Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103006504/gg1163sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103006504/gg1163VIsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103006504/gg1163VIIsup3.hkl |
CCDC references: 214167; 214168
Compounds (VI) and (VII) were obtained by the [2 + 3]-dipolar cycloaddition of the azomethine ylide (III), generated in situ by thermal ring opening of dimethyl-1,3-diphenylaziridine-2,2-dicarboxylate, (II), with adamantanethione, (IV), and thiofluorenone, (V), respectively (Mlostoń & Skrzypek, 1990, Mlostoń et al., 2002). Suitable crystals were obtained by slow evaporation of methanolic solutions of the compounds at room temperature [m.p.: 423 and 476 K for (VI) and (VII), respectively].
The asymmetric unit of (VI) contains two molecules of the adamantanyl derivative plus one site for a methanol molecule which is partially occupied. A common site-occupation factor for the atoms of the methanol molecule initially refined to a value close to 0.55. In the final refinement, this site-occupation factor was held fixed at 0.55. The position of the hydroxy H atom of the methanol molecule in (VI) was located in a difference Fourier map and its position was refined freely along with an isotropic displacement parameter. In both structures, the methyl H atoms were constrained to an ideal geometry [C—H = 0.98 Å for (VI) and 0.96 Å for (VII)], with Uiso(H) = 1.5Ueq(C), but were allowed to rotate freely about the parent C—C bonds. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances in the range 0.93–1.00 Å and Uiso(H) = 1.2Ueq(C). Three low-angle reflections were omitted from the final cycles of refinement of (VI) because their observed intensities were much lower than the calculated values as a result of being partially obscured by the beam stop.
Data collection: COLLECT (Nonius, 2000) for (VI); MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1989) for (VII). Cell refinement: DENZO–SMN (Otwinowski & Minor, 1997) for (VI); MSC/AFC Diffractometer Control Software for (VII). Data reduction: DENZO–MN and SCALEPACK (Otwinowski & Minor, 1997) for (VI); TEXSAN (Molecular Structure Corporation, 1989) for (VII). Program(s) used to solve structure: SIR92 (Altomare et al., 1994) for (VI); SHELXS86 (Sheldrick, 1990) for (VII). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2003) for (VI); PLATON (Spek, 2003) for (VII). For both compounds, software used to prepare material for publication: SHELXL97 and PLATON.
C28H31NO4S·0.275CH4O | F(000) = 2071.6 |
Mr = 486.43 | Dx = 1.317 Mg m−3 |
Monoclinic, P21/n | Melting point: 423 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 15.6658 (2) Å | Cell parameters from 11543 reflections |
b = 18.1538 (3) Å | θ = 2.0–27.5° |
c = 17.2513 (3) Å | µ = 0.17 mm−1 |
β = 90.2397 (6)° | T = 160 K |
V = 4906.12 (13) Å3 | Prism, colourless |
Z = 8 | 0.35 × 0.18 × 0.15 mm |
Nonius KappaCCD area-detector diffractometer | 7745 reflections with I > 2σ(I) |
Radiation source: Nonius FR590 sealed tube generator | Rint = 0.071 |
Horizontally mounted graphite crystal monochromator | θmax = 27.5°, θmin = 2.1° |
Detector resolution: 9 pixels mm-1 | h = 0→20 |
ϕ and ω scans with κ offsets | k = 0→23 |
76328 measured reflections | l = −22→22 |
11220 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: geom & difmap |
R[F2 > 2σ(F2)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.110 | w = 1/[σ2(Fo2) + (0.0462P)2 + 0.6825P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
11217 reflections | Δρmax = 0.39 e Å−3 |
641 parameters | Δρmin = −0.29 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0024 (3) |
C28H31NO4S·0.275CH4O | V = 4906.12 (13) Å3 |
Mr = 486.43 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 15.6658 (2) Å | µ = 0.17 mm−1 |
b = 18.1538 (3) Å | T = 160 K |
c = 17.2513 (3) Å | 0.35 × 0.18 × 0.15 mm |
β = 90.2397 (6)° |
Nonius KappaCCD area-detector diffractometer | 7745 reflections with I > 2σ(I) |
76328 measured reflections | Rint = 0.071 |
11220 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.110 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.39 e Å−3 |
11217 reflections | Δρmin = −0.29 e Å−3 |
641 parameters |
Experimental. Solvent used: methanol Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.627 (1) Frames collected: 290 Seconds exposure per frame: 45 Degrees rotation per frame: 1.5 Crystal-Detector distance (mm): 30.0 |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 6.2944 (0.0096) x + 11.5610 (0.0093) y + 11.3228 (0.0089) z = 15.3657 (0.0080) * −0.0058 (0.0011) C21A * 0.0016 (0.0012) C22A * 0.0033 (0.0012) C23A * −0.0039 (0.0012) C24A * −0.0003 (0.0011) C25A * 0.0051 (0.0011) C26A Rms deviation of fitted atoms = 0.0038 12.2927 (0.0062) x − 7.9895 (0.0089) y − 7.5879 (0.0120) z = 2.5437 (0.0119) Angle to previous plane (with approximate e.s.d.) = 75.39 (0.05) * −0.1893 (0.0008) S1A * 0.1024 (0.0009) C2A * 0.0575 (0.0010) N3A * −0.2146 (0.0010) C4A * 0.2441 (0.0009) C5A Rms deviation of fitted atoms = 0.1762 13.2083 (0.0057) x − 1.5883 (0.0122) y − 9.2134 (0.0099) z = 3.7010 (0.0134) Angle to previous plane (with approximate e.s.d.) = 21.30 (0.08) * 0.0106 (0.0011) C31A * −0.0060 (0.0012) C32A * −0.0038 (0.0012) C33A * 0.0090 (0.0012) C34A * −0.0043 (0.0012) C35A * −0.0055 (0.0011) C36A Rms deviation of fitted atoms = 0.0070 4.8377 (0.0100) x − 11.8069 (0.0092) y + 11.9501 (0.0085) z = 4.5978 (0.0046) * 0.0004 (0.0011) C21B * −0.0060 (0.0011) C22B * 0.0074 (0.0012) C23B * −0.0032 (0.0012) C24B * −0.0024 (0.0012) C25B * 0.0038 (0.0012) C26B Rms deviation of fitted atoms = 0.0045 12.4157 (0.0061) x + 9.6499 (0.0086) y − 5.2131 (0.0130) z = 2.6253 (0.0086) Angle to previous plane (with approximate e.s.d.) = 72.04 (0.05) * 0.2277 (0.0008) S1B * −0.1350 (0.0009) C2B * −0.0440 (0.0010) N3B * 0.2330 (0.0010) C4B * −0.2816 (0.0009) C5B Rms deviation of fitted atoms = 0.2028 -13.5929 (0.0057) x − 3.5995 (0.0135) y + 7.9269 (0.0115) z = 0.1786 (0.0084) Angle to previous plane (with approximate e.s.d.) = 21.67 (0.08) * 0.0106 (0.0012) C31B * −0.0052 (0.0013) C32B * −0.0045 (0.0014) C33B * 0.0086 (0.0014) C34B * −0.0030 (0.0013) C35B * −0.0066 (0.0012) C36B Rms deviation of fitted atoms = 0.0069 |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1A | 0.69996 (3) | 0.13116 (2) | 0.68558 (2) | 0.02919 (12) | |
C2A | 0.78558 (10) | 0.17525 (9) | 0.73942 (9) | 0.0266 (4) | |
H21 | 0.7638 | 0.1870 | 0.7924 | 0.032* | |
N3A | 0.80272 (8) | 0.24492 (7) | 0.69975 (7) | 0.0240 (3) | |
C4A | 0.74984 (10) | 0.26187 (8) | 0.63209 (9) | 0.0245 (4) | |
C5A | 0.71550 (10) | 0.18538 (8) | 0.59655 (9) | 0.0237 (4) | |
C21A | 0.86309 (11) | 0.12554 (9) | 0.74857 (9) | 0.0263 (4) | |
C22A | 0.86137 (12) | 0.07120 (9) | 0.80566 (10) | 0.0351 (4) | |
H221 | 0.8128 | 0.0663 | 0.8380 | 0.042* | |
C23A | 0.93056 (13) | 0.02419 (10) | 0.81534 (11) | 0.0417 (5) | |
H231 | 0.9291 | −0.0127 | 0.8544 | 0.050* | |
C24A | 1.00141 (12) | 0.03083 (10) | 0.76854 (11) | 0.0392 (5) | |
H241 | 1.0484 | −0.0017 | 0.7749 | 0.047* | |
C25A | 1.00358 (11) | 0.08498 (9) | 0.71237 (11) | 0.0348 (4) | |
H251 | 1.0524 | 0.0897 | 0.6803 | 0.042* | |
C26A | 0.93483 (11) | 0.13261 (9) | 0.70243 (10) | 0.0285 (4) | |
H261 | 0.9371 | 0.1700 | 0.6640 | 0.034* | |
C31A | 0.83676 (10) | 0.30274 (9) | 0.74453 (9) | 0.0249 (4) | |
C32A | 0.82939 (11) | 0.37698 (9) | 0.72297 (10) | 0.0291 (4) | |
H321 | 0.7982 | 0.3896 | 0.6775 | 0.035* | |
C33A | 0.86702 (11) | 0.43236 (9) | 0.76713 (10) | 0.0339 (4) | |
H331 | 0.8614 | 0.4822 | 0.7512 | 0.041* | |
C34A | 0.91243 (11) | 0.41604 (10) | 0.83366 (10) | 0.0356 (4) | |
H341 | 0.9389 | 0.4539 | 0.8632 | 0.043* | |
C35A | 0.91841 (11) | 0.34292 (10) | 0.85627 (10) | 0.0312 (4) | |
H351 | 0.9485 | 0.3309 | 0.9025 | 0.037* | |
C36A | 0.88153 (10) | 0.28704 (9) | 0.81317 (9) | 0.0276 (4) | |
H361 | 0.8866 | 0.2375 | 0.8302 | 0.033* | |
C41A | 0.67047 (10) | 0.30796 (9) | 0.65598 (9) | 0.0263 (4) | |
O42A | 0.64711 (7) | 0.29070 (6) | 0.72797 (6) | 0.0310 (3) | |
C43A | 0.56790 (11) | 0.32449 (10) | 0.75323 (10) | 0.0355 (4) | |
H431 | 0.5742 | 0.3782 | 0.7532 | 0.053* | |
H432 | 0.5544 | 0.3077 | 0.8058 | 0.053* | |
H433 | 0.5216 | 0.3104 | 0.7178 | 0.053* | |
O44A | 0.63285 (7) | 0.35120 (6) | 0.61570 (7) | 0.0340 (3) | |
C45A | 0.80460 (10) | 0.30608 (9) | 0.57352 (9) | 0.0267 (4) | |
O46A | 0.88695 (7) | 0.28542 (6) | 0.57673 (6) | 0.0284 (3) | |
C47A | 0.94297 (11) | 0.32506 (10) | 0.52448 (10) | 0.0372 (4) | |
H471 | 0.9250 | 0.3162 | 0.4708 | 0.056* | |
H472 | 1.0017 | 0.3078 | 0.5316 | 0.056* | |
H473 | 0.9400 | 0.3779 | 0.5357 | 0.056* | |
O48A | 0.77841 (7) | 0.35288 (6) | 0.53010 (7) | 0.0333 (3) | |
C51A | 0.77718 (10) | 0.14516 (8) | 0.53963 (9) | 0.0251 (4) | |
H511 | 0.8355 | 0.1423 | 0.5632 | 0.030* | |
C52A | 0.74316 (11) | 0.06671 (9) | 0.52439 (10) | 0.0296 (4) | |
H521 | 0.7830 | 0.0401 | 0.4899 | 0.035* | |
H522 | 0.7399 | 0.0394 | 0.5740 | 0.035* | |
C53A | 0.65440 (11) | 0.06964 (9) | 0.48662 (9) | 0.0303 (4) | |
H531 | 0.6326 | 0.0185 | 0.4783 | 0.036* | |
C54A | 0.59407 (11) | 0.11157 (9) | 0.53994 (10) | 0.0296 (4) | |
H541 | 0.5888 | 0.0848 | 0.5897 | 0.036* | |
H542 | 0.5367 | 0.1141 | 0.5157 | 0.036* | |
C55A | 0.62709 (10) | 0.19032 (9) | 0.55549 (9) | 0.0268 (4) | |
H551 | 0.5859 | 0.2171 | 0.5895 | 0.032* | |
C56A | 0.63413 (11) | 0.23026 (9) | 0.47721 (9) | 0.0300 (4) | |
H561 | 0.5768 | 0.2344 | 0.4532 | 0.036* | |
H562 | 0.6565 | 0.2806 | 0.4855 | 0.036* | |
C57A | 0.69358 (11) | 0.18799 (9) | 0.42305 (10) | 0.0316 (4) | |
H571 | 0.6976 | 0.2147 | 0.3725 | 0.038* | |
C58A | 0.65953 (12) | 0.11013 (9) | 0.40878 (10) | 0.0321 (4) | |
H581 | 0.6980 | 0.0833 | 0.3732 | 0.039* | |
H582 | 0.6022 | 0.1126 | 0.3845 | 0.039* | |
C59A | 0.78232 (11) | 0.18275 (9) | 0.45982 (9) | 0.0285 (4) | |
H591 | 0.8066 | 0.2328 | 0.4658 | 0.034* | |
H592 | 0.8205 | 0.1541 | 0.4255 | 0.034* | |
S1B | 0.33165 (3) | 0.15900 (2) | 0.53693 (2) | 0.03103 (12) | |
C2B | 0.24528 (10) | 0.20583 (9) | 0.48748 (9) | 0.0257 (4) | |
H22 | 0.2678 | 0.2249 | 0.4372 | 0.031* | |
N3B | 0.22370 (8) | 0.26920 (7) | 0.53594 (7) | 0.0249 (3) | |
C4B | 0.27088 (10) | 0.27658 (9) | 0.60882 (9) | 0.0255 (4) | |
C5B | 0.30277 (10) | 0.19523 (9) | 0.63291 (9) | 0.0270 (4) | |
C21B | 0.17043 (10) | 0.15546 (8) | 0.46939 (9) | 0.0252 (4) | |
C22B | 0.18054 (11) | 0.10222 (9) | 0.41216 (9) | 0.0300 (4) | |
H222 | 0.2334 | 0.0983 | 0.3857 | 0.036* | |
C23B | 0.11454 (12) | 0.05504 (9) | 0.39339 (10) | 0.0342 (4) | |
H232 | 0.1226 | 0.0182 | 0.3551 | 0.041* | |
C24B | 0.03674 (12) | 0.06138 (10) | 0.43026 (10) | 0.0362 (4) | |
H242 | −0.0091 | 0.0296 | 0.4167 | 0.043* | |
C25B | 0.02614 (12) | 0.11441 (10) | 0.48702 (10) | 0.0372 (4) | |
H252 | −0.0272 | 0.1188 | 0.5127 | 0.045* | |
C26B | 0.09265 (11) | 0.16110 (9) | 0.50673 (10) | 0.0310 (4) | |
H262 | 0.0849 | 0.1971 | 0.5460 | 0.037* | |
C31B | 0.18910 (10) | 0.33143 (9) | 0.49863 (9) | 0.0269 (4) | |
C32B | 0.19050 (11) | 0.40190 (9) | 0.53104 (10) | 0.0333 (4) | |
H322 | 0.2178 | 0.4093 | 0.5797 | 0.040* | |
C33B | 0.15306 (13) | 0.46092 (10) | 0.49373 (11) | 0.0434 (5) | |
H332 | 0.1549 | 0.5082 | 0.5172 | 0.052* | |
C34B | 0.11290 (13) | 0.45252 (10) | 0.42270 (11) | 0.0440 (5) | |
H342 | 0.0863 | 0.4932 | 0.3977 | 0.053* | |
C35B | 0.11243 (12) | 0.38356 (10) | 0.38911 (10) | 0.0360 (4) | |
H352 | 0.0859 | 0.3770 | 0.3400 | 0.043* | |
C36B | 0.14978 (11) | 0.32363 (9) | 0.42549 (9) | 0.0297 (4) | |
H362 | 0.1489 | 0.2768 | 0.4009 | 0.036* | |
C41B | 0.35077 (11) | 0.32677 (9) | 0.59924 (10) | 0.0316 (4) | |
O42B | 0.37348 (8) | 0.32989 (7) | 0.52474 (7) | 0.0403 (3) | |
C43B | 0.44923 (12) | 0.37337 (12) | 0.50825 (13) | 0.0535 (6) | |
H434 | 0.4381 | 0.4252 | 0.5204 | 0.080* | |
H435 | 0.4637 | 0.3686 | 0.4533 | 0.080* | |
H436 | 0.4970 | 0.3556 | 0.5400 | 0.080* | |
O44B | 0.38778 (8) | 0.35729 (7) | 0.65094 (7) | 0.0403 (3) | |
C45B | 0.21085 (11) | 0.31077 (9) | 0.67004 (10) | 0.0285 (4) | |
O46B | 0.12951 (7) | 0.29085 (6) | 0.65682 (6) | 0.0311 (3) | |
C47B | 0.06827 (12) | 0.32173 (12) | 0.71024 (11) | 0.0465 (5) | |
H474 | 0.0815 | 0.3050 | 0.7630 | 0.070* | |
H475 | 0.0107 | 0.3055 | 0.6958 | 0.070* | |
H476 | 0.0711 | 0.3756 | 0.7082 | 0.070* | |
O48B | 0.23219 (8) | 0.35017 (6) | 0.72270 (7) | 0.0376 (3) | |
C51B | 0.23460 (11) | 0.14583 (9) | 0.67323 (9) | 0.0284 (4) | |
H512 | 0.1794 | 0.1491 | 0.6441 | 0.034* | |
C52B | 0.26578 (12) | 0.06530 (9) | 0.67390 (10) | 0.0351 (4) | |
H523 | 0.2221 | 0.0335 | 0.6983 | 0.042* | |
H524 | 0.2743 | 0.0481 | 0.6200 | 0.042* | |
C53B | 0.35021 (12) | 0.05930 (10) | 0.71928 (10) | 0.0389 (5) | |
H532 | 0.3711 | 0.0073 | 0.7178 | 0.047* | |
C54B | 0.41664 (12) | 0.10990 (10) | 0.68332 (11) | 0.0377 (4) | |
H543 | 0.4280 | 0.0941 | 0.6294 | 0.045* | |
H544 | 0.4707 | 0.1063 | 0.7131 | 0.045* | |
C55B | 0.38520 (11) | 0.19049 (9) | 0.68331 (10) | 0.0312 (4) | |
H552 | 0.4302 | 0.2229 | 0.6606 | 0.037* | |
C56B | 0.36863 (11) | 0.21352 (10) | 0.76760 (10) | 0.0341 (4) | |
H563 | 0.4227 | 0.2116 | 0.7975 | 0.041* | |
H564 | 0.3472 | 0.2648 | 0.7689 | 0.041* | |
C57B | 0.30298 (12) | 0.16205 (9) | 0.80468 (10) | 0.0344 (4) | |
H572 | 0.2926 | 0.1776 | 0.8595 | 0.041* | |
C58B | 0.33577 (13) | 0.08269 (10) | 0.80346 (10) | 0.0412 (5) | |
H583 | 0.2936 | 0.0496 | 0.8281 | 0.049* | |
H584 | 0.3900 | 0.0792 | 0.8330 | 0.049* | |
C59B | 0.22001 (11) | 0.16737 (9) | 0.75842 (9) | 0.0313 (4) | |
H593 | 0.1979 | 0.2184 | 0.7610 | 0.038* | |
H594 | 0.1768 | 0.1342 | 0.7815 | 0.038* | |
O61 | 0.63047 (17) | 0.46395 (14) | 0.50595 (14) | 0.0510 (7) | 0.55 |
H61 | 0.651 (3) | 0.429 (2) | 0.533 (2) | 0.073 (14)* | 0.55 |
C61 | 0.6467 (2) | 0.4489 (2) | 0.4291 (2) | 0.0463 (9) | 0.55 |
H611 | 0.6062 | 0.4118 | 0.4103 | 0.069* | 0.55 |
H612 | 0.7051 | 0.4301 | 0.4239 | 0.069* | 0.55 |
H613 | 0.6405 | 0.4941 | 0.3985 | 0.069* | 0.55 |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1A | 0.0322 (3) | 0.0306 (2) | 0.0247 (2) | −0.00689 (18) | −0.00235 (18) | 0.00402 (18) |
C2A | 0.0314 (10) | 0.0272 (9) | 0.0211 (8) | −0.0033 (7) | 0.0004 (7) | 0.0026 (7) |
N3A | 0.0272 (8) | 0.0226 (7) | 0.0221 (7) | −0.0009 (6) | −0.0025 (6) | 0.0009 (6) |
C4A | 0.0255 (9) | 0.0234 (8) | 0.0245 (9) | 0.0011 (7) | −0.0026 (7) | 0.0013 (7) |
C5A | 0.0264 (9) | 0.0219 (8) | 0.0229 (8) | 0.0002 (7) | −0.0020 (7) | 0.0022 (7) |
C21A | 0.0313 (10) | 0.0243 (9) | 0.0232 (9) | −0.0023 (7) | −0.0056 (7) | −0.0011 (7) |
C22A | 0.0459 (12) | 0.0316 (10) | 0.0279 (9) | −0.0018 (8) | −0.0031 (8) | 0.0041 (8) |
C23A | 0.0586 (14) | 0.0288 (10) | 0.0377 (11) | 0.0018 (9) | −0.0134 (10) | 0.0064 (8) |
C24A | 0.0398 (12) | 0.0314 (10) | 0.0463 (12) | 0.0043 (8) | −0.0173 (10) | −0.0039 (9) |
C25A | 0.0286 (10) | 0.0336 (10) | 0.0423 (11) | −0.0024 (8) | −0.0067 (8) | −0.0048 (8) |
C26A | 0.0298 (10) | 0.0269 (9) | 0.0287 (9) | −0.0022 (7) | −0.0048 (8) | −0.0008 (7) |
C31A | 0.0217 (9) | 0.0292 (9) | 0.0238 (8) | 0.0004 (7) | 0.0039 (7) | −0.0038 (7) |
C32A | 0.0290 (10) | 0.0313 (9) | 0.0269 (9) | 0.0007 (7) | 0.0020 (7) | −0.0022 (7) |
C33A | 0.0358 (10) | 0.0291 (9) | 0.0367 (10) | −0.0027 (8) | 0.0047 (8) | −0.0038 (8) |
C34A | 0.0339 (10) | 0.0374 (11) | 0.0356 (10) | −0.0063 (8) | 0.0019 (8) | −0.0122 (8) |
C35A | 0.0254 (10) | 0.0431 (11) | 0.0252 (9) | 0.0005 (8) | 0.0002 (7) | −0.0067 (8) |
C36A | 0.0253 (9) | 0.0336 (9) | 0.0238 (9) | 0.0008 (7) | 0.0027 (7) | −0.0016 (7) |
C41A | 0.0259 (9) | 0.0247 (9) | 0.0284 (9) | −0.0025 (7) | −0.0024 (8) | −0.0042 (7) |
O42A | 0.0282 (7) | 0.0363 (7) | 0.0286 (6) | 0.0036 (5) | 0.0028 (5) | −0.0025 (5) |
C43A | 0.0258 (10) | 0.0446 (11) | 0.0362 (10) | 0.0030 (8) | 0.0040 (8) | −0.0095 (8) |
O44A | 0.0345 (7) | 0.0316 (7) | 0.0360 (7) | 0.0091 (5) | −0.0019 (6) | 0.0009 (6) |
C45A | 0.0292 (10) | 0.0250 (9) | 0.0257 (9) | −0.0011 (7) | −0.0035 (7) | −0.0030 (7) |
O46A | 0.0256 (7) | 0.0321 (6) | 0.0275 (6) | −0.0011 (5) | 0.0016 (5) | 0.0056 (5) |
C47A | 0.0326 (11) | 0.0425 (11) | 0.0366 (10) | −0.0060 (8) | 0.0067 (8) | 0.0089 (8) |
O48A | 0.0375 (7) | 0.0292 (7) | 0.0331 (7) | 0.0003 (5) | −0.0042 (6) | 0.0091 (5) |
C51A | 0.0241 (9) | 0.0267 (9) | 0.0244 (9) | 0.0032 (7) | −0.0016 (7) | 0.0007 (7) |
C52A | 0.0322 (10) | 0.0278 (9) | 0.0287 (9) | 0.0055 (7) | −0.0018 (8) | −0.0020 (7) |
C53A | 0.0358 (10) | 0.0238 (9) | 0.0314 (9) | −0.0002 (7) | −0.0037 (8) | −0.0026 (7) |
