triazinanes with an axial tert-butyl group esi for

ESI for manuscript:

Raise the anchor! Synthesis, X-ray and NMR characterization of 1,3,5-

triazinanes with an axial tert-butyl group

By Alexey V. Kletskov, Anastasya D. Zatykina, Mariya V. Grudova, Anna A. Sinelshchikova,

Mikhail S. Grigoriev, Vladimir P. Zaytsev, Diego M. Gil, Roman A. Novikov, Fedor I. Zubkov, and

Antonio Frontera

Table of contents

№ Part Pages

1. General procedure for the synthesis of triazinanes 1−4 2

2. X-ray experimental part and Tables from S1 to S34, Schemes from

S1 to S5

5

3. Copies of NMR spectra of synthesised compounds 1−4 35

4. Experimental details for 2D low temperature NMR 49

5. Copies of 1D and 2D dynamic NMR spectra at various temperatures

for fluoro-triazinane 1

53

6 Copies of 1D and 2D dynamic NMR spectra at various temperatures

for bromo-triazinane 3

88

7 DFT calculations using methyl instead of t-Bu 97

8 Cartesian coordinates and energies 98

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2020

1. General procedure for the synthesis of triazinanes 1-4 (Scheme S1).

Starting reagents were purchased from commercial sources and were used without any additional

purification or were prepared according to literature procedures. The routine 1H, 13C and 19F NMR

spectra were acquired on a Jeol JNM-ECA 600 spectrometer (with operating frequencies of 600, 150,

565 MHz for 1H, С13 and 19F, respectively) at r.t and referenced to the residual signals of the CDCl3.

Chemical shifts are reported in parts per million (δ/ppm) referenced internal (NMR) solvent signal.

Coupling constants are reported in Hertz (J/Hz). The peak patterns are indicated as follows: s,

singlet; d, doublet; t, triplet; q, quadruplet; m, multiplet; dd, doublet of doublets; ddd, doublet of

doublet of doublets; tt, triplet of triplets, and br s, broad singlet. The 2D NMR data were collected as

described below (see Part 4 of the ESI). Infrared spectra were measured on an Infralum FT-801

FT/IR instrument. The wavelengths are reported in reciprocal centimetres (max /cm-1). HRMS

spectra were recorded on a tandem quadrupole time-of-flight (QTOF) accurate mass detector

(Agilent 6545 Q-TOF LC/MS; Agilent Technologies, USA). Melting points were determined on a

SMP-10 apparatus and not corrected. Solvents were distilled and dried according to standard

procedures, silica gel 5-40 µ was used for filtration. Microanalyses were performed for C, H, N and

S on an Eurovector EA 3000 (CHNS) elemental analysis system and were within ±0.4% of

theoretical values (the data were obtained in Center for Collective Use of RUDN University - CCU-

PCMR PFUR).

To 1.57 mmol of 4-halosulfamide and 71 mg (0.16 mmol) of Sm(NO3)3•6H2O in chloroform (5

mL), 250 mg (1.57 mmol) of 3-tert-butyl-1,5,3-dioxazepane was added, and the reaction mixture was

stirred for 48 h at r.t. The reaction mixture was combined with chloroform (35 mL) and washed

twice with water (2 × 20 mL) in a separatory funnel. The organic layer was separated, dried over

anhydrous Na2SO4, and filtrated through thin layer of silica gel. The filtrate was concentrated to

approximately 0.5-0.7 mL under reduced pressure, and 5 mL of diethyl ether was added. The

obtained solution was cooled below −20 °C, formed solids were filtered off, washed with cold

ethanol (1 mL), dried in air, and further dried in a vacuum desiccator over P2O5 for 24 h to give the

target products 1-4 as white powder.

3

Scheme S1. 1: Hal = F; 2: Hal = Cl; 3: Hal = Br; 4: Hal = I.

Hal

SO

O

NH2

N O

O+

N

Hal

SO

O

N

Hal

SO

O N

1-4

Sm(NO3)3•6H2O, r.t., 48 h

CHCl3

5

6

The used method of synthesis of triazinanes (1-4) are new and its mechanism needs explanation

(Scheme S2).

It is likely that the formation of 1,3,5-triazinane core proceeds through alkylation of two starting

molecules of sulfonamide by one molecule of 1,5,3-dioxazepane 6 under catalysis by samarium

trinitrate and through the further reaction of the obtained intermediate with formaldehyde, formed as

a result of dioxazepane 6 hydrolysis. We successfully extended this approach to synthesize all

triazinanes (1-4) in good yields.

Scheme S2. Plausible mechanism of 1,3,5-triazinanes (1-4) formation.

N O

O

But

6

1-4

ButN

OO

H2N SO

O Ar

ButN

HNSO

O Ar

NH

NO

ONH2 + HO OH

OSm(NO3)3

-

HH

ArSO2NH2 (5)Sm(NO3)3N O

O

But

Sm(NO3)3-

+Sm(NO3)3

-

+SN2

-Sm(NO3)3But

NOH

O

HNSO

O Ar

Sm(NO3)3But

NOH

O

HNSO

O Ar

Sm(NO3)3-

ArSO2NH2 (5)

-Sm(NO3)3-HO(CH2)2OH

+

ButN

HNSO

O Ar

NSO OