Supporting Information
Synthesis and Stereochemistry of New Spiro[5.5]undecane Derivatives with 1,3-Dioxane, 1,3-Dithiane or 1,3-Oxathiane Rings
AlinMihiş, LigiaMirabelaGolban, CiprianI.Raţ, Elena Bogdan, AnamariaTerec* and Ion Grosu*
Babes-BolyaiUniversity, Center of Supramolecular Organic and Organometallic Chemistry, Cluj-Napoca, 11 Arany Janos, 400028, Cluj-Napoca, Romania;
Contents
Theoretical calculations details21
References22
Figure S1. Optimized structure (ADF BP86/TZ2P) of 12.23
Figure S2. Optimized structure (ADF BP86/TZ2P) of the ax-ax isomer of 15.23
Figure S3. Optimized structure (ADF BP86/TZ2P) of the ax-eq isomer of 15.24
Figure S4. Optimized structure (ADF BP86/TZ2P) of the eq-eq isomer of 15.24
Table S1. Cartesian coordinates (Å) of the optimized structure (ADF BP86/TZ2P) of the 1,3-dioxane-1,3-dithiane derivative 12. 25
Table S2. Cartesian coordinates (Å) of the optimized structure (ADF BP86/TZ2P) of the ax-ax isomer of the bis(1,3-oxathiane) derivatives 15. 26
Table S3. Cartesian coordinates (Å) of the optimized structure (ADF BP86/TZ2P) of the ax-eq isomer of the bis(1,3-oxathiane) derivatives 15. 27
Table S4. Cartesian coordinates (Å) of the optimized structure (ADF BP86/TZ2P) of the eq-eq isomer of the bis(1,3-oxathiane) derivatives 15. 28
Table S5. Cartesian coordinates (Å) of the optimized structure (GAMESS B3LYP/6-31G(d)) of the 1,3-dioxane-1,3-dithiane derivative 12. 29
Table S6. Cartesian coordinates (Å) of the optimized structure (GAMESS B3LYP/6-31G(d)) of the ax-ax isomer of the bis(1,3-oxathiane) derivatives 15. 30
Table S7. Cartesian coordinates (Å) of the optimized structure (GAMESS B3LYP/6-31G(d)) of the ax-eq isomer of the bis(1,3-oxathiane) derivatives 15. 31
Table S8. Cartesian coordinates (Å) of the optimized structure (GAMESS B3LYP/6-31G(d)) of the eq-eq isomer of the bis(1,3-oxathiane) derivatives 15. 32
Table S9. Cartesian coordinates (Å) of the optimized structure (ORCA B3LYP/6-31G(d,p)) of the 1,3-dioxane-1,3-dithiane derivative 12. 33
Table S10. Cartesian coordinates (Å) of the optimized structure (ORCA B3LYP/6-31G(d,p)) of the ax-ax isomer of the bis(1,3-oxathiane) derivatives 15. 34
Table S11. Cartesian coordinates (Å) of the optimized structure (ORCA B3LYP/6-31G(d,p)) of the ax-eq isomer of the bis(1,3-oxathiane) derivatives 15. 35
Table S12. Cartesian coordinates (Å) of the optimized structure (ORCA B3LYP/6-31G(d,p)) of the eq-eq isomer of the bis(1,3-oxathiane) derivatives 15. 36
Theoretical calculations details
Theoretical calculations for 12 and the ax-ax, ax-eq, and eq-eq isomers of 15 were carried out using the ADF2008.1e,S1–S3 GAMESS 2010 R2,S4,S5 and ORCA 2.7 software packages.
For the geometry optimizations calculations performed with with ADF software package the BP86 functional and a TZ2P basis set with a large frozen core were used. The energy minimum of the optimized structures was confirmed by frequency calculations performed at the same theory level as the geometry optimization calculations. The frequencies were calculated analytically and for all compounds the IR spectra showed a number of imaginary frequencies: 1 for 12 at –5.182 cm–1, 2 for ax-ax15 at –8.975 and –6.804 cm–1, 1 for ax-eq15 at –4.921 cm–1, and 1 for eq-eq10b at –13.881 cm–1. Calculations of the gradients along the corresponding normal modes of the imaginary frequencies revealed that they emerge from the summation of the numerical errors.
The calculations with the GAMESS software package were performed using the B3LYP functional (with VWN5 for the local correlation part) and using the 6-31G basis set augmented with one d function for all the atoms.
Geometry optimizations and frequency calculations with ORCA were carried out using B3LYP functional and the 6-31G(d,p) basis set as implemented in the software package. For all the calculations the Grid 4 and TightSCF options were selected. The frequency calculations on the 15 isomers revealed that the optimized geometries are energy minima. In the frequency calculation of 12 a negative value was obtained at –12.42 cm–1. The small value corresponding to the negative calculated frequency suggests that it is likely to emerge from the summation of the numerical errors.
The cartesian coordinates of the optimized structures are listed in Tables S1 - S12 and graphical representations of the structures optimized with ADF are shown in Figures S1 - S4.
References
(S1) G. te Velde, F. M. Bickelhaupt, S. J. A. van Gisbergen, C. Fonseca Guerra, E. J. Baerends, J. G. Snijders and T. Ziegler, J. Comp. Chem. 2001, 22, 931.
(S2) C. Fonseca Guerra, J. G. Snijders, G. te Velde, E. J. Baerends, Theor. Chem. Acc. 1998, 99, 391.
(S3) E. J. Baerends, J. Autschbach, A. Bérces, F. M. Bickelhaupt, C. Bo, P. M. Boerrigter, L. Cavallo, D. P. Chong, L. Deng, R. M. Dickson, D. E. Ellis, M. van Faassen, L. Fan, T. H. Fischer, C. Fonseca Guerra, S. J. A. van Gisbergen, A. W. Götz, J .A. Groeneveld, O. V. Gritsenko, M. Grüning, F. E. Harris, P. van den Hoek, C. R. Jacob, H. Jacobsen, L. Jensen, G. van Kessel, F. Kootstra, M. V. Krykunov, E. van Lenthe, D. A. McCormack, A. Michalak, J. Neugebauer, V. P. Nicu, V. P. Osinga, S. Patchkovskii, P. H. T. Philipsen, D. Post, C. C. Pye, W. Ravenek, J. I. Rodríguez, P. Ros, P. R. T. Schipper, G. Schreckenbach, J. G. Snijders, M. Solà, M. Swart, D. Swerhone, G. te Velde, P. Vernooijs, L. Versluis, L. Visscher, O. Visser, F. Wang, T.A. Wesolowski, E. M. van Wezenbeek, G. Wiesenekker, S. K. Wolff, T. K. Woo, A. L. Yakovlev, T. Ziegler, ADF2008.01e, SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands,
(S4) M. W. Schmidt, K. K.Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. Su, T. L. Windus, M. Dupuis, J. A. Montgomery J. Comput. Chem.1993,14, 1347.
(S5) M. S. Gordon, M. W. Schmidt, Advances in electronic structure theory: GAMESS a decade later, , in "Theory and Applications of Computational Chemistry: the first forty years" C. E. Dykstra, G. Frenking, K. S. Kim, G. E. Scuseria (editors), Elsevier, Amsterdam, 2005, pp. 1167-1189.
(S6) Neese, F. ORCA, version 2.7; University of Bonn: Bonn, Germany, 2008.
Figure S1. Optimized structure (ADF BP86/TZ2P) of 12.
Figure S2. Optimized structure (ADF BP86/TZ2P) of the ax-ax isomer of 15.
Figure S3. Optimized structure (ADF BP86/TZ2P) of the ax-eq isomer of 15.
Figure S4. Optimized structure (ADF BP86/TZ2P) of the eq-eq isomer of 15.
Table S1. Cartesian coordinates (Å) of the optimized structure (ADFBP86/TZ2P) of the 1,3-dioxane-1,3-dithiane derivative 12.
Atom / x / y / z1 / C / 0.983739 / -0.280600 / -1.988783
2 / C / 3.162724 / -0.564111 / -0.259889
3 / C / 0.699502 / 0.585292 / 0.379309
4 / C / 0.002558 / -0.083871 / -0.815777
5 / H / 1.386029 / 0.696684 / -2.300049
6 / H / 0.455475 / -0.712589 / -2.848247
7 / H / -0.020118 / 0.780367 / 1.188126
8 / H / 1.110928 / 1.558591 / 0.066419
9 / H / 3.451646 / 0.444015 / -0.585775
10 / C / -0.688931 / -1.400599 / -0.413856
11 / H / -1.297067 / -1.233503 / 0.496135
12 / H / 0.041790 / -2.190671 / -0.211824
13 / C / -1.126027 / 0.869051 / -1.275428
14 / H / -1.753626 / 1.132559 / -0.401380
15 / H / -0.720372 / 1.794895 / -1.705076
16 / C / -2.514900 / -0.940402 / -1.827420
17 / H / -3.118042 / -0.706331 / -0.919425
18 / S / 2.033648 / -0.377734 / 1.188143
19 / S / 2.383326 / -1.422809 / -1.689277
20 / O / -1.527003 / -1.887013 / -1.473619
21 / O / -1.938159 / 0.276819 / -2.291471
22 / C / 4.384636 / -1.329095 / 0.179884
23 / C / 5.646005 / -0.719057 / 0.142864
24 / C / 4.274683 / -2.651512 / 0.638963
25 / C / 6.782493 / -1.407407 / 0.558559
26 / H / 5.738737 / 0.306356 / -0.213576
27 / C / 5.401847 / -3.351995 / 1.057938
28 / H / 3.296095 / -3.129490 / 0.666759
29 / C / 6.641607 / -2.716468 / 1.013257
30 / H / 7.769102 / -0.951965 / 0.539146
31 / H / 5.339197 / -4.375631 / 1.418184
32 / C / -3.396971 / -1.509456 / -2.916913
33 / C / -3.563205 / -2.894328 / -3.042599
34 / C / -4.080343 / -0.644765 / -3.781829
35 / C / -4.400380 / -3.415485 / -4.026315
36 / H / -3.021913 / -3.561424 / -2.375277
37 / C / -4.919016 / -1.153963 / -4.768993
38 / H / -3.939198 / 0.429831 / -3.687466
39 / C / -5.066264 / -2.535252 / -4.876196
40 / H / -4.541199 / -4.486186 / -4.149428
41 / H / -5.454502 / -0.504894 / -5.456884
42 / N / -5.953297 / -3.082744 / -5.928173
43 / N / 7.844926 / -3.452915 / 1.465378
44 / O / -6.526078 / -2.276758 / -6.670138
45 / O / -6.066519 / -4.311443 / -5.999289
46 / O / 7.689454 / -4.612424 / 1.863159
47 / O / 8.929005 / -2.861037 / 1.417342
Table S2. Cartesian coordinates (Å) of the optimized structure (ADFBP86/TZ2P) of the ax-ax isomer of the bis(1,3-oxathiane) derivatives 15.
Atom / x / y / z1 / C / 0.532154 / -0.457039 / -1.208301
2 / C / 2.992392 / -0.211099 / -0.018718
3 / C / 1.162057 / 1.176540 / 0.592016
4 / C / 0.018124 / 0.308074 / 0.026013
5 / H / 0.805960 / 0.255743 / -2.002244
6 / H / -0.245392 / -1.125572 / -1.598853
7 / H / 0.823050 / 1.737778 / 1.473305
8 / H / 1.481572 / 1.904371 / -0.179221
9 / H / 3.234517 / 0.533353 / -0.798997
10 / C / -0.515689 / -0.628715 / 1.126327
11 / H / -0.773899 / -0.043010 / 2.022769
12 / H / 0.245307 / -1.368293 / 1.405462
13 / C / -1.104061 / 1.281143 / -0.394722
14 / H / -1.406965 / 1.887125 / 0.481429
15 / H / -0.750669 / 1.964703 / -1.178582
16 / C / -2.967408 / -0.141257 / -0.003331
17 / H / -3.191332 / 0.477150 / 0.885017
18 / O / 2.293201 / 0.425097 / 1.035631
19 / S / 1.969108 / -1.532603 / -0.834902
20 / S / -1.976877 / -1.598568 / 0.592112
21 / O / -2.252383 / 0.635296 / -0.947188
22 / C / 4.248183 / -0.855893 / 0.506850
23 / C / 5.283766 / -1.174542 / -0.383719
24 / C / 4.381253 / -1.170978 / 1.864949
25 / C / 6.438237 / -1.803932 / 0.069652
26 / H / 5.181707 / -0.932431 / -1.441730
27 / C / 5.533811 / -1.798103 / 2.331981
28 / H / 3.579485 / -0.916011 / 2.554025
29 / C / 6.545405 / -2.107874 / 1.426170
30 / H / 7.253436 / -2.060694 / -0.601624
31 / H / 5.661195 / -2.052498 / 3.381092
32 / C / -4.238738 / -0.664775 / -0.618731
33 / C / -5.278434 / -1.101806 / 0.215081
34 / C / -4.383169 / -0.751240 / -2.009033
35 / C / -6.448273 / -1.623398 / -0.326913
36 / H / -5.167511 / -1.037851 / 1.297674
37 / C / -5.551156 / -1.268425 / -2.564138
38 / H / -3.577987 / -0.404893 / -2.652720
39 / C / -6.566579 / -1.699589 / -1.714059
40 / H / -7.267016 / -1.968179 / 0.299056
41 / H / -5.687718 / -1.345306 / -3.639770
42 / N / 7.770727 / -2.776873 / 1.917991
43 / N / -7.808848 / -2.251248 / -2.300076
44 / O / 8.651036 / -3.038870 / 1.090555
45 / O / 7.837780 / -3.032582 / 3.125513
46 / O / -8.693073 / -2.623550 / -1.520487
47 / O / -7.885130 / -2.305806 / -3.532642
Table S3. Cartesian coordinates (Å) of the optimized structure (ADFBP86/TZ2P) of the ax-eq isomer of the bis(1,3-oxathiane) derivatives 15.
Atom / x / y / z1 / C / 0.638142 / -0.424947 / -1.187000
2 / C / 2.894327 / -0.558160 / -0.440949
3 / C / 1.167334 / 1.360186 / 0.495239
4 / C / 0.065443 / 0.416103 / -0.029445
5 / H / 0.965815 / 0.251683 / -1.999522
6 / H / -0.126250 / -1.103922 / -1.578707
7 / H / 0.809258 / 1.954449 / 1.348242
8 / H / 1.467647 / 2.061012 / -0.300199
9 / H / 3.160163 / 0.153057 / -1.244425
10 / C / -0.477095 / -0.461290 / 1.115249
11 / H / -0.789578 / 0.180092 / 1.954718
12 / H / 0.300525 / -1.141319 / 1.484293
13 / C / -1.075587 / 1.304282 / -0.567771
14 / H / -1.430698 / 1.963344 / 0.247743
15 / H / -0.718482 / 1.940022 / -1.389411
16 / C / -2.902492 / -0.155922 / -0.134202
17 / H / -3.184895 / 0.519323 / 0.693892
18 / S / 2.651763 / 0.467278 / 1.103839
19 / O / 1.729437 / -1.264078 / -0.793325
20 / S / -1.881787 / -1.522741 / 0.608647
21 / O / -2.179671 / 0.573204 / -1.109257
22 / C / -4.126201 / -0.780477 / -0.751705
23 / C / -5.190809 / -1.170835 / 0.073589
24 / C / -4.198199 / -1.012500 / -2.131031
25 / C / -6.313091 / -1.791377 / -0.464917
26 / H / -5.136368 / -0.993349 / 1.147853
27 / C / -5.318154 / -1.629379 / -2.683121
28 / H / -3.374199 / -0.702025 / -2.769301
29 / C / -6.358825 / -2.013130 / -1.840623
30 / H / -7.149300 / -2.103737 / 0.154986
31 / H / -5.397962 / -1.820664 / -3.750198
32 / C / 4.026213 / -1.520974 / -0.187036
33 / C / 5.346852 / -1.049146 / -0.166216
34 / C / 3.771592 / -2.878865 / 0.043303
35 / C / 6.403742 / -1.916907 / 0.088186
36 / H / 5.548030 / 0.006910 / -0.347335
37 / C / 4.821683 / -3.758073 / 0.296627
38 / H / 2.747423 / -3.242926 / 0.012118
39 / C / 6.123297 / -3.263340 / 0.317942
40 / H / 7.435138 / -1.575030 / 0.108523
41 / H / 4.649866 / -4.816170 / 0.476968
42 / N / 7.241745 / -4.194622 / 0.588098
43 / N / -7.548808 / -2.673394 / -2.422781
44 / O / -8.456287 / -3.001867 / -1.650234
45 / O / -7.560931 / -2.856416 / -3.645214
46 / O / 8.386185 / -3.726965 / 0.598189
47 / O / 6.962176 / -5.381898 / 0.787885
Table S4. Cartesian coordinates (Å) of the optimized structure (ADFBP86/TZ2P) of the eq-eq isomer of the bis(1,3-oxathiane) derivatives 15.
Atom / x / y / z1 / C / 0.520969 / -0.176361 / -1.259960
2 / C / 2.780904 / -0.559196 / -0.605104
3 / C / 1.174792 / 1.291181 / 0.663238
4 / C / 0.012652 / 0.499869 / 0.028305
5 / H / 0.878193 / 0.604086 / -1.959117
6 / H / -0.285872 / -0.733672 / -1.745836
7 / H / 0.870620 / 1.757241 / 1.611514
8 / H / 1.486582 / 2.096253 / -0.020433
9 / H / 3.086815 / 0.237741 / -1.307297
10 / C / -0.524406 / -0.532557 / 1.039045
11 / H / -0.851618 / -0.002836 / 1.954314
12 / H / 0.259373 / -1.245467 / 1.312892
13 / C / -1.117370 / 1.492237 / -0.315744
14 / H / -1.403448 / 2.049298 / 0.590157
15 / H / -0.792034 / 2.224025 / -1.069068
16 / C / -2.794989 / -0.598109 / 0.321626
17 / H / -3.060836 / -0.043523 / 1.240088
18 / S / 2.633785 / 0.246947 / 1.077539
19 / O / 1.564161 / -1.126227 / -1.025522
20 / O / -1.604502 / -1.318471 / 0.527241
21 / S / -2.611294 / 0.685041 / -1.028197
22 / C / 3.836566 / -1.633285 / -0.519073
23 / C / 5.193387 / -1.281324 / -0.467041
24 / C / 3.469560 / -2.984823 / -0.481742
25 / C / 6.174824 / -2.263004 / -0.370450
26 / H / 5.484006 / -0.231160 / -0.501316
27 / C / 4.442571 / -3.976319 / -0.390193
28 / H / 2.417573 / -3.254018 / -0.536054
29 / C / 5.781748 / -3.600397 / -0.331122
30 / H / 4.183125 / -5.031576 / -0.363870
31 / N / 6.815922 / -4.654272 / -0.225654
32 / C / -3.903678 / -1.544562 / -0.067758
33 / C / -5.238756 / -1.119086 / -0.005103
34 / C / -3.611537 / -2.847493 / -0.492199
35 / C / -6.272340 / -1.978221 / -0.364386
36 / H / -5.470623 / -0.107015 / 0.326922
37 / C / -4.637647 / -3.717883 / -0.850649
38 / H / -2.576490 / -3.178352 / -0.527880
39 / C / -5.954126 / -3.269864 / -0.782272
40 / H / -7.314407 / -1.672553 / -0.322256
41 / H / -4.436300 / -4.734441 / -1.179021
42 / N / -7.046879 / -4.194486 / -1.158466
43 / O / -8.206306 / -3.773037 / -1.077703
44 / O / -6.732070 / -5.330067 / -1.531776
45 / H / 7.232286 / -2.015568 / -0.330338
46 / O / 6.433113 / -5.828538 / -0.175652
47 / O / 7.997957 / -4.294529 / -0.191689
Table S5. Cartesian coordinates (Å) of the optimized structure (GAMESSB3LYP/6-31G(d)) of the 1,3-dioxane-1,3-dithiane derivative 12.
Atom / x / y / zCARBON / 1.0552155080 / -0.9658406918 / -2.3738663573
CARBON / 5.9368742816 / -0.9919252633 / -0.2871387157
CARBON / 2.0225364311 / 2.3686740751 / 0.9562550218
CARBON / -0.0058979308 / 0.6030140877 / -0.1508598146
HYDROGEN / 1.7332876440 / 0.3115213559 / -3.8608699751
HYDROGEN / -0.4478005673 / -2.1244274075 / -3.1881566283
HYDROGEN / 1.2195731310 / 3.5520980717 / 2.4554990946
HYDROGEN / 2.7129566236 / 3.6494503541 / -0.5232931004
HYDROGEN / 6.4222700171 / 0.3646160790 / -1.7723819305
CARBON / -1.2122471838 / -1.0967029165 / 1.8890242272
HYDROGEN / -1.7735704688 / 0.0675585512 / 3.5242943401
HYDROGEN / 0.0903948417 / -2.5556145988 / 2.5361399617
CARBON / -2.1674910436 / 2.2854999608 / -1.1882065104
HYDROGEN / -2.7847612610 / 3.6198900883 / 0.2918249249
HYDROGEN / -1.5572185605 / 3.3788066244 / -2.8348936661
CARBON / -5.2081386523 / -0.7047395602 / -0.0057955874
HYDROGEN / -5.7653231666 / 0.5699965009 / 1.5619702266
SULFUR / 4.7573796164 / 0.8326494772 / 2.4515400399
SULFUR / 3.5812716416 / -3.2091335564 / -1.5934147936
OXYGEN / -3.3646432262 / -2.3926550084 / 0.9010453057
OXYGEN / -4.2604696386 / 0.8037446559 / -2.0021555120
CARBON / 8.2702492078 / -2.4513590077 / 0.4742974419
CARBON / 10.5602620629 / -2.0427835115 / -0.7938218285
CARBON / 8.1747375763 / -4.2430992168 / 2.4297103603
CARBON / 12.7227014504 / -3.3900692681 / -0.1387210531
HYDROGEN / 10.6534741716 / -0.6636995408 / -2.3124013452
CARBON / 10.3215383506 / -5.6001125888 / 3.1109212865
HYDROGEN / 6.4071378431 / -4.5744741010 / 3.4164121710
CARBON / 12.5673963751 / -5.1527228348 / 1.8104673226
HYDROGEN / 14.5051507721 / -3.1009020155 / -1.1023996061
HYDROGEN / 10.2803929215 / -6.9859219740 / 4.6168493028
CARBON / -7.4788323562 / -2.1695132774 / -0.9422160560
CARBON / -8.0056659998 / -4.5786378220 / 0.0167611369
CARBON / -9.1218017517 / -1.0659202893 / -2.7006158095
CARBON / -10.1510436220 / -5.8857841658 / -0.7694867823
HYDROGEN / -6.7194566875 / -5.4296802945 / 1.3650045223
CARBON / -11.2719429219 / -2.3508392039 / -3.5011586385
HYDROGEN / -8.6987585207 / 0.7925258590 / -3.4534424889
CARBON / -11.7561801996 / -4.7462256717 / -2.5178224395
HYDROGEN / -10.5918231673 / -7.7545826078 / -0.0592159227
HYDROGEN / -12.5648880283 / -1.5366671197 / -4.8631530471
NITROGEN / -14.0347328933 / -6.1048336531 / -3.3561772154
NITROGEN / 14.8469970466 / -6.5859615452 / 2.5138144575
OXYGEN / -15.4116375152 / -5.0483546958 / -4.9051877599
OXYGEN / -14.4296869035 / -8.2133573171 / -2.4566041691
OXYGEN / 14.6648548511 / -8.1165670362 / 4.2549428724
OXYGEN / 16.7962394613 / -6.1660956904 / 1.3163245415
Table S6. Cartesian coordinates (Å) of the optimized structure (GAMESSB3LYP/6-31G(d)) of the ax-ax isomer of the bis(1,3-oxathiane) derivatives 15.
Atom / x / y / zCARBON / 0.9851082182 / -1.0514607950 / -2.2519463766
CARBON / 5.6453440920 / -0.5371516822 / -0.0324125705
CARBON / 2.2022990081 / 2.0825195387 / 1.1253197707
CARBON / 0.0262378377 / 0.4528835481 / 0.0581172975
HYDROGEN / 1.4988824150 / 0.2606378804 / -3.7745731748
HYDROGEN / -0.4907564333 / -2.3028422175 / -2.9691870135
HYDROGEN / 1.5755846654 / 3.1402575573 / 2.7898147797
HYDROGEN / 2.8162560738 / 3.4583747983 / -0.3179121824
HYDROGEN / 6.0643136647 / 0.8612760177 / -1.5155338778
CARBON / -1.0063844465 / -1.2707618872 / 2.1718995173
HYDROGEN / -1.4641304892 / -0.1286120768 / 3.8410429368
HYDROGEN / 0.4126731030 / -2.6633617065 / 2.7276406636
CARBON / -2.0740033686 / 2.2889316637 / -0.8043222374
HYDROGEN / -2.6494421013 / 3.4983317438 / 0.7948867063
HYDROGEN / -1.3894451796 / 3.5147534046 / -2.3237117793
CARBON / -5.6340064471 / -0.3226427573 / -0.0109137473
HYDROGEN / -6.0530181817 / 0.8962263111 / 1.6228692084
OXYGEN / 4.3233669336 / 0.6505157958 / 1.9509447016
SULFUR / 3.7180515495 / -3.0719234257 / -1.5359627633
SULFUR / -3.8178270440 / -3.0784998471 / 1.2228372619
OXYGEN / -4.2353750386 / 1.0475282501 / -1.8115986034
CARBON / 8.0624427547 / -1.6805983269 / 0.9546386454
CARBON / 10.1319061105 / -1.9649085237 / -0.6739436578
CARBON / 8.2441027001 / -2.5159624141 / 3.4598763220
CARBON / 12.3633648325 / -3.0676862307 / 0.1732224336
HYDROGEN / 9.9953525171 / -1.3210993859 / -2.6194691516
CARBON / 10.4686330710 / -3.6123879665 / 4.3374286364
HYDROGEN / 6.6434780289 / -2.2849865878 / 4.7174284042
CARBON / 12.4960510373 / -3.8748450028 / 2.6767053868
HYDROGEN / 13.9850481918 / -3.2989798411 / -1.0542467062
HYDROGEN / 10.6553991705 / -4.2645056350 / 6.2687288542
CARBON / -8.0551220211 / -1.2739388065 / -1.1817679912
CARBON / -10.0897319665 / -1.9340830122 / 0.3824189365
CARBON / -8.2776894218 / -1.5541409420 / -3.8043537648
CARBON / -12.3235715218 / -2.8632930115 / -0.6455431540
HYDROGEN / -9.9224596045 / -1.7265273196 / 2.4189461787
CARBON / -10.5059413697 / -2.4725658234 / -4.8600713481
HYDROGEN / -6.7066846855 / -1.0302610915 / -5.0092094562
CARBON / -12.4959735903 / -3.1171443662 / -3.2618535636
HYDROGEN / -13.9181231785 / -3.3804343763 / 0.5288643696
HYDROGEN / -10.7238140123 / -2.6982959818 / -6.8829191998
NITROGEN / 14.8539661648 / -5.0295433185 / 3.5963691662
NITROGEN / -14.8564312727 / -4.0897729224 / -4.3681101091
OXYGEN / 16.6110160957 / -5.2438647581 / 2.0869334849
OXYGEN / 14.9277483594 / -5.7103688787 / 5.8191268518
OXYGEN / -16.5849145975 / -4.6398369097 / -2.9116614205
OXYGEN / -14.9604659540 / -4.2947961982 / -6.6826955091
Table S7. Cartesian coordinates (Å) of the optimized structure (GAMESSB3LYP/6-31G(d)) of the ax-eq isomer of the bis(1,3-oxathiane) derivatives 15.