C54A | 0.0279 (9) | 0.0306 (9) | 0.0302 (9) | −0.0023 (7) | −0.0048 (8) | 0.0004 (7) |
C55A | 0.0264 (9) | 0.0259 (9) | 0.0280 (9) | 0.0028 (7) | −0.0016 (7) | −0.0020 (7) |
C56A | 0.0321 (10) | 0.0270 (9) | 0.0307 (9) | 0.0022 (7) | −0.0094 (8) | −0.0001 (7) |
C57A | 0.0402 (11) | 0.0321 (10) | 0.0224 (9) | −0.0002 (8) | −0.0040 (8) | 0.0021 (7) |
C58A | 0.0374 (11) | 0.0316 (10) | 0.0272 (9) | 0.0008 (8) | −0.0059 (8) | −0.0044 (7) |
C59A | 0.0313 (10) | 0.0305 (9) | 0.0236 (9) | 0.0003 (7) | 0.0004 (7) | −0.0011 (7) |
S1B | 0.0279 (3) | 0.0408 (3) | 0.0244 (2) | 0.00832 (19) | −0.00176 (18) | −0.00383 (19) |
C2B | 0.0245 (9) | 0.0306 (9) | 0.0220 (8) | 0.0034 (7) | 0.0005 (7) | −0.0001 (7) |
N3B | 0.0248 (8) | 0.0283 (7) | 0.0216 (7) | 0.0013 (6) | −0.0029 (6) | −0.0017 (6) |
C4B | 0.0257 (9) | 0.0292 (9) | 0.0216 (8) | −0.0014 (7) | −0.0033 (7) | −0.0004 (7) |
C5B | 0.0274 (9) | 0.0297 (9) | 0.0239 (9) | 0.0021 (7) | −0.0037 (7) | −0.0024 (7) |
C21B | 0.0277 (9) | 0.0260 (9) | 0.0219 (8) | 0.0034 (7) | −0.0044 (7) | 0.0015 (7) |
C22B | 0.0304 (10) | 0.0324 (10) | 0.0273 (9) | 0.0057 (8) | −0.0032 (8) | −0.0006 (7) |
C23B | 0.0438 (12) | 0.0270 (9) | 0.0318 (10) | 0.0029 (8) | −0.0086 (9) | −0.0021 (8) |
C24B | 0.0390 (11) | 0.0341 (10) | 0.0354 (10) | −0.0087 (8) | −0.0090 (9) | 0.0034 (8) |
C25B | 0.0303 (10) | 0.0454 (11) | 0.0360 (10) | −0.0053 (8) | 0.0021 (8) | 0.0020 (9) |
C26B | 0.0300 (10) | 0.0358 (10) | 0.0271 (9) | −0.0002 (8) | −0.0016 (8) | −0.0020 (8) |
C31B | 0.0230 (9) | 0.0332 (9) | 0.0245 (9) | 0.0001 (7) | 0.0025 (7) | 0.0033 (7) |
C32B | 0.0378 (11) | 0.0323 (10) | 0.0298 (9) | 0.0002 (8) | −0.0047 (8) | −0.0006 (8) |
C33B | 0.0580 (13) | 0.0316 (10) | 0.0404 (11) | 0.0060 (9) | −0.0047 (10) | −0.0002 (9) |
C34B | 0.0554 (13) | 0.0374 (11) | 0.0392 (11) | 0.0107 (9) | −0.0036 (10) | 0.0085 (9) |
C35B | 0.0363 (11) | 0.0453 (11) | 0.0264 (9) | 0.0018 (9) | −0.0016 (8) | 0.0069 (8) |
C36B | 0.0291 (10) | 0.0339 (10) | 0.0260 (9) | 0.0000 (7) | 0.0010 (7) | 0.0007 (8) |
C41B | 0.0275 (10) | 0.0342 (10) | 0.0331 (10) | 0.0018 (8) | −0.0047 (8) | 0.0028 (8) |
O42B | 0.0292 (7) | 0.0558 (8) | 0.0360 (7) | −0.0119 (6) | 0.0004 (6) | 0.0096 (6) |
C43B | 0.0307 (11) | 0.0704 (15) | 0.0596 (14) | −0.0166 (10) | 0.0005 (10) | 0.0235 (12) |
O44B | 0.0360 (8) | 0.0426 (7) | 0.0420 (8) | −0.0104 (6) | −0.0104 (6) | −0.0015 (6) |
C45B | 0.0303 (10) | 0.0297 (9) | 0.0256 (9) | 0.0005 (7) | −0.0032 (8) | 0.0016 (8) |
O46B | 0.0250 (7) | 0.0429 (7) | 0.0256 (6) | 0.0021 (5) | 0.0017 (5) | −0.0056 (5) |
C47B | 0.0336 (11) | 0.0718 (14) | 0.0342 (11) | 0.0132 (10) | 0.0072 (9) | −0.0111 (10) |
O48B | 0.0416 (8) | 0.0413 (7) | 0.0298 (7) | 0.0006 (6) | −0.0051 (6) | −0.0102 (6) |
C51B | 0.0291 (10) | 0.0317 (9) | 0.0244 (9) | −0.0013 (7) | −0.0027 (7) | −0.0018 (7) |
C52B | 0.0434 (11) | 0.0295 (10) | 0.0324 (10) | −0.0004 (8) | −0.0042 (8) | 0.0001 (8) |
C53B | 0.0489 (12) | 0.0325 (10) | 0.0354 (10) | 0.0091 (9) | −0.0081 (9) | −0.0014 (8) |
C54B | 0.0352 (11) | 0.0436 (11) | 0.0344 (10) | 0.0098 (9) | −0.0091 (8) | −0.0015 (8) |
C55B | 0.0269 (10) | 0.0369 (10) | 0.0296 (9) | 0.0002 (8) | −0.0061 (8) | −0.0002 (8) |
C56B | 0.0350 (10) | 0.0370 (10) | 0.0302 (10) | 0.0020 (8) | −0.0105 (8) | −0.0013 (8) |
C57B | 0.0443 (11) | 0.0353 (10) | 0.0236 (9) | 0.0026 (8) | −0.0056 (8) | 0.0006 (8) |
C58B | 0.0521 (12) | 0.0397 (11) | 0.0316 (10) | 0.0015 (9) | −0.0101 (9) | 0.0050 (8) |
C59B | 0.0346 (10) | 0.0331 (10) | 0.0262 (9) | −0.0019 (8) | 0.0001 (8) | 0.0018 (7) |
O61 | 0.0661 (19) | 0.0484 (16) | 0.0387 (15) | 0.0228 (14) | 0.0108 (13) | 0.0126 (12) |
C61 | 0.051 (2) | 0.050 (2) | 0.038 (2) | 0.0011 (18) | −0.0053 (18) | 0.0086 (17) |
S1A—C2A | 1.8144 (16) | C2B—C21B | 1.518 (2) |
S1A—C5A | 1.8413 (16) | C2B—H22 | 1.0000 |
C2A—N3A | 1.464 (2) | N3B—C31B | 1.408 (2) |
C2A—C21A | 1.521 (2) | N3B—C4B | 1.4619 (19) |
C2A—H21 | 1.0000 | C4B—C45B | 1.547 (2) |
N3A—C31A | 1.407 (2) | C4B—C41B | 1.557 (2) |
N3A—C4A | 1.4612 (19) | C4B—C5B | 1.613 (2) |
C4A—C45A | 1.552 (2) | C5B—C55B | 1.556 (2) |
C4A—C41A | 1.556 (2) | C5B—C51B | 1.560 (2) |
C4A—C5A | 1.609 (2) | C21B—C26B | 1.384 (2) |
C5A—C55A | 1.556 (2) | C21B—C22B | 1.391 (2) |
C5A—C51A | 1.562 (2) | C22B—C23B | 1.380 (2) |
C21A—C26A | 1.386 (2) | C22B—H222 | 0.9500 |
C21A—C22A | 1.394 (2) | C23B—C24B | 1.382 (3) |
C22A—C23A | 1.389 (2) | C23B—H232 | 0.9500 |
C22A—H221 | 0.9500 | C24B—C25B | 1.384 (3) |
C23A—C24A | 1.381 (3) | C24B—H242 | 0.9500 |
C23A—H231 | 0.9500 | C25B—C26B | 1.384 (2) |
C24A—C25A | 1.381 (3) | C25B—H252 | 0.9500 |
C24A—H241 | 0.9500 | C26B—H262 | 0.9500 |
C25A—C26A | 1.391 (2) | C31B—C32B | 1.396 (2) |
C25A—H251 | 0.9500 | C31B—C36B | 1.409 (2) |
C26A—H261 | 0.9500 | C32B—C33B | 1.380 (2) |
C31A—C32A | 1.403 (2) | C32B—H322 | 0.9500 |
C31A—C36A | 1.403 (2) | C33B—C34B | 1.384 (3) |
C32A—C33A | 1.391 (2) | C33B—H332 | 0.9500 |
C32A—H321 | 0.9500 | C34B—C35B | 1.380 (3) |
C33A—C34A | 1.380 (2) | C34B—H342 | 0.9500 |
C33A—H331 | 0.9500 | C35B—C36B | 1.384 (2) |
C34A—C35A | 1.387 (2) | C35B—H352 | 0.9500 |
C34A—H341 | 0.9500 | C36B—H362 | 0.9500 |
C35A—C36A | 1.383 (2) | C41B—O44B | 1.198 (2) |
C35A—H351 | 0.9500 | C41B—O42B | 1.336 (2) |
C36A—H361 | 0.9500 | O42B—C43B | 1.454 (2) |
C41A—O44A | 1.2012 (19) | C43B—H434 | 0.9800 |
C41A—O42A | 1.3334 (19) | C43B—H435 | 0.9800 |
O42A—C43A | 1.4527 (19) | C43B—H436 | 0.9800 |
C43A—H431 | 0.9800 | C45B—O48B | 1.2026 (19) |
C43A—H432 | 0.9800 | C45B—O46B | 1.343 (2) |
C43A—H433 | 0.9800 | O46B—C47B | 1.446 (2) |
C45A—O48A | 1.2036 (18) | C47B—H474 | 0.9800 |
C45A—O46A | 1.3445 (19) | C47B—H475 | 0.9800 |
O46A—C47A | 1.4516 (19) | C47B—H476 | 0.9800 |
C47A—H471 | 0.9800 | C51B—C59B | 1.539 (2) |
C47A—H472 | 0.9800 | C51B—C52B | 1.541 (2) |
C47A—H473 | 0.9800 | C51B—H512 | 1.0000 |
C51A—C59A | 1.539 (2) | C52B—C53B | 1.538 (2) |
C51A—C52A | 1.543 (2) | C52B—H523 | 0.9900 |
C51A—H511 | 1.0000 | C52B—H524 | 0.9900 |
C52A—C53A | 1.534 (2) | C53B—C54B | 1.522 (3) |
C52A—H521 | 0.9900 | C53B—C58B | 1.531 (2) |
C52A—H522 | 0.9900 | C53B—H532 | 1.0000 |
C53A—C54A | 1.525 (2) | C54B—C55B | 1.544 (2) |
C53A—C58A | 1.533 (2) | C54B—H543 | 0.9900 |
C53A—H531 | 1.0000 | C54B—H544 | 0.9900 |
C54A—C55A | 1.543 (2) | C55B—C56B | 1.536 (2) |
C54A—H541 | 0.9900 | C55B—H552 | 1.0000 |
C54A—H542 | 0.9900 | C56B—C57B | 1.532 (2) |
C55A—C56A | 1.537 (2) | C56B—H563 | 0.9900 |
C55A—H551 | 1.0000 | C56B—H564 | 0.9900 |
C56A—C57A | 1.529 (2) | C57B—C59B | 1.525 (2) |
C56A—H561 | 0.9900 | C57B—C58B | 1.530 (2) |
C56A—H562 | 0.9900 | C57B—H572 | 1.0000 |
C57A—C59A | 1.529 (2) | C58B—H583 | 0.9900 |
C57A—C58A | 1.530 (2) | C58B—H584 | 0.9900 |
C57A—H571 | 1.0000 | C59B—H593 | 0.9900 |
C58A—H581 | 0.9900 | C59B—H594 | 0.9900 |
C58A—H582 | 0.9900 | O61—C61 | 1.378 (4) |
C59A—H591 | 0.9900 | O61—H61 | 0.85 (4) |
C59A—H592 | 0.9900 | C61—H611 | 0.9800 |
S1B—C2B | 1.8087 (16) | C61—H612 | 0.9800 |
S1B—C5B | 1.8400 (16) | C61—H613 | 0.9800 |
C2B—N3B | 1.463 (2) | ||
C2A—S1A—C5A | 95.23 (7) | N3B—C2B—H22 | 107.8 |
N3A—C2A—C21A | 114.42 (14) | C21B—C2B—H22 | 107.8 |
N3A—C2A—S1A | 106.17 (10) | S1B—C2B—H22 | 107.8 |
C21A—C2A—S1A | 112.31 (11) | C31B—N3B—C4B | 120.81 (13) |
N3A—C2A—H21 | 107.9 | C31B—N3B—C2B | 117.35 (12) |
C21A—C2A—H21 | 107.9 | C4B—N3B—C2B | 116.51 (12) |
S1A—C2A—H21 | 107.9 | N3B—C4B—C45B | 108.49 (13) |
C31A—N3A—C4A | 119.59 (12) | N3B—C4B—C41B | 111.46 (13) |
C31A—N3A—C2A | 117.24 (12) | C45B—C4B—C41B | 109.19 (13) |
C4A—N3A—C2A | 116.81 (12) | N3B—C4B—C5B | 107.02 (12) |
N3A—C4A—C45A | 108.41 (12) | C45B—C4B—C5B | 112.33 (13) |
N3A—C4A—C41A | 110.65 (13) | C41B—C4B—C5B | 108.35 (13) |
C45A—C4A—C41A | 109.81 (13) | C55B—C5B—C51B | 106.69 (13) |
N3A—C4A—C5A | 108.06 (12) | C55B—C5B—C4B | 116.74 (13) |
C45A—C4A—C5A | 112.52 (12) | C51B—C5B—C4B | 115.42 (13) |
C41A—C4A—C5A | 107.38 (12) | C55B—C5B—S1B | 106.05 (11) |
C55A—C5A—C51A | 107.02 (12) | C51B—C5B—S1B | 111.53 (11) |
C55A—C5A—C4A | 114.79 (12) | C4B—C5B—S1B | 99.93 (10) |
C51A—C5A—C4A | 115.86 (13) | C26B—C21B—C22B | 118.98 (15) |
C55A—C5A—S1A | 106.85 (11) | C26B—C21B—C2B | 122.71 (14) |
C51A—C5A—S1A | 111.03 (10) | C22B—C21B—C2B | 118.30 (15) |
C4A—C5A—S1A | 100.87 (10) | C23B—C22B—C21B | 120.68 (17) |
C26A—C21A—C22A | 119.29 (16) | C23B—C22B—H222 | 119.7 |
C26A—C21A—C2A | 122.32 (14) | C21B—C22B—H222 | 119.7 |
C22A—C21A—C2A | 118.38 (15) | C22B—C23B—C24B | 120.12 (16) |
C23A—C22A—C21A | 120.15 (18) | C22B—C23B—H232 | 119.9 |
C23A—C22A—H221 | 119.9 | C24B—C23B—H232 | 119.9 |
C21A—C22A—H221 | 119.9 | C23B—C24B—C25B | 119.49 (16) |
C24A—C23A—C22A | 120.32 (17) | C23B—C24B—H242 | 120.3 |
C24A—C23A—H231 | 119.8 | C25B—C24B—H242 | 120.3 |
C22A—C23A—H231 | 119.8 | C24B—C25B—C26B | 120.48 (17) |
C23A—C24A—C25A | 119.65 (17) | C24B—C25B—H252 | 119.8 |
C23A—C24A—H241 | 120.2 | C26B—C25B—H252 | 119.8 |
C25A—C24A—H241 | 120.2 | C25B—C26B—C21B | 120.23 (16) |
C24A—C25A—C26A | 120.51 (18) | C25B—C26B—H262 | 119.9 |
C24A—C25A—H251 | 119.7 | C21B—C26B—H262 | 119.9 |
C26A—C25A—H251 | 119.7 | C32B—C31B—N3B | 123.14 (14) |
C21A—C26A—C25A | 120.06 (16) | C32B—C31B—C36B | 117.18 (15) |
C21A—C26A—H261 | 120.0 | N3B—C31B—C36B | 119.67 (14) |
C25A—C26A—H261 | 120.0 | C33B—C32B—C31B | 121.25 (16) |
C32A—C31A—C36A | 117.34 (15) | C33B—C32B—H322 | 119.4 |
C32A—C31A—N3A | 122.73 (14) | C31B—C32B—H322 | 119.4 |
C36A—C31A—N3A | 119.92 (14) | C32B—C33B—C34B | 121.23 (17) |
C33A—C32A—C31A | 121.00 (16) | C32B—C33B—H332 | 119.4 |
C33A—C32A—H321 | 119.5 | C34B—C33B—H332 | 119.4 |
C31A—C32A—H321 | 119.5 | C35B—C34B—C33B | 118.27 (17) |
C34A—C33A—C32A | 121.08 (16) | C35B—C34B—H342 | 120.9 |
C34A—C33A—H331 | 119.5 | C33B—C34B—H342 | 120.9 |
C32A—C33A—H331 | 119.5 | C34B—C35B—C36B | 121.41 (17) |
C33A—C34A—C35A | 118.26 (16) | C34B—C35B—H352 | 119.3 |
C33A—C34A—H341 | 120.9 | C36B—C35B—H352 | 119.3 |
C35A—C34A—H341 | 120.9 | C35B—C36B—C31B | 120.62 (16) |
C36A—C35A—C34A | 121.57 (16) | C35B—C36B—H362 | 119.7 |
C36A—C35A—H351 | 119.2 | C31B—C36B—H362 | 119.7 |
C34A—C35A—H351 | 119.2 | O44B—C41B—O42B | 124.52 (16) |
C35A—C36A—C31A | 120.73 (15) | O44B—C41B—C4B | 125.34 (16) |
C35A—C36A—H361 | 119.6 | O42B—C41B—C4B | 110.13 (14) |
C31A—C36A—H361 | 119.6 | C41B—O42B—C43B | 115.59 (14) |
O44A—C41A—O42A | 123.81 (15) | O42B—C43B—H434 | 109.5 |
O44A—C41A—C4A | 126.08 (15) | O42B—C43B—H435 | 109.5 |
O42A—C41A—C4A | 110.07 (13) | H434—C43B—H435 | 109.5 |
C41A—O42A—C43A | 114.73 (13) | O42B—C43B—H436 | 109.5 |
O42A—C43A—H431 | 109.5 | H434—C43B—H436 | 109.5 |
O42A—C43A—H432 | 109.5 | H435—C43B—H436 | 109.5 |
H431—C43A—H432 | 109.5 | O48B—C45B—O46B | 123.29 (16) |
O42A—C43A—H433 | 109.5 | O48B—C45B—C4B | 125.90 (15) |
H431—C43A—H433 | 109.5 | O46B—C45B—C4B | 110.80 (13) |
H432—C43A—H433 | 109.5 | C45B—O46B—C47B | 114.77 (13) |
O48A—C45A—O46A | 123.17 (15) | O46B—C47B—H474 | 109.5 |
O48A—C45A—C4A | 125.62 (15) | O46B—C47B—H475 | 109.5 |
O46A—C45A—C4A | 111.21 (13) | H474—C47B—H475 | 109.5 |
C45A—O46A—C47A | 114.74 (13) | O46B—C47B—H476 | 109.5 |
O46A—C47A—H471 | 109.5 | H474—C47B—H476 | 109.5 |
O46A—C47A—H472 | 109.5 | H475—C47B—H476 | 109.5 |
H471—C47A—H472 | 109.5 | C59B—C51B—C52B | 106.39 (13) |
O46A—C47A—H473 | 109.5 | C59B—C51B—C5B | 112.59 (13) |
H471—C47A—H473 | 109.5 | C52B—C51B—C5B | 109.33 (14) |
H472—C47A—H473 | 109.5 | C59B—C51B—H512 | 109.5 |
C59A—C51A—C52A | 106.03 (13) | C52B—C51B—H512 | 109.5 |
C59A—C51A—C5A | 112.95 (13) | C5B—C51B—H512 | 109.5 |
C52A—C51A—C5A | 108.94 (13) | C53B—C52B—C51B | 110.05 (14) |
C59A—C51A—H511 | 109.6 | C53B—C52B—H523 | 109.7 |
C52A—C51A—H511 | 109.6 | C51B—C52B—H523 | 109.7 |
C5A—C51A—H511 | 109.6 | C53B—C52B—H524 | 109.7 |
C53A—C52A—C51A | 110.62 (13) | C51B—C52B—H524 | 109.7 |
C53A—C52A—H521 | 109.5 | H523—C52B—H524 | 108.2 |
C51A—C52A—H521 | 109.5 | C54B—C53B—C58B | 108.87 (15) |
C53A—C52A—H522 | 109.5 | C54B—C53B—C52B | 109.74 (14) |
C51A—C52A—H522 | 109.5 | C58B—C53B—C52B | 109.46 (16) |
H521—C52A—H522 | 108.1 | C54B—C53B—H532 | 109.6 |
C54A—C53A—C58A | 108.90 (14) | C58B—C53B—H532 | 109.6 |
C54A—C53A—C52A | 108.91 (13) | C52B—C53B—H532 | 109.6 |
C58A—C53A—C52A | 109.75 (14) | C53B—C54B—C55B | 110.69 (15) |
C54A—C53A—H531 | 109.8 | C53B—C54B—H543 | 109.5 |
C58A—C53A—H531 | 109.8 | C55B—C54B—H543 | 109.5 |
C52A—C53A—H531 | 109.8 | C53B—C54B—H544 | 109.5 |
C53A—C54A—C55A | 111.04 (14) | C55B—C54B—H544 | 109.5 |
C53A—C54A—H541 | 109.4 | H543—C54B—H544 | 108.1 |
C55A—C54A—H541 | 109.4 | C56B—C55B—C54B | 108.24 (14) |
C53A—C54A—H542 | 109.4 | C56B—C55B—C5B | 111.76 (14) |
C55A—C54A—H542 | 109.4 | C54B—C55B—C5B | 108.45 (13) |
H541—C54A—H542 | 108.0 | C56B—C55B—H552 | 109.5 |
C56A—C55A—C54A | 108.02 (13) | C54B—C55B—H552 | 109.5 |
C56A—C55A—C5A | 111.11 (13) | C5B—C55B—H552 | 109.5 |
C54A—C55A—C5A | 108.84 (13) | C57B—C56B—C55B | 110.23 (14) |
C56A—C55A—H551 | 109.6 | C57B—C56B—H563 | 109.6 |
C54A—C55A—H551 | 109.6 | C55B—C56B—H563 | 109.6 |
C5A—C55A—H551 | 109.6 | C57B—C56B—H564 | 109.6 |
C57A—C56A—C55A | 110.26 (13) | C55B—C56B—H564 | 109.6 |
C57A—C56A—H561 | 109.6 | H563—C56B—H564 | 108.1 |
C55A—C56A—H561 | 109.6 | C59B—C57B—C58B | 109.74 (14) |
C57A—C56A—H562 | 109.6 | C59B—C57B—C56B | 108.36 (14) |
C55A—C56A—H562 | 109.6 | C58B—C57B—C56B | 110.04 (15) |
H561—C56A—H562 | 108.1 | C59B—C57B—H572 | 109.6 |
C56A—C57A—C59A | 109.45 (13) | C58B—C57B—H572 | 109.6 |
C56A—C57A—C58A | 110.44 (14) | C56B—C57B—H572 | 109.6 |
C59A—C57A—C58A | 108.96 (14) | C57B—C58B—C53B | 108.98 (14) |
C56A—C57A—H571 | 109.3 | C57B—C58B—H583 | 109.9 |
C59A—C57A—H571 | 109.3 | C53B—C58B—H583 | 109.9 |
C58A—C57A—H571 | 109.3 | C57B—C58B—H584 | 109.9 |
C57A—C58A—C53A | 108.75 (13) | C53B—C58B—H584 | 109.9 |
C57A—C58A—H581 | 109.9 | H583—C58B—H584 | 108.3 |
C53A—C58A—H581 | 109.9 | C57B—C59B—C51B | 110.73 (14) |
C57A—C58A—H582 | 109.9 | C57B—C59B—H593 | 109.5 |
C53A—C58A—H582 | 109.9 | C51B—C59B—H593 | 109.5 |
H581—C58A—H582 | 108.3 | C57B—C59B—H594 | 109.5 |
C57A—C59A—C51A | 110.36 (14) | C51B—C59B—H594 | 109.5 |
C57A—C59A—H591 | 109.6 | H593—C59B—H594 | 108.1 |
C51A—C59A—H591 | 109.6 | C61—O61—H61 | 107 (3) |
C57A—C59A—H592 | 109.6 | O61—C61—H611 | 109.5 |
C51A—C59A—H592 | 109.6 | O61—C61—H612 | 109.5 |
H591—C59A—H592 | 108.1 | H611—C61—H612 | 109.5 |
C2B—S1B—C5B | 94.02 (7) | O61—C61—H613 | 109.5 |
N3B—C2B—C21B | 114.27 (13) | H611—C61—H613 | 109.5 |
N3B—C2B—S1B | 105.93 (10) | H612—C61—H613 | 109.5 |
C21B—C2B—S1B | 112.92 (11) | ||
C5A—S1A—C2A—N3A | 19.30 (12) | C5B—S1B—C2B—N3B | 24.47 (11) |
C5A—S1A—C2A—C21A | −106.45 (12) | C5B—S1B—C2B—C21B | −101.32 (12) |
C21A—C2A—N3A—C31A | −82.61 (17) | C21B—C2B—N3B—C31B | −83.25 (17) |
S1A—C2A—N3A—C31A | 152.94 (11) | S1B—C2B—N3B—C31B | 151.79 (12) |
C21A—C2A—N3A—C4A | 125.44 (14) | C21B—C2B—N3B—C4B | 122.28 (14) |
S1A—C2A—N3A—C4A | 0.98 (16) | S1B—C2B—N3B—C4B | −2.67 (16) |
C31A—N3A—C4A—C45A | 61.50 (17) | C31B—N3B—C4B—C45B | 60.07 (18) |
C2A—N3A—C4A—C45A | −147.23 (13) | C2B—N3B—C4B—C45B | −146.40 (13) |
C31A—N3A—C4A—C41A | −58.97 (18) | C31B—N3B—C4B—C41B | −60.19 (19) |
C2A—N3A—C4A—C41A | 92.29 (16) | C2B—N3B—C4B—C41B | 93.34 (16) |
C31A—N3A—C4A—C5A | −176.28 (13) | C31B—N3B—C4B—C5B | −178.50 (13) |
C2A—N3A—C4A—C5A | −25.01 (18) | C2B—N3B—C4B—C5B | −24.97 (18) |
N3A—C4A—C5A—C55A | 149.87 (13) | N3B—C4B—C5B—C55B | 152.75 (13) |
C45A—C4A—C5A—C55A | −90.46 (16) | C45B—C4B—C5B—C55B | −88.28 (17) |
C41A—C4A—C5A—C55A | 30.48 (17) | C41B—C4B—C5B—C55B | 32.43 (18) |
N3A—C4A—C5A—C51A | −84.52 (15) | N3B—C4B—C5B—C51B | −80.70 (16) |
C45A—C4A—C5A—C51A | 35.14 (17) | C45B—C4B—C5B—C51B | 38.27 (18) |
C41A—C4A—C5A—C51A | 156.09 (13) | C41B—C4B—C5B—C51B | 158.98 (13) |
N3A—C4A—C5A—S1A | 35.42 (14) | N3B—C4B—C5B—S1B | 39.01 (13) |
C45A—C4A—C5A—S1A | 155.09 (11) | C45B—C4B—C5B—S1B | 157.98 (11) |
C41A—C4A—C5A—S1A | −83.97 (12) | C41B—C4B—C5B—S1B | −81.31 (13) |
C2A—S1A—C5A—C55A | −151.32 (11) | C2B—S1B—C5B—C55B | −157.79 (11) |
C2A—S1A—C5A—C51A | 92.31 (12) | C2B—S1B—C5B—C51B | 86.45 (12) |
C2A—S1A—C5A—C4A | −31.04 (11) | C2B—S1B—C5B—C4B | −36.07 (11) |
N3A—C2A—C21A—C26A | −20.6 (2) | N3B—C2B—C21B—C26B | −11.3 (2) |
S1A—C2A—C21A—C26A | 100.57 (16) | S1B—C2B—C21B—C26B | 109.83 (15) |
N3A—C2A—C21A—C22A | 159.31 (14) | N3B—C2B—C21B—C22B | 167.81 (13) |
S1A—C2A—C21A—C22A | −79.56 (16) | S1B—C2B—C21B—C22B | −71.03 (16) |
C26A—C21A—C22A—C23A | −0.8 (2) | C26B—C21B—C22B—C23B | −0.8 (2) |
C2A—C21A—C22A—C23A | 179.35 (15) | C2B—C21B—C22B—C23B | −179.96 (14) |
C21A—C22A—C23A—C24A | −0.1 (3) | C21B—C22B—C23B—C24B | 1.5 (2) |
