
S1—C102—C103—C104 | −178.67 (11) | C101—C201—C209—C210 | −177.69 (13) |
C102—C103—C104—C110 | −3.1 (2) | C202—C201—C209—C208 | 174.08 (13) |
C110—C105—C106—C107 | 0.6 (2) | C101—C201—C209—C208 | −0.9 (2) |
C105—C106—C107—C108 | 0.2 (2) | C206—C205—C210—C209 | −1.1 (2) |
C106—C107—C108—C109 | −1.0 (2) | C206—C205—C210—C204 | 176.20 (14) |
C107—C108—C109—C110 | 1.1 (2) | C208—C209—C210—C205 | 0.1 (2) |
C107—C108—C109—C101 | −176.80 (13) | C201—C209—C210—C205 | 177.02 (13) |
C102—C101—C109—C108 | 172.88 (13) | C208—C209—C210—C204 | −177.26 (13) |
C201—C101—C109—C108 | −7.1 (2) | C201—C209—C210—C204 | −0.3 (2) |
C102—C101—C109—C110 | −4.99 (19) | C203—C204—C210—C205 | −174.84 (13) |
C201—C101—C109—C110 | 175.03 (12) | C203—C204—C210—C209 | 2.4 (2) |
C103—C104—C110—C105 | −173.53 (14) | C202—S2—C1—C2 | −175.38 (10) |
C103—C104—C110—C109 | 4.2 (2) | C202—S2—C1—S1 | −46.11 (9) |
C106—C105—C110—C104 | 177.19 (14) | C102—S1—C1—C2 | 96.29 (11) |
C106—C105—C110—C109 | −0.6 (2) | C102—S1—C1—S2 | −33.06 (9) |
C108—C109—C110—C104 | −178.13 (13) | S2—C1—C2—O2 | −179.74 (10) |
C101—C109—C110—C104 | −0.16 (19) | S1—C1—C2—O2 | 50.90 (14) |
C108—C109—C110—C105 | −0.3 (2) | S2—C1—C2—C22 | 61.78 (15) |
C101—C109—C110—C105 | 177.67 (13) | S1—C1—C2—C22 | −67.57 (15) |
C102—C101—C201—C202 | −63.95 (19) | S2—C1—C2—C3 | −65.97 (15) |
C109—C101—C201—C202 | 116.03 (15) | S1—C1—C2—C3 | 164.68 (10) |
C102—C101—C201—C209 | 110.97 (15) | O2—C2—C3—C6 | 74.26 (16) |
C109—C101—C201—C209 | −69.05 (17) | C22—C2—C3—C6 | −167.15 (15) |
C209—C201—C202—C203 | 3.8 (2) | C1—C2—C3—C6 | −40.19 (18) |
C101—C201—C202—C203 | 178.76 (13) | O2—C2—C3—C5 | −162.86 (13) |
C209—C201—C202—S2 | −175.52 (10) | C22—C2—C3—C5 | −44.27 (18) |
C101—C201—C202—S2 | −0.57 (18) | C1—C2—C3—C5 | 82.69 (16) |
C1—S2—C202—C201 | 79.99 (12) | O2—C2—C3—C4 | −43.37 (18) |
C1—S2—C202—C203 | −99.36 (12) | C22—C2—C3—C4 | 75.21 (18) |
C201—C202—C203—C204 | −1.8 (2) | C1—C2—C3—C4 | −157.83 (14) |
S2—C202—C203—C204 | 177.58 (11) |
Cg2 and Cg4 are the centroids of the C105–C110 and C205–C210 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···S1 | 0.84 | 2.52 | 2.9942 (14) | 117 |
C203—H203···Cg2i | 0.95 | 2.60 | 3.4606 (19) | 151 |
C103—H103···Cg4ii | 0.95 | 2.93 | 3.443 (2) | 115 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+3/2, y−1/2, z. |
Acknowledgements
This paper is dedicated to Emeritus Professors Jim Simpson and Rob A. J. Smith, University of Otago, who (wishing to enjoy their retirement) have abdicated co-authorial responsibilities. We also thank Emeritus Professor Ward T. Robinson, University of Canterbury, for the X-ray data collection. These true gentlemen between them mentored dozens of young scientists, and without them this work would never have occurred.
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