Atom / x / y / zCARBON / 1.2171235247 / -0.9662492861 / -2.1609444921
CARBON / 5.4806936343 / -1.1122069599 / -0.7679359948
CARBON / 2.1467352148 / 2.4397404952 / 1.0424453407
CARBON / 0.0968868784 / 0.6338321201 / 0.0075662629
HYDROGEN / 1.8044031339 / 0.2959221021 / -3.7132998968
HYDROGEN / -0.1946378554 / -2.2802654077 / -2.8866355447
HYDROGEN / 1.4406127183 / 3.5181615326 / 2.6630367207
HYDROGEN / 2.6849295552 / 3.8085500713 / -0.4224099823
HYDROGEN / 5.9268183317 / 0.2374538565 / -2.2883335972
CARBON / -0.9419913925 / -1.0423744569 / 2.1587415380
HYDROGEN / -1.4923401258 / 0.1450737818 / 3.7673606363
HYDROGEN / 0.5101414033 / -2.3516377979 / 2.8189728078
CARBON / -2.0447513854 / 2.3075296785 / -1.0565501522
HYDROGEN / -2.7259262902 / 3.5900481644 / 0.4396959224
HYDROGEN / -1.3495102033 / 3.4675935788 / -2.6227224462
CARBON / -5.5239384535 / -0.3993453831 / -0.2371599072
HYDROGEN / -6.0478579708 / 0.8954342540 / 1.3055339790
SULFUR / 5.0040449343 / 0.8049065333 / 2.1587957960
OXYGEN / 3.3065711920 / -2.4884593892 / -1.4010111933
SULFUR / -3.6467234683 / -3.0047431719 / 1.2090881447
OXYGEN / -4.1144581148 / 0.9189174529 / -2.0680225905
CARBON / -7.8653441815 / -1.5098559228 / -1.4293289592
CARBON / -9.9554482580 / -2.0867050040 / 0.0930996285
CARBON / -7.9574043668 / -2.0204780064 / -4.0250326235
CARBON / -12.1168120387 / -3.1602757496 / -0.9493224928
HYDROGEN / -9.8914196472 / -1.6977428935 / 2.1088832215
CARBON / -10.1128970327 / -3.0831713229 / -5.0964668345
HYDROGEN / -6.3428332275 / -1.5611023119 / -5.1985169214
CARBON / -12.1608175365 / -3.6411045588 / -3.5385213724
HYDROGEN / -13.7514291844 / -3.6178304437 / 0.1941909652
HYDROGEN / -10.2315714708 / -3.4856193104 / -7.0999281371
CARBON / 7.6750512856 / -2.8824218955 / -0.3356370828
CARBON / 10.1509583490 / -1.9632932309 / -0.5458185107
CARBON / 7.2691107608 / -5.4136636793 / 0.3231983993
CARBON / 12.2075488504 / -3.5389257284 / -0.1018999705
HYDROGEN / 10.4710787687 / 0.0002403854 / -1.0564807189
CARBON / 9.3101492694 / -7.0145608282 / 0.7649993020
HYDROGEN / 5.3519765275 / -6.1205913388 / 0.4640268282
CARBON / 11.7511113589 / -6.0498569016 / 0.5506481124
HYDROGEN / 14.1341791087 / -2.8656704901 / -0.2570007216
HYDROGEN / 9.0443644822 / -8.9793510816 / 1.2739345277
NITROGEN / 13.9142483676 / -7.7340448517 / 1.0264962471
NITROGEN / -14.4458945296 / -4.7644404319 / -4.6603043992
OXYGEN / -16.2251058310 / -5.2385380639 / -3.2386592061
OXYGEN / -14.4409259799 / -5.1621314683 / -6.9520898918
OXYGEN / 16.0492927687 / -6.8337135166 / 0.8193818423
OXYGEN / 13.4578580607 / -9.9398218915 / 1.6051227140
Table S8. Cartesian coordinates (Å) of the optimized structure (GAMESSB3LYP/6-31G(d)) of the eq-eq isomer of the bis(1,3-oxathiane) derivatives 15.
Atom / x / y / zCARBON / 0.3153236034 / -1.0986295263 / 1.9638111704
CARBON / 1.4050415179 / -0.5925515378 / 4.0141187709
CARBON / 0.3995712882 / 1.3892194036 / 2.3968422453
CARBON / -0.4120192504 / 0.2461045402 / 1.7437879552
HYDROGEN / 1.2955829243 / -1.0743754985 / 1.4587181721
HYDROGEN / -0.2668536676 / -1.9192600169 / 1.5445764092
HYDROGEN / -0.1349598349 / 2.3430566698 / 2.3217222347
HYDROGEN / 1.3545107769 / 1.5085429117 / 1.8695099981
HYDROGEN / 2.3376208688 / -0.5087830389 / 3.4348008905
CARBON / -1.8359757636 / 0.2024422116 / 2.3373811061
HYDROGEN / -2.3096813578 / 1.1918969288 / 2.2234410793
HYDROGEN / -1.7997658313 / -0.0411841455 / 3.3996303694
CARBON / -0.4949737073 / 0.5569033858 / 0.2310840371
HYDROGEN / -0.8956227107 / 1.5681556465 / 0.0854630682
HYDROGEN / 0.4992509927 / 0.5300950228 / -0.2284338539
CARBON / -3.0121145300 / -0.5458133239 / 0.4090807536
HYDROGEN / -3.4151784333 / 0.4740105371 / 0.3112032411
SULFUR / 0.7352165356 / 1.1413412055 / 4.1915793533
OXYGEN / 0.4986369124 / -1.4237571206 / 3.3397141210
OXYGEN / -2.6648762908 / -0.7956654886 / 1.7456404501
SULFUR / -1.5239872938 / -0.6398254535 / -0.7187173802
CARBON / 1.6887863148 / -1.1470375296 / 5.3892998993
CARBON / 0.7817203633 / -2.0141597074 / 6.0116517051
CARBON / 2.8644015866 / -0.7768894825 / 6.0580065323
CARBON / 1.0450082995 / -2.5137041832 / 7.2844241989
HYDROGEN / -0.1220949507 / -2.3031708577 / 5.4880122242
CARBON / 3.1377161129 / -1.2640133410 / 7.3317542137
HYDROGEN / 3.5709437411 / -0.1035804617 / 5.5795005420
CARBON / 2.2203579916 / -2.1294599886 / 7.9258382943
HYDROGEN / 4.0417222588 / -0.9959438581 / 7.8645595658
NITROGEN / 2.5110703569 / -2.6571234722 / 9.2697315560
CARBON / -4.0296735924 / -1.5617863806 / -0.0506725034
CARBON / -4.9389571660 / -1.2308765109 / -1.0641422301
CARBON / -4.0587213672 / -2.8433906638 / 0.5146645463
CARBON / -5.8728855861 / -2.1614798237 / -1.5112196113
HYDROGEN / -4.9201300948 / -0.2376329330 / -1.5051950541
CARBON / -4.9886208789 / -3.7830675002 / 0.0798989927
HYDROGEN / -3.3605943899 / -3.0929857636 / 1.3053856563
CARBON / -5.8833291421 / -3.4272608268 / -0.9279601927
HYDROGEN / -6.5894168585 / -1.9232524770 / -2.2879584754
HYDROGEN / -5.0312739861 / -4.7775648206 / 0.5070660842
NITROGEN / -6.8750830960 / -4.4156052810 / -1.3811685165
OXYGEN / -7.6633657120 / -4.0716420478 / -2.2620577671
OXYGEN / -6.8579519572 / -5.5263809966 / -0.8513923890
HYDROGEN / 0.3610186069 / -3.1901304154 / 7.7825838490
OXYGEN / 3.5555744624 / -2.2942821066 / 9.8107204094
OXYGEN / 1.6934319340 / -3.4284018824 / 9.7710142782
Table S9. Cartesian coordinates (Å) of the optimized structure (ORCA B3LYP/6-31G(d,p)) of the 1,3-dioxane-1,3-dithiane derivative 12.