C22A—C23A—C24A—C25A | 0.6 (3) | C22B—C23B—C24B—C25B | −1.2 (3) |
C23A—C24A—C25A—C26A | −0.3 (3) | C23B—C24B—C25B—C26B | 0.3 (3) |
C22A—C21A—C26A—C25A | 1.1 (2) | C24B—C25B—C26B—C21B | 0.4 (3) |
C2A—C21A—C26A—C25A | −179.02 (14) | C22B—C21B—C26B—C25B | −0.2 (2) |
C24A—C25A—C26A—C21A | −0.6 (2) | C2B—C21B—C26B—C25B | 178.98 (15) |
C4A—N3A—C31A—C32A | −6.5 (2) | C4B—N3B—C31B—C32B | −5.9 (2) |
C2A—N3A—C31A—C32A | −157.66 (15) | C2B—N3B—C31B—C32B | −159.18 (15) |
C4A—N3A—C31A—C36A | 174.65 (14) | C4B—N3B—C31B—C36B | 175.02 (14) |
C2A—N3A—C31A—C36A | 23.5 (2) | C2B—N3B—C31B—C36B | 21.7 (2) |
C36A—C31A—C32A—C33A | 1.6 (2) | N3B—C31B—C32B—C33B | −177.59 (17) |
N3A—C31A—C32A—C33A | −177.26 (15) | C36B—C31B—C32B—C33B | 1.5 (3) |
C31A—C32A—C33A—C34A | −0.3 (3) | C31B—C32B—C33B—C34B | −0.2 (3) |
C32A—C33A—C34A—C35A | −1.1 (3) | C32B—C33B—C34B—C35B | −1.1 (3) |
C33A—C34A—C35A—C36A | 1.2 (3) | C33B—C34B—C35B—C36B | 1.0 (3) |
C34A—C35A—C36A—C31A | 0.2 (3) | C34B—C35B—C36B—C31B | 0.4 (3) |
C32A—C31A—C36A—C35A | −1.5 (2) | C32B—C31B—C36B—C35B | −1.7 (2) |
N3A—C31A—C36A—C35A | 177.35 (14) | N3B—C31B—C36B—C35B | 177.49 (15) |
N3A—C4A—C41A—O44A | 151.90 (15) | N3B—C4B—C41B—O44B | 159.84 (16) |
C45A—C4A—C41A—O44A | 32.3 (2) | C45B—C4B—C41B—O44B | 40.0 (2) |
C5A—C4A—C41A—O44A | −90.38 (18) | C5B—C4B—C41B—O44B | −82.7 (2) |
N3A—C4A—C41A—O42A | −30.47 (17) | N3B—C4B—C41B—O42B | −21.40 (18) |
C45A—C4A—C41A—O42A | −150.11 (12) | C45B—C4B—C41B—O42B | −141.25 (14) |
C5A—C4A—C41A—O42A | 87.25 (14) | C5B—C4B—C41B—O42B | 96.11 (15) |
O44A—C41A—O42A—C43A | 4.2 (2) | O44B—C41B—O42B—C43B | 0.6 (3) |
C4A—C41A—O42A—C43A | −173.48 (12) | C4B—C41B—O42B—C43B | −178.14 (14) |
N3A—C4A—C45A—O48A | −147.77 (15) | N3B—C4B—C45B—O48B | −148.67 (16) |
C41A—C4A—C45A—O48A | −26.8 (2) | C41B—C4B—C45B—O48B | −27.0 (2) |
C5A—C4A—C45A—O48A | 92.77 (18) | C5B—C4B—C45B—O48B | 93.23 (19) |
N3A—C4A—C45A—O46A | 32.42 (17) | N3B—C4B—C45B—O46B | 31.10 (17) |
C41A—C4A—C45A—O46A | 153.42 (13) | C41B—C4B—C45B—O46B | 152.76 (13) |
C5A—C4A—C45A—O46A | −87.04 (15) | C5B—C4B—C45B—O46B | −87.01 (15) |
O48A—C45A—O46A—C47A | 1.1 (2) | O48B—C45B—O46B—C47B | 1.2 (2) |
C4A—C45A—O46A—C47A | −179.06 (13) | C4B—C45B—O46B—C47B | −178.59 (14) |
C55A—C5A—C51A—C59A | 55.62 (16) | C55B—C5B—C51B—C59B | 55.28 (17) |
C4A—C5A—C51A—C59A | −73.85 (17) | C4B—C5B—C51B—C59B | −76.22 (17) |
S1A—C5A—C51A—C59A | 171.89 (11) | S1B—C5B—C51B—C59B | 170.65 (11) |
C55A—C5A—C51A—C52A | −61.92 (15) | C55B—C5B—C51B—C52B | −62.75 (16) |
C4A—C5A—C51A—C52A | 168.61 (12) | C4B—C5B—C51B—C52B | 165.75 (13) |
S1A—C5A—C51A—C52A | 54.34 (14) | S1B—C5B—C51B—C52B | 52.63 (15) |
C59A—C51A—C52A—C53A | −60.57 (17) | C59B—C51B—C52B—C53B | −61.20 (18) |
C5A—C51A—C52A—C53A | 61.27 (17) | C5B—C51B—C52B—C53B | 60.64 (18) |
C51A—C52A—C53A—C54A | −58.47 (17) | C51B—C52B—C53B—C54B | −57.59 (19) |
C51A—C52A—C53A—C58A | 60.66 (17) | C51B—C52B—C53B—C58B | 61.82 (19) |
C58A—C53A—C54A—C55A | −61.10 (17) | C58B—C53B—C54B—C55B | −61.28 (18) |
C52A—C53A—C54A—C55A | 58.56 (17) | C52B—C53B—C54B—C55B | 58.50 (18) |
C53A—C54A—C55A—C56A | 59.35 (17) | C53B—C54B—C55B—C56B | 59.52 (18) |
C53A—C54A—C55A—C5A | −61.40 (17) | C53B—C54B—C55B—C5B | −61.91 (18) |
C51A—C5A—C55A—C56A | −57.14 (16) | C51B—C5B—C55B—C56B | −56.53 (17) |
C4A—C5A—C55A—C56A | 72.95 (16) | C4B—C5B—C55B—C56B | 74.23 (18) |
S1A—C5A—C55A—C56A | −176.14 (11) | S1B—C5B—C55B—C56B | −175.54 (12) |
C51A—C5A—C55A—C54A | 61.69 (16) | C51B—C5B—C55B—C54B | 62.71 (17) |
C4A—C5A—C55A—C54A | −168.22 (13) | C4B—C5B—C55B—C54B | −166.53 (14) |
S1A—C5A—C55A—C54A | −57.31 (14) | S1B—C5B—C55B—C54B | −56.30 (15) |
C54A—C55A—C56A—C57A | −57.92 (17) | C54B—C55B—C56B—C57B | −58.04 (18) |
C5A—C55A—C56A—C57A | 61.40 (17) | C5B—C55B—C56B—C57B | 61.32 (18) |
C55A—C56A—C57A—C59A | −60.11 (17) | C55B—C56B—C57B—C59B | −60.39 (18) |
C55A—C56A—C57A—C58A | 59.85 (17) | C55B—C56B—C57B—C58B | 59.61 (18) |
C56A—C57A—C58A—C53A | −60.18 (18) | C59B—C57B—C58B—C53B | 58.9 (2) |
C59A—C57A—C58A—C53A | 60.08 (18) | C56B—C57B—C58B—C53B | −60.26 (19) |
C54A—C53A—C58A—C57A | 60.17 (18) | C54B—C53B—C58B—C57B | 60.71 (19) |
C52A—C53A—C58A—C57A | −58.97 (18) | C52B—C53B—C58B—C57B | −59.2 (2) |
C56A—C57A—C59A—C51A | 57.55 (18) | C58B—C57B—C59B—C51B | −61.25 (18) |
C58A—C57A—C59A—C51A | −63.31 (17) | C56B—C57B—C59B—C51B | 58.93 (18) |
C52A—C51A—C59A—C57A | 62.06 (16) | C52B—C51B—C59B—C57B | 61.13 (17) |
C5A—C51A—C59A—C57A | −57.18 (17) | C5B—C51B—C59B—C57B | −58.61 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
O61—H61···O44A | 0.85 (4) | 2.03 (4) | 2.788 (3) | 148 (4) |
O61—H61···O48A | 0.85 (4) | 2.43 (4) | 3.099 (3) | 136 (4) |
C43A—H433···O44B | 0.98 | 2.54 | 3.375 (2) | 144 |
C43B—H436···O44A | 0.98 | 2.49 | 3.439 (2) | 162 |
C43B—H434···O61i | 0.98 | 2.33 | 3.215 (3) | 151 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
C31H25NO4S | Z = 2 |
Mr = 507.58 | F(000) = 532 |
Triclinic, P1 | Dx = 1.291 Mg m−3 Dm = 1.249 Mg m−3 Dm measured by flotation in KBr and KI |
Hall symbol: -P 1 | Melting point: 476(1) K |
a = 9.817 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.233 (2) Å | Cell parameters from 25 reflections |
c = 12.459 (2) Å | θ = 20.0–21.3° |
α = 102.53 (1)° | µ = 0.16 mm−1 |
β = 97.91 (1)° | T = 293 K |
γ = 98.52 (1)° | Prism, colourless |
V = 1305.7 (4) Å3 | 0.8 × 0.7 × 0.5 mm |
Rigaku AFC-5S diffractometer | 6330 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 32.6°, θmin = 3.4° |
ω scans | h = −14→14 |
Absorption correction: analytical (de Meulenaer & Tompa, 1965) | k = −17→17 |
Tmin = 0.897, Tmax = 0.937 | l = −18→18 |
18942 measured reflections | 3 standard reflections every 150 reflections |
9471 independent reflections | intensity decay: <2% |
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.036 | w = 1/[σ2(Fo2) + (0.0687P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.121 | (Δ/σ)max = 0.001 |
S = 1.06 | Δρmax = 0.29 e Å−3 |
9471 reflections | Δρmin = −0.24 e Å−3 |
337 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.045 (3) |
Primary atom site location: structure-invariant direct methods |
C31H25NO4S | γ = 98.52 (1)° |
Mr = 507.58 | V = 1305.7 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.817 (1) Å | Mo Kα radiation |
b = 11.233 (2) Å | µ = 0.16 mm−1 |
c = 12.459 (2) Å | T = 293 K |
α = 102.53 (1)° | 0.8 × 0.7 × 0.5 mm |
β = 97.91 (1)° |
Rigaku AFC-5S diffractometer | 6330 reflections with I > 2σ(I) |
Absorption correction: analytical (de Meulenaer & Tompa, 1965) | Rint = 0.017 |
Tmin = 0.897, Tmax = 0.937 | 3 standard reflections every 150 reflections |
18942 measured reflections | intensity decay: <2% |
9471 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.29 e Å−3 |
9471 reflections | Δρmin = −0.24 e Å−3 |
337 parameters |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 9.1645 (0.0026) x + 2.2346 (0.0059) y − 3.9441 (0.0074) z = 2.5395 (0.0029) * 0.0073 (0.0008) C31 * 0.0056 (0.0008) C32 * −0.0108 (0.0009) C33 * 0.0030 (0.0011) C34 * 0.0100 (0.0012) C35 * −0.0150 (0.0010) C36 Rms deviation of fitted atoms = 0.0094 4.1396 (0.0032) x + 4.9427 (0.0038) y + 6.7495 (0.0049) z = 4.5007 (0.0010) Angle to previous plane (with approximate e.s.d.) = 61.06 (0.04) * 0.0870 (0.0004) S1 * 0.0558 (0.0005) C2 * −0.2294 (0.0006) N3 * 0.3102 (0.0006) C4 * −0.2236 (0.0005) C5 Rms deviation of fitted atoms = 0.2047 0.0377 (0.0044) x + 11.0295 (0.0022) y − 4.3482 (0.0058) z = 1.6708 (0.0025) Angle to previous plane (with approximate e.s.d.) = 65.14 (0.03) * −0.0030 (0.0007) C41 * 0.0032 (0.0007) C42 * −0.0016 (0.0008) C43 * −0.0003 (0.0008) C44 * 0.0005 (0.0008) C45 * 0.0012 (0.0008) C46 Rms deviation of fitted atoms = 0.0020 7.1944 (0.0024) x − 8.3318 (0.0030) y − 2.1001 (0.0029) z = 0.4837 (0.0009) * −0.0638 (0.0009) C51 * −0.0089 (0.0009) C52 * 0.0589 (0.0011) C53 * 0.0429 (0.0010) C54 * −0.0010 (0.0010) C55 * −0.0380 (0.0009) C56 * −0.0343 (0.0009) C57 * −0.0257 (0.0010) C58 * −0.0045 (0.0010) C59 * 0.0590 (0.0010) C60 * 0.0469 (0.0009) C61 * −0.0315 (0.0008) C62 − 0.1896 (0.0011) C5 Rms deviation of fitted atoms = 0.0402 7.1187 (0.0036) x − 8.2351 (0.0040) y − 2.6065 (0.0057) z = 0.1893 (0.0032) * −0.0093 (0.0007) C51 * −0.0027 (0.0008) C52 * 0.0117 (0.0009) C53 * −0.0084 (0.0009) C54 * −0.0038 (0.0008) C55 * 0.0125 (0.0007) C56 Rms deviation of fitted atoms = 0.0089 7.2321 (0.0033) x − 8.4173 (0.0038) y − 1.6686 (0.0056) z = 0.5923 (0.0015) Angle to previous plane (with approximate e.s.d.) = 4.50 (0.07) * 0.0119 (0.0007) C57 * 0.0078 (0.0008) C58 * −0.0187 (0.0008) C59 * 0.0099 (0.0008) C60 * 0.0099 (0.0007) C61 * −0.0207 (0.0007) C62 Rms deviation of fitted atoms = 0.0140 |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. H-atoms were clearly revealed in the difference map and constrained to ride on their parent atoms, with Uiso(H)=1.2Ueq(C) [or 1.5Ueq(C) for the methyl groups]. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.47266 (2) | 0.15786 (2) | 0.27421 (2) | 0.04390 (8) | |
C2 | 0.43433 (9) | 0.27966 (9) | 0.20390 (7) | 0.03812 (18) | |
C21 | 0.43466 (11) | 0.22312 (9) | 0.08031 (8) | 0.0447 (2) | |
O22 | 0.56275 (8) | 0.20262 (8) | 0.06906 (6) | 0.05527 (19) | |
C23 | 0.58258 (18) | 0.14639 (16) | −0.04158 (12) | 0.0823 (4) | |
H231 | 0.6764 | 0.1309 | −0.0389 | 0.123* | |
H232 | 0.5671 | 0.2013 | −0.0894 | 0.123* | |
H233 | 0.5175 | 0.0695 | −0.0703 | 0.123* | |
O24 | 0.33602 (9) | 0.19505 (9) | 0.00628 (7) | 0.0668 (2) | |
C25 | 0.54619 (10) | 0.39882 (9) | 0.25092 (8) | 0.0429 (2) | |
O26 | 0.57617 (10) | 0.45153 (7) | 0.16975 (7) | 0.0635 (2) | |
C27 | 0.6732 (2) | 0.56893 (15) | 0.20392 (16) | 0.1058 (7) | |
H271 | 0.6409 | 0.6246 | 0.2608 | 0.159* | |
H272 | 0.6788 | 0.6043 | 0.1408 | 0.159* | |
H273 | 0.7640 | 0.5556 | 0.2328 | 0.159* | |
O28 | 0.58971 (8) | 0.44182 (8) | 0.34843 (7) | 0.0580 (2) | |
N3 | 0.29697 (8) | 0.30504 (7) | 0.22731 (6) | 0.03793 (16) | |
C31 | 0.26510 (10) | 0.42140 (9) | 0.20902 (9) | 0.0439 (2) | |
C32 | 0.27735 (11) | 0.52530 (10) | 0.29679 (10) | 0.0521 (2) | |
H321 | 0.3105 | 0.5221 | 0.3695 | 0.062* | |
C33 | 0.23992 (14) | 0.63407 (12) | 0.27560 (13) | 0.0665 (3) | |
H331 | 0.2463 | 0.7027 | 0.3346 | 0.080* | |
C34 | 0.19394 (17) | 0.64059 (15) | 0.16895 (15) | 0.0824 (5) | |
H341 | 0.1707 | 0.7138 | 0.1552 | 0.099* | |
C35 | 0.1821 (2) | 0.53782 (18) | 0.08133 (15) | 0.0924 (5) | |
H351 | 0.1519 | 0.5428 | 0.0086 | 0.111* | |
C36 | 0.21478 (15) | 0.42719 (14) | 0.10103 (11) | 0.0677 (3) | |
H361 | 0.2030 | 0.3575 | 0.0421 | 0.081* | |
C4 | 0.27737 (9) | 0.28160 (8) | 0.33645 (7) | 0.03611 (17) | |
H41 | 0.3463 | 0.3420 | 0.3948 | 0.043* | |
C41 | 0.13248 (9) | 0.29317 (8) | 0.36124 (8) | 0.03849 (18) | |
C42 | 0.11811 (11) | 0.33714 (10) | 0.47121 (9) | 0.0468 (2) | |
H421 | 0.1969 | 0.3596 | 0.5272 | 0.056* | |
C43 | −0.01254 (13) | 0.34800 (11) | 0.49874 (11) | 0.0585 (3) | |
H431 | −0.0210 | 0.3769 | 0.5729 | 0.070* | |
C44 | −0.12940 (12) | 0.31609 (12) | 0.41651 (12) | 0.0603 (3) | |
H441 | −0.2169 | 0.3236 | 0.4349 | 0.072* | |
C45 | −0.11651 (11) | 0.27319 (12) | 0.30760 (11) | 0.0591 (3) | |
H451 | −0.1957 | 0.2516 | 0.2521 | 0.071* | |
C46 | 0.01367 (10) | 0.26157 (10) | 0.27909 (9) | 0.0490 (2) | |
H461 | 0.0212 | 0.2325 | 0.2047 | 0.059* | |
C5 | 0.31191 (9) | 0.15025 (8) | 0.33236 (7) | 0.03803 (18) | |
C51 | 0.33326 (10) | 0.12451 (9) | 0.44774 (8) | 0.04175 (19) | |
C52 | 0.43511 (12) | 0.18285 (12) | 0.53906 (9) | 0.0553 (3) | |
H521 | 0.5058 | 0.2459 | 0.5350 | 0.066* | |
C53 | 0.42914 (15) | 0.14456 (14) | 0.63821 (10) | 0.0660 (3) | |
H531 | 0.4980 | 0.1815 | 0.7006 | 0.079* | |
C54 | 0.32346 (15) | 0.05361 (13) | 0.64464 (10) | 0.0648 (3) | |
H541 | 0.3201 | 0.0315 | 0.7121 | 0.078* | |
C55 | 0.22128 (13) | −0.00618 (11) | 0.55273 (10) | 0.0576 (3) | |
H551 | 0.1502 | −0.0683 | 0.5577 | 0.069* | |
C56 | 0.22739 (11) | 0.02863 (9) | 0.45315 (8) | 0.0444 (2) | |
C57 | 0.13980 (10) | −0.01955 (9) | 0.34247 (9) | 0.0437 (2) | |
C58 | 0.02203 (12) | −0.11279 (10) | 0.30486 (11) | 0.0559 (3) | |
H581 | −0.0144 | −0.1555 | 0.3537 | 0.067* | |
C59 | −0.03979 (12) | −0.14080 (11) | 0.19411 (11) | 0.0601 (3) | |
H591 | −0.1207 | −0.2008 | 0.1687 | 0.072* | |
C60 | 0.01684 (12) | −0.08088 (11) | 0.12014 (10) | 0.0571 (3) | |
H601 | −0.0241 | −0.1035 | 0.0450 | 0.069* | |
C61 | 0.13470 (11) | 0.01311 (10) | 0.15679 (9) | 0.0477 (2) | |
H611 | 0.1728 | 0.0533 | 0.1070 | 0.057* | |
C62 | 0.19344 (10) | 0.04506 (8) | 0.26857 (8) | 0.04010 (19) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.03917 (12) | 0.04737 (14) | 0.05093 (14) | 0.01507 (9) | 0.01164 (9) | 0.01707 (10) |
C2 | 0.0356 (4) | 0.0407 (4) | 0.0386 (4) | 0.0073 (3) | 0.0087 (3) | 0.0092 (3) |
C21 | 0.0479 (5) | 0.0439 (5) | 0.0419 (5) | 0.0062 (4) | 0.0113 (4) | 0.0088 (4) |
O22 | 0.0544 (4) | 0.0618 (5) | 0.0504 (4) | 0.0144 (4) | 0.0214 (3) | 0.0050 (3) |
C23 | 0.1013 (11) | 0.0899 (10) | 0.0622 (8) | 0.0268 (9) | 0.0455 (8) | 0.0066 (7) |
O24 | 0.0627 (5) | 0.0847 (6) | 0.0433 (4) | 0.0098 (4) | 0.0007 (4) | 0.0028 (4) |
C25 | 0.0364 (4) | 0.0439 (5) | 0.0485 (5) | 0.0078 (4) | 0.0120 (4) | 0.0082 (4) |
O26 | 0.0785 (6) | 0.0480 (4) | 0.0615 (5) | −0.0063 (4) | 0.0252 (4) | 0.0119 (4) |
C27 | 0.1428 (16) | 0.0568 (8) | 0.1052 (13) | −0.0311 (9) | 0.0529 (12) | 0.0070 (8) |
O28 | 0.0505 (4) | 0.0599 (5) | 0.0528 (4) | 0.0002 (3) | 0.0004 (3) | 0.0029 (4) |
N3 | 0.0355 (3) | 0.0421 (4) | 0.0404 (4) | 0.0107 (3) | 0.0095 (3) | 0.0146 (3) |
C31 | 0.0388 (4) | 0.0480 (5) | 0.0538 (5) | 0.0137 (4) | 0.0143 (4) | 0.0237 (4) |
C32 | 0.0502 (5) | 0.0447 (5) | 0.0669 (7) | 0.0122 (4) | 0.0158 (5) | 0.0196 (5) |
C33 | 0.0649 (7) | 0.0506 (6) | 0.1009 (10) | 0.0222 (5) | 0.0368 (7) | 0.0323 (6) |
C34 | 0.0895 (10) | 0.0796 (9) | 0.1174 (13) | 0.0507 (8) | 0.0524 (9) | 0.0623 (10) |
C35 | 0.1108 (13) | 0.1153 (13) | 0.0874 (11) | 0.0623 (11) | 0.0307 (9) | 0.0653 (11) |
C36 | 0.0813 (9) | 0.0794 (8) | 0.0571 (7) | 0.0365 (7) | 0.0145 (6) | 0.0314 (6) |
C4 | 0.0341 (4) | 0.0374 (4) | 0.0370 (4) | 0.0062 (3) | 0.0064 (3) | 0.0097 (3) |
C41 | 0.0369 (4) | 0.0362 (4) | 0.0454 (5) | 0.0075 (3) | 0.0110 (3) | 0.0133 (4) |
C42 | 0.0476 (5) | 0.0469 (5) | 0.0485 (5) | 0.0094 (4) | 0.0143 (4) | 0.0127 (4) |
C43 | 0.0627 (7) | 0.0582 (6) | 0.0656 (7) | 0.0181 (5) | 0.0337 (6) | 0.0198 (5) |
C44 | 0.0444 (6) | 0.0604 (7) | 0.0877 (9) | 0.0167 (5) | 0.0289 (6) | 0.0271 (6) |
C45 | 0.0379 (5) | 0.0635 (7) | 0.0784 (8) | 0.0107 (5) | 0.0075 (5) | 0.0232 (6) |
C46 | 0.0400 (5) | 0.0551 (6) | 0.0520 (5) | 0.0103 (4) | 0.0062 (4) | 0.0133 (5) |
C5 | 0.0370 (4) | 0.0397 (4) | 0.0390 (4) | 0.0084 (3) | 0.0065 (3) | 0.0123 (3) |
C51 | 0.0445 (5) | 0.0443 (5) | 0.0405 (4) | 0.0139 (4) | 0.0077 (4) | 0.0146 (4) |
C52 | 0.0554 (6) | 0.0646 (7) | 0.0454 (5) | 0.0095 (5) | 0.0008 (5) | 0.0182 (5) |
C53 | 0.0718 (8) | 0.0851 (9) | 0.0434 (6) | 0.0231 (7) | 0.0002 (5) | 0.0209 (6) |
C54 | 0.0833 (9) | 0.0776 (8) | 0.0500 (6) | 0.0329 (7) | 0.0190 (6) | 0.0337 (6) |
C55 | 0.0710 (7) | 0.0568 (6) | 0.0586 (6) | 0.0212 (5) | 0.0225 (6) | 0.0296 (5) |
C56 | 0.0506 (5) | 0.0424 (5) | 0.0471 (5) | 0.0166 (4) | 0.0135 (4) | 0.0170 (4) |
C57 | 0.0458 (5) | 0.0371 (4) | 0.0514 (5) | 0.0113 (4) | 0.0115 (4) | 0.0134 (4) |
C58 | 0.0537 (6) | 0.0437 (5) | 0.0736 (7) | 0.0051 (4) | 0.0184 (5) | 0.0196 (5) |
C59 | 0.0497 (6) | 0.0456 (6) | 0.0772 (8) | −0.0020 (4) | 0.0021 (5) | 0.0117 (5) |
C60 | 0.0552 (6) | 0.0475 (6) | 0.0599 (6) | 0.0043 (5) | −0.0048 (5) | 0.0072 (5) |
C61 | 0.0483 (5) | 0.0452 (5) | 0.0472 (5) | 0.0059 (4) | 0.0028 (4) | 0.0114 (4) |
C62 | 0.0393 (4) | 0.0370 (4) | 0.0449 (5) | 0.0084 (3) | 0.0069 (4) | 0.0112 (4) |
S1—C2 | 1.8338 (10) | C41—C42 | 1.3860 (14) |
S1—C5 | 1.8232 (9) | C42—C43 | 1.3882 (15) |
C2—N3 | 1.4734 (11) | C42—H421 | 0.9300 |
C2—C21 | 1.5336 (13) | C43—C44 | 1.3746 (19) |
C2—C25 | 1.5453 (13) | C43—H431 | 0.9300 |
C21—O24 | 1.1938 (13) | C44—C45 | 1.3679 (19) |
C21—O22 | 1.3321 (12) | C44—H441 | 0.9300 |
O22—C23 | 1.4385 (14) | C45—C46 | 1.3895 (15) |
C23—H231 | 0.9600 | C45—H451 | 0.9300 |
C23—H232 | 0.9600 | C46—H461 | 0.9300 |
C23—H233 | 0.9600 | C5—C51 | 1.5196 (13) |
C25—O28 | 1.1972 (12) | C5—C62 | 1.5203 (13) |
C25—O26 | 1.3229 (13) | C51—C52 | 1.3759 (14) |
O26—C27 | 1.4492 (16) | C51—C56 | 1.4013 (14) |
C27—H271 | 0.9600 | C52—C53 | 1.3991 (16) |
C27—H272 | 0.9600 | C52—H521 | 0.9300 |
C27—H273 | 0.9600 | C53—C54 | 1.368 (2) |
N3—C31 | 1.4454 (12) | C53—H531 | 0.9300 |
N3—C4 | 1.4722 (11) | C54—C55 | 1.3853 (18) |
C31—C36 | 1.3868 (16) | C54—H541 | 0.9300 |
C31—C32 | 1.3931 (16) | C55—C56 | 1.3856 (14) |
C32—C33 | 1.3942 (15) | C55—H551 | 0.9300 |
C32—H321 | 0.9300 | C56—C57 | 1.4649 (14) |
C33—C34 | 1.364 (2) | C57—C58 | 1.3901 (15) |
C33—H331 | 0.9300 | C57—C62 | 1.4006 (14) |
C34—C35 | 1.384 (3) | C58—C59 | 1.3769 (17) |
C34—H341 | 0.9300 | C58—H581 | 0.9300 |
C35—C36 | 1.392 (2) | C59—C60 | 1.3823 (18) |
C35—H351 | 0.9300 | C59—H591 | 0.9300 |
C36—H361 | 0.9300 | C60—C61 | 1.3948 (15) |
C4—C41 | 1.5145 (12) | C60—H601 | 0.9300 |
C4—C5 | 1.5540 (13) | C61—C62 | 1.3790 (14) |
C4—H41 | 0.9800 | C61—H611 | 0.9300 |
C41—C46 | 1.3875 (13) | ||
C5—S1—C2 | 93.89 (4) | C41—C42—C43 | 120.73 (10) |
N3—C2—C21 | 113.81 (7) | C41—C42—H421 | 119.6 |
N3—C2—C25 | 109.60 (7) | C43—C42—H421 | 119.6 |
C21—C2—C25 | 111.95 (7) | C44—C43—C42 | 120.07 (11) |
N3—C2—S1 | 106.14 (6) | C44—C43—H431 | 120.0 |
C21—C2—S1 | 104.40 (6) | C42—C43—H431 | 120.0 |
C25—C2—S1 | 110.67 (6) | C45—C44—C43 | 119.77 (10) |
O24—C21—O22 | 124.68 (10) | C45—C44—H441 | 120.1 |
O24—C21—C2 | 126.50 (9) | C43—C44—H441 | 120.1 |
O22—C21—C2 | 108.70 (8) | C44—C45—C46 | 120.67 (11) |
C21—O22—C23 | 116.73 (10) | C44—C45—H451 | 119.7 |
O22—C23—H231 | 109.5 | C46—C45—H451 | 119.7 |
O22—C23—H232 | 109.5 | C41—C46—C45 | 120.18 (11) |
H231—C23—H232 | 109.5 | C41—C46—H461 | 119.9 |
O22—C23—H233 | 109.5 | C45—C46—H461 | 119.9 |
H231—C23—H233 | 109.5 | C51—C5—C62 | 102.15 (7) |
H232—C23—H233 | 109.5 | C51—C5—C4 | 111.78 (7) |
O28—C25—O26 | 125.31 (10) | C62—C5—C4 | 113.87 (7) |
O28—C25—C2 | 123.90 (9) | C51—C5—S1 | 111.91 (6) |
O26—C25—C2 | 110.50 (8) | C62—C5—S1 | 115.28 (6) |
C25—O26—C27 | 115.97 (10) | C4—C5—S1 | 102.24 (6) |
O26—C27—H271 | 109.5 | C52—C51—C56 | 121.18 (9) |
O26—C27—H272 | 109.5 | C52—C51—C5 | 128.95 (9) |
H271—C27—H272 | 109.5 | C56—C51—C5 | 109.85 (8) |
O26—C27—H273 | 109.5 | C51—C52—C53 | 118.02 (12) |
H271—C27—H273 | 109.5 | C51—C52—H521 | 121.0 |
H272—C27—H273 | 109.5 | C53—C52—H521 | 121.0 |
C31—N3—C4 | 115.46 (7) | C54—C53—C52 | 120.89 (12) |
C31—N3—C2 | 115.12 (7) | C54—C53—H531 | 119.6 |
C4—N3—C2 | 109.65 (7) | C52—C53—H531 | 119.6 |
C36—C31—C32 | 119.41 (10) | C53—C54—C55 | 121.33 (11) |
C36—C31—N3 | 118.49 (10) | C53—C54—H541 | 119.3 |
C32—C31—N3 | 122.03 (9) | C55—C54—H541 | 119.3 |
C31—C32—C33 | 120.01 (12) | C54—C55—C56 | 118.52 (12) |
C31—C32—H321 | 120.0 | C54—C55—H551 | 120.7 |
C33—C32—H321 | 120.0 | C56—C55—H551 | 120.7 |
C34—C33—C32 | 120.48 (14) | C55—C56—C51 | 120.01 (10) |
C34—C33—H331 | 119.8 | C55—C56—C57 | 131.24 (10) |
C32—C33—H331 | 119.8 | C51—C56—C57 | 108.74 (8) |
C33—C34—C35 | 119.78 (12) | C58—C57—C62 | 120.20 (10) |
C33—C34—H341 | 120.1 | C58—C57—C56 | 131.07 (10) |
C35—C34—H341 | 120.1 | C62—C57—C56 | 108.73 (9) |
C34—C35—C36 | 120.64 (14) | C59—C58—C57 | 118.92 (11) |
C34—C35—H351 | 119.7 | C59—C58—H581 | 120.5 |
C36—C35—H351 | 119.7 | C57—C58—H581 | 120.5 |
C31—C36—C35 | 119.62 (14) | C58—C59—C60 | 120.85 (10) |
C31—C36—H361 | 120.2 | C58—C59—H591 | 119.6 |
C35—C36—H361 | 120.2 | C60—C59—H591 | 119.6 |
N3—C4—C41 | 112.73 (7) | C59—C60—C61 | 120.80 (11) |
N3—C4—C5 | 105.01 (7) | C59—C60—H601 | 119.6 |
C41—C4—C5 | 113.31 (7) | C61—C60—H601 | 119.6 |
N3—C4—H41 | 108.5 | C62—C61—C60 | 118.50 (10) |
C41—C4—H41 | 108.5 | C62—C61—H611 | 120.8 |
C5—C4—H41 | 108.5 | C60—C61—H611 | 120.8 |
C46—C41—C42 | 118.58 (9) | C61—C62—C57 | 120.61 (9) |
C46—C41—C4 | 123.05 (9) | C61—C62—C5 | 129.51 (9) |
C42—C41—C4 | 118.37 (8) | C57—C62—C5 | 109.81 (8) |
C5—S1—C2—N3 | −1.44 (6) | C42—C41—C46—C45 | −0.52 (15) |
C5—S1—C2—C21 | −121.98 (6) | C4—C41—C46—C45 | 179.34 (9) |
C5—S1—C2—C25 | 117.40 (6) | C44—C45—C46—C41 | 0.19 (17) |
N3—C2—C21—O24 | −3.04 (15) | N3—C4—C5—C51 | 165.36 (7) |
C25—C2—C21—O24 | −128.00 (11) | C41—C4—C5—C51 | −71.19 (10) |
S1—C2—C21—O24 | 112.24 (11) | N3—C4—C5—C62 | −79.51 (9) |
N3—C2—C21—O22 | −179.19 (8) | C41—C4—C5—C62 | 43.93 (10) |
C25—C2—C21—O22 | 55.85 (10) | N3—C4—C5—S1 | 45.50 (7) |
S1—C2—C21—O22 | −63.91 (9) | C41—C4—C5—S1 | 168.95 (6) |
O24—C21—O22—C23 | 2.21 (17) | C2—S1—C5—C51 | −144.65 (7) |
C2—C21—O22—C23 | 178.45 (10) | C2—S1—C5—C62 | 99.20 (7) |
N3—C2—C25—O28 | 71.96 (12) | C2—S1—C5—C4 | −24.88 (6) |
C21—C2—C25—O28 | −160.77 (10) | C62—C5—C51—C52 | 173.74 (10) |
S1—C2—C25—O28 | −44.76 (12) | C4—C5—C51—C52 | −64.14 (13) |
N3—C2—C25—O26 | −102.18 (9) | S1—C5—C51—C52 | 49.86 (13) |
C21—C2—C25—O26 | 25.08 (11) | C62—C5—C51—C56 | −7.75 (10) |
S1—C2—C25—O26 | 141.10 (7) | C4—C5—C51—C56 | 114.37 (9) |
O28—C25—O26—C27 | 1.98 (18) | S1—C5—C51—C56 | −131.63 (7) |
C2—C25—O26—C27 | 176.03 (13) | C56—C51—C52—C53 | −0.69 (16) |
C21—C2—N3—C31 | −83.48 (10) | C5—C51—C52—C53 | 177.68 (10) |
C25—C2—N3—C31 | 42.73 (10) | C51—C52—C53—C54 | −1.33 (19) |
S1—C2—N3—C31 | 162.27 (7) | C52—C53—C54—C55 | 1.9 (2) |
C21—C2—N3—C4 | 144.33 (8) | C53—C54—C55—C56 | −0.43 (19) |
C25—C2—N3—C4 | −89.46 (9) | C54—C55—C56—C51 | −1.57 (16) |
S1—C2—N3—C4 | 30.08 (8) | C54—C55—C56—C57 | 177.23 (11) |
C4—N3—C31—C36 | −149.05 (10) | C52—C51—C56—C55 | 2.16 (15) |
C2—N3—C31—C36 | 81.56 (12) | C5—C51—C56—C55 | −176.49 (9) |
C4—N3—C31—C32 | 27.96 (12) | C52—C51—C56—C57 | −176.89 (9) |
C2—N3—C31—C32 | −101.43 (10) | C5—C51—C56—C57 | 4.46 (11) |
C36—C31—C32—C33 | −0.36 (16) | C55—C56—C57—C58 | 1.82 (19) |
N3—C31—C32—C33 | −177.34 (9) | C51—C56—C57—C58 | −179.27 (10) |
C31—C32—C33—C34 | −1.38 (18) | C55—C56—C57—C62 | −177.77 (10) |
C32—C33—C34—C35 | 1.1 (2) | C51—C56—C57—C62 | 1.14 (11) |
C33—C34—C35—C36 | 0.9 (3) | C62—C57—C58—C59 | 0.48 (16) |
C32—C31—C36—C35 | 2.31 (19) | C56—C57—C58—C59 | −179.07 (11) |
N3—C31—C36—C35 | 179.40 (13) | C57—C58—C59—C60 | 2.45 (18) |
C34—C35—C36—C31 | −2.6 (2) | C58—C59—C60—C61 | −2.70 (19) |
C31—N3—C4—C41 | 53.79 (10) | C59—C60—C61—C62 | −0.07 (17) |
C2—N3—C4—C41 | −174.21 (7) | C60—C61—C62—C57 | 3.00 (15) |
C31—N3—C4—C5 | 177.60 (7) | C60—C61—C62—C5 | −173.75 (10) |
C2—N3—C4—C5 | −50.39 (9) | C58—C57—C62—C61 | −3.25 (14) |
N3—C4—C41—C46 | 33.13 (12) | C56—C57—C62—C61 | 176.40 (9) |
C5—C4—C41—C46 | −85.97 (11) | C58—C57—C62—C5 | 174.09 (9) |
N3—C4—C41—C42 | −147.02 (9) | C56—C57—C62—C5 | −6.27 (10) |
C5—C4—C41—C42 | 93.88 (10) | C51—C5—C62—C61 | −174.52 (10) |
C46—C41—C42—C43 | 0.72 (15) | C4—C5—C62—C61 | 64.80 (13) |
C4—C41—C42—C43 | −179.14 (9) | S1—C5—C62—C61 | −52.93 (12) |
C41—C42—C43—C44 | −0.59 (17) | C51—C5—C62—C57 | 8.45 (9) |
C42—C43—C44—C45 | 0.25 (18) | C4—C5—C62—C57 | −112.23 (9) |
C43—C44—C45—C46 | −0.05 (19) | S1—C5—C62—C57 | 130.04 (7) |
Experimental details
(VI) | (VII) | |
Crystal data | ||
Chemical formula | C28H31NO4S·0.275CH4O | C31H25NO4S |
Mr | 486.43 | 507.58 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 160 | 293 |
a, b, c (Å) | 15.6658 (2), 18.1538 (3), 17.2513 (3) | 9.817 (1), 11.233 (2), 12.459 (2) |
α, β, γ (°) | 90, 90.2397 (6), 90 | 102.53 (1), 97.91 (1), 98.52 (1) |
V (Å3) | 4906.12 (13) | 1305.7 (4) |
Z | 8 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.17 | 0.16 |
Crystal size (mm) | 0.35 × 0.18 × 0.15 | 0.8 × 0.7 × 0.5 |
Data collection | ||
Diffractometer | Nonius KappaCCD area-detector diffractometer | Rigaku AFC-5S diffractometer |
Absorption correction | – | Analytical (de Meulenaer & Tompa, 1965) |
Tmin, Tmax | – | 0.897, 0.937 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 76328, 11220, 7745 | 18942, 9471, 6330 |
Rint | 0.071 | 0.017 |
(sin θ/λ)max (Å−1) | 0.649 | 0.758 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.110, 1.02 | 0.036, 0.121, 1.06 |
No. of reflections | 11217 | 9471 |
No. of parameters | 641 | 337 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.39, −0.29 | 0.29, −0.24 |
Computer programs: COLLECT (Nonius, 2000), MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1989), DENZO–SMN (Otwinowski & Minor, 1997), MSC/AFC Diffractometer Control Software, DENZO–MN and SCALEPACK (Otwinowski & Minor, 1997), TEXSAN (Molecular Structure Corporation, 1989), SIR92 (Altomare et al., 1994), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and PLATON (Spek, 2003), PLATON (Spek, 2003), SHELXL97 and PLATON.
S1A—C2A | 1.8144 (16) | S1B—C2B | 1.8087 (16) |
S1A—C5A | 1.8413 (16) | S1B—C5B | 1.8400 (16) |
C2A—N3A | 1.464 (2) | C2B—N3B | 1.463 (2) |