Atom / x / y / zC / 0,545432 / -0,539858 / -1,249168
C / 3,127109 / -0,563098 / -0,157828
C / 1,077074 / 1,230696 / 0,506566
C / -0,004279 / 0,305284 / -0,078819
H / 0,906542 / 0,123222 / -2,044926
H / -0,259544 / -1,148498 / -1,666793
H / 0,657226 / 1,857999 / 1,300630
H / 1,448349 / 1,906062 / -0,274711
H / 3,373420 / 0,154672 / -0,946465
C / -0,651392 / -0,580597 / 1,006796
H / -0,942077 / 0,044987 / 1,867331
H / 0,032949 / -1,354208 / 1,355083
C / -1,139447 / 1,204711 / -0,631881
H / -1,454876 / 1,917658 / 0,149125
H / -0,810094 / 1,777314 / -1,504570
C / -2,764227 / -0,358503 / 0,002147
H / -3,058394 / 0,323470 / 0,826730
S / 2,515457 / 0,402990 / 1,295332
S / 1,873472 / -1,734970 / -0,835215
O / -1,797245 / -1,257760 / 0,488648
O / -2,254287 / 0,428853 / -1,057520
C / 4,370692 / -1,324049 / 0,238170
C / 5,591992 / -1,043700 / -0,391393
C / 4,322753 / -2,313752 / 1,233607
C / 6,749579 / -1,732820 / -0,040556
H / 5,637657 / -0,280229 / -1,162696
C / 5,471432 / -3,010957 / 1,595484
H / 3,380270 / -2,536253 / 1,723409
C / 6,669379 / -2,707991 / 0,950876
H / 7,701753 / -1,530802 / -0,515181
H / 5,456483 / -3,777693 / 2,360105
C / -3,968213 / -1,131177 / -0,491942
C / -4,275727 / -2,382052 / 0,057532
C / -4,805678 / -0,572099 / -1,465935
C / -5,409351 / -3,074395 / -0,360734
H / -3,617595 / -2,812346 / 0,803358
C / -5,941878 / -1,253808 / -1,892785
H / -4,555685 / 0,391466 / -1,895096
C / -6,226646 / -2,496697 / -1,330169
H / -5,667492 / -4,044769 / 0,044993
H / -6,603451 / -0,845925 / -2,646920
N / -7,428766 / -3,222032 / -1,775027
N / 7,889668 / -3,441270 / 1,329460
O / -8,131952 / -2,688944 / -2,633164
O / -7,658140 / -4,316482 / -1,261125
O / 7,790599 / -4,296957 / 2,207895
O / 8,932680 / -3,152023 / 0,744027
Table S10. Cartesian coordinates (Å) of the optimized structure (ORCA B3LYP/6-31G(d,p)) of the ax-ax isomer of the bis(1,3-oxathiane) derivatives 15.
Atom / x / y / zC / 0.540474 / -0.553136 / -1.220538
C / 3.001850 / -0.274168 / -0.028119
C / 1.159691 / 1.084135 / 0.594504
C / 0.019423 / 0.218296 / 0.011804
H / 0.802410 / 0.155044 / -2.015854
H / -0.229427 / -1.222965 / -1.608022
H / 0.816269 / 1.626374 / 1.481403
H / 1.475615 / 1.828057 / -0.157122
H / 3.229493 / 0.476178 / -0.801246
C / -0.522110 / -0.719460 / 1.113001
H / -0.768502 / -0.134788 / 2.007494
H / 0.231039 / -1.458550 / 1.392161
C / -1.098809 / 1.189841 / -0.429637
H / -1.397993 / 1.817883 / 0.427223
H / -0.741191 / 1.852440 / -1.224362
C / -2.973496 / -0.202945 / -0.017459
H / -3.182348 / 0.426256 / 0.862003
O / 2.287245 / 0.331475 / 1.023593
S / 2.000225 / -1.607926 / -0.854975
S / -2.005563 / -1.671288 / 0.593778
O / -2.243393 / 0.538245 / -0.965778
C / 4.277669 / -0.880449 / 0.502630
C / 5.370076 / -1.059358 / -0.357561
C / 4.372910 / -1.290667 / 1.838930
C / 6.547856 / -1.639163 / 0.103874
H / 5.298714 / -0.744122 / -1.394857
C / 5.547031 / -1.867110 / 2.315836
H / 3.528306 / -1.143435 / 2.501637
C / 6.617157 / -2.033677 / 1.438914
H / 7.405218 / -1.784661 / -0.541378
H / 5.647498 / -2.187956 / 3.345339
C / -4.265051 / -0.689647 / -0.628374
C / -5.332812 / -1.046385 / 0.207847
C / -4.401399 / -0.811375 / -2.017111
C / -6.525863 / -1.519078 / -0.329274
H / -5.229085 / -0.955519 / 1.285526
C / -5.591751 / -1.278314 / -2.568631
H / -3.575847 / -0.528088 / -2.659062
C / -6.636185 / -1.626586 / -1.714825
H / -7.364320 / -1.798050 / 0.296629
H / -5.723577 / -1.377399 / -3.639017
N / 7.862233 / -2.640506 / 1.938650
N / -7.897538 / -2.118976 / -2.292885
O / 8.791886 / -2.772031 / 1.142870
O / 7.898354 / -2.975953 / 3.122096
O / -8.803315 / -2.417092 / -1.514684
O / -7.969660 / -2.201322 / -3.518647
Table S11. Cartesian coordinates (Å) of the optimized structure (ORCA B3LYP/6-31G(d,p)) of the ax-eq isomer of the bis(1,3-oxathiane) derivatives 15.