N3A—C4A | 1.4612 (19) | N3B—C4B | 1.4619 (19) |
C4A—C5A | 1.609 (2) | C4B—C5B | 1.613 (2) |
C2A—S1A—C5A | 95.23 (7) | C2B—S1B—C5B | 94.02 (7) |
N3A—C2A—S1A | 106.17 (10) | N3B—C2B—S1B | 105.93 (10) |
C4A—N3A—C2A | 116.81 (12) | C4B—N3B—C2B | 116.51 (12) |
N3A—C4A—C5A | 108.06 (12) | N3B—C4B—C5B | 107.02 (12) |
C4A—C5A—S1A | 100.87 (10) | C4B—C5B—S1B | 99.93 (10) |
S1A—C2A—C21A—C26A | 100.57 (16) | S1B—C2B—C21B—C26B | 109.83 (15) |
C2A—N3A—C31A—C36A | 23.5 (2) | C2B—N3B—C31B—C36B | 21.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O61—H61···O44A | 0.85 (4) | 2.03 (4) | 2.788 (3) | 148 (4) |
O61—H61···O48A | 0.85 (4) | 2.43 (4) | 3.099 (3) | 136 (4) |
C43A—H433···O44B | 0.98 | 2.54 | 3.375 (2) | 144 |
C43B—H436···O44A | 0.98 | 2.49 | 3.439 (2) | 162 |
C43B—H434···O61i | 0.98 | 2.33 | 3.215 (3) | 151 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
S1—C2 | 1.8338 (10) | N3—C4 | 1.4722 (11) |
S1—C5 | 1.8232 (9) | C4—C5 | 1.5540 (13) |
C2—N3 | 1.4734 (11) | ||
C5—S1—C2 | 93.89 (4) | N3—C4—C5 | 105.01 (7) |
N3—C2—S1 | 106.14 (6) | C4—C5—S1 | 102.24 (6) |
C4—N3—C2 | 109.65 (7) | ||
C2—N3—C31—C36 | 81.56 (12) |
1,3-Thiazolidines may be used in the synthesis of pharmaceuticals such as immunomodulating drugs or antibiotics (Hwu et al., 1999; Pellegrini et al., 1999). Thioketones are recognized as `superdipolarophilic' compounds and combine smoothly with 1,3-dipoles to yield sulfur-containing five-membered heterocycles (Huisgen et al., 1995). However, there are few papers dealing with the reactions of azomethine ylides with thioketones. Heating 1,2,3-triazoline, (I), with adamantane-2-thione, (IV), or 9H-fluorene-9-thione, (V), in boiling toluene, resulted in the formation of 1,3-thiazolidines (VI) or (VII), respectively (Mlostoń & Skrzypek, 1990) (see Scheme). The molecular formulae of C28H31NO4S for (VI) and C31H25NO4S for (VII) were established from elemental analyses and mass spectra. Desulfurization of (VII) with Raney nickel resulted unexpectedly in ring contraction and formation of the corresponding azetidine derivative (Mlostoń et al., 2000, 2002). On the other hand, the same procedure with (VI) led to recovery of the starting material, which suggested that the formation of (VI) and (VII) had occurred with different regioselectivity. The X-ray crystallographic analyses of (VI) and (VII) were undertaken to elucidate their structures and thereby determine the influence of the location of the ester groups on the course of the subsequent desulfurization reaction. The two structures (Figs. 1 and 2) confirm that the regioselectivity of the addition step leading to the formation of the heterocyclic ring from thioketones and azomethine ylides is dependent on the type of thioketone used (see Scheme).
The asymmetric unit of compound (VI) contains two independent molecules of the thiazolidine derivative plus a site for a methanol molecule which is approximately 55% occupied. Although the unit cell is metrically very close to orthorhombic, tests with PLATON (Spek, 2003) indicated the absence of any additional crystallographic symmetry. The two symmetry-independent thiazolidine molecules have the same configuration and almost identical conformations. The weighted r.m.s. fit (Mackay, 1984) of the atoms from the two molecules is 0.18 Å and the two molecules are related by a rotation of approximately 175°. Compound (VII) crystallizes with just one independent molecule in the asymmetric unit. The bond lengths and angles in the two structures are generally in good agreement with expected values (Allen et al., 1987), although in (VI), the C4A—C5A and C4B—C5B bonds are quite long at about 1.61 Å and the S—C bond lengths are asymmetric (Table 1). As a consequence of the long C—C bonds, the C2A—N3A—C4A and C2B—N3B—C4B bond angles are larger than the corresponding angles in compound (VII), where the C4—C5 bond is not unduly long and the S—C bonds are more symmetrical (Table 2). Elongation of C—C bonds in the range 1.56–1.61 Å has been observed frequently in spirocyclic thiazolidine, thiazole, oxathiolane and dithiolane ring systems (Linden et al., 1998). Steric crowding is probably responsible for the observed geometry of the thiazolidine ring in compound (VI). There are several very short intramolecular contacts between the H atoms of the adamantanyl group and the ester C and O atoms, as well as with the thiazolidine S atom. The shortest contacts of this type are 2.29 and 2.31 Å for H591···C45A and H593···C45B, respectively, which are approximately 0.6 Å shorter than the sum of the van der Waals radii of these atoms, and three other H···C or H···S contacts in each of the independent molecules are between 0.37–0.51 Å shorter than the sum of the van der Waals radii. The steric constraints introduced by the adamantanyl group also severely restrict the orientations that can be adopted by the ester substituents, which results in additional short intramolecular contacts, namely O44A···O48A [2.7221 (16) Å], O44B···O48B [2.7415 (18) Å], O42A···N3A [2.6230 (17) Å], O46A···N3A [2.6094 (16) Å], O42B···N3B [2.6001 (18) Å] and O46B···N3B [2.5896 (16) Å]. By contrast, the less bulky planar fluorenyl substituent in compound (VII) is not involved in any unduly short intramolecular contacts and the bond lengths and angles within the thiazolidine ring are consequently less distorted than in compound (VI).
The 1,3-thiazolidine rings of both compounds have envelope conformations. For compound (VI), the puckering parameters (Cremer & Pople, 1975) are q2 = 0.3953 (14) and 0.4549 (14) Å, and ϕ2 = 146.7 (2) and 150.87 (19)° for the rings defined by the atom sequences S1A—C2A—N3A—C4A—C5A and S1B—C2B—N3B—C4B—C5B, respectively, and the envelope flaps are formed by the spiro-C atoms C5A and C5B, respectively. For compound (VII), the puckering parameters are q2 = 0.4592 (9) Å and ϕ2 = 110.25 (10)° for the atom sequence S1—C2—N3—C4—C5, with atom C4 forming the envelope flap.
The phenyl substituents at atoms C2A and C2B of compound (VI) occupy pseudo-axial positions, while those at atoms N3A and N3B, as well as all the phenyl substituents in compound (VII), occupy pseudo-equatorial positions. In compound (VII), the planes of both phenyl substituents lie almost perpendicular to the mean plane of the 1,3-thiazolidine ring, with interplanar angles of 61.06 (4) and 65.14 (3)° for the phenyl substituents at N3 and C4, respectively. The planes of the phenyl substituents at atoms C2A and C2B of compound (VI) are aligned similarly, with the corresponding interplanar angles being 75.39 (5) and 72.04 (5)°, respectively. In contrast, the planes of the phenyl substituents at atoms N3A and N3B of compound (VI) lie almost parallel to the planes of the respective 1,3-thiazolidine rings, with interplanar angles of 21.30 (8) and 21.67 (8)°, respectively.
The fluorene substituent in compound (VII) is almost planar, although slight envelope puckering of the central five-membered ring pushes the spiro-C atom, C5, out of the plane and gives the entire fluorene moiety a flat-dish shape. Excluding atom C5, the r.m.s. deviation of atoms C51 to C62 from their mean plane is 0.040 Å, with a maximum deviation of 0.0638 (9) Å for atom C51. Atom C5 lies 0.1896 (11) Å from this plane. The flatness of the dish is shown by the angle of intersection between the two phenyl rings of the fluorene moiety, which is 4.50 (7)°.
In compound (VI), the hydroxy group of the methanol molecule forms bifurcated intermolecular hydrogen bonds with both of the ester carbonyl O atoms of a neighbouring thiazolidine molecule, although one interaction is significantly weaker then the other (Table 2). These interactions form a six-membered loop with a graph-set motif of R21(6) (Bernstein et al., 1995). Two intermolecular C—H···O interactions link the independent thiazolidine molecules to each other and a third interaction links one of these molecules to a neighbouring methanol molecule. The combination of O—H···O and C—H···O interactions links two of each of the independent thiazolidine molecules and two methanol molecules into a closed centrosymmetric hexameric unit (Fig. 3). Compound (VII) does not display any significant intermolecular C—H···O interactions.