Atom / x / y / zC / 0.655645 / -0.514091 / -1.151316
C / 2.906836 / -0.583712 / -0.400173
C / 1.132491 / 1.292505 / 0.541419
C / 0.053097 / 0.331336 / -0.008749
H / 0.971224 / 0.153808 / -1.970086
H / -0.087758 / -1.210634 / -1.540099
H / 0.753047 / 1.863084 / 1.395361
H / 1.418902 / 2.013557 / -0.234616
H / 3.147078 / 0.129129 / -1.204523
C / -0.496393 / -0.558392 / 1.128620
H / -0.791811 / 0.067226 / 1.979336
H / 0.272666 / -1.250126 / 1.476704
C / -1.082660 / 1.212109 / -0.576393
H / -1.444006 / 1.891011 / 0.214331
H / -0.714537 / 1.826909 / -1.404241
C / -2.919716 / -0.220724 / -0.136720
H / -3.189483 / 0.465420 / 0.681292
S / 2.643610 / 0.435296 / 1.142959
O / 1.759135 / -1.315524 / -0.736026
S / -1.924828 / -1.597980 / 0.623387
O / -2.175789 / 0.472990 / -1.109698
C / -4.164231 / -0.805240 / -0.758942
C / -5.264212 / -1.112569 / 0.054592
C / -4.224100 / -1.067291 / -2.133732
C / -6.414098 / -1.674430 / -0.491137
H / -5.220173 / -0.912532 / 1.121558
C / -5.370411 / -1.624661 / -2.694264
H / -3.374440 / -0.821227 / -2.759458
C / -6.448370 / -1.921241 / -1.862679
H / -7.276210 / -1.917347 / 0.117376
H / -5.442950 / -1.832661 / -3.754624
C / 4.068841 / -1.518203 / -0.164756
C / 5.379743 / -1.028668 / -0.256421
C / 3.851437 / -2.862251 / 0.164626
C / 6.466282 / -1.865511 / -0.022449
H / 5.551173 / 0.013521 / -0.511194
C / 4.929882 / -3.712157 / 0.396602
H / 2.836712 / -3.237438 / 0.223870
C / 6.221865 / -3.199267 / 0.301167
H / 7.486956 / -1.510310 / -0.090151
H / 4.788485 / -4.756020 / 0.648152
N / 7.365669 / -4.093922 / 0.544399
N / -7.663518 / -2.509040 / -2.450510
O / -8.600331 / -2.758568 / -1.692255
O / -7.668350 / -2.714479 / -3.663849
O / 8.495132 / -3.613920 / 0.449499
O / 7.122779 / -5.266508 / 0.827659
Table S12. Cartesian coordinates (Å) of the optimized structure (ORCA B3LYP/6-31G(d,p)) of the eq-eq isomer of the bis(1,3-oxathiane) derivatives 15.
Atom / x / y / zC / 0.552311 / -0.368200 / -1.250374
C / 2.805720 / -0.646960 / -0.548956
C / 1.141140 / 1.161199 / 0.672551
C / 0.006191 / 0.353800 / 0.001202
H / 0.889031 / 0.379243 / -1.987776
H / -0.230198 / -0.973723 / -1.707921
H / 0.796242 / 1.624055 / 1.603099
H / 1.459445 / 1.970373 / 0.003988
H / 3.067994 / 0.161605 / -1.249395
C / -0.580825 / -0.666346 / 1.001578
H / -0.887765 / -0.142582 / 1.922070
H / 0.169809 / -1.411836 / 1.264523
C / -1.085742 / 1.369610 / -0.406947
H / -1.370398 / 1.970817 / 0.465200
H / -0.713730 / 2.060000 / -1.171186
C / -2.840478 / -0.632199 / 0.265439
H / -3.071962 / -0.044082 / 1.167337
S / 2.611243 / 0.152290 / 1.126895
O / 1.618787 / -1.269127 / -0.959952
O / -1.685930 / -1.398914 / 0.476266
S / -2.598248 / 0.599164 / -1.117170
C / 3.925531 / -1.657342 / -0.474771
C / 5.256280 / -1.214196 / -0.471770
C / 3.650807 / -3.028102 / -0.391006
C / 6.305313 / -2.123613 / -0.385715
H / 5.472473 / -0.151366 / -0.535639
C / 4.691695 / -3.949839 / -0.308648
H / 2.621238 / -3.365199 / -0.402512
C / 6.004109 / -3.482524 / -0.305514
H / 4.505148 / -5.014897 / -0.246940
N / 7.108180 / -4.452705 / -0.219475
C / -4.002935 / -1.528305 / -0.087929
C / -5.313809 / -1.062755 / 0.088932
C / -3.786408 / -2.809581 / -0.610901
C / -6.401009 / -1.861291 / -0.251455
H / -5.484796 / -0.069195 / 0.494007
C / -4.865423 / -3.621275 / -0.951605
H / -2.771496 / -3.167667 / -0.736207
C / -6.157398 / -3.132863 / -0.768290
H / -7.421694 / -1.523910 / -0.121261
H / -4.724503 / -4.616877 / -1.353922
N / -7.301812 / -3.986890 / -1.127245
O / -8.431240 / -3.530431 / -0.950977
O / -7.059388 / -5.104187 / -1.582363
H / 7.340208 / -1.804889 / -0.384292
O / 6.815272 / -5.645956 / -0.151201
O / 8.256975 / -4.010705 / -0.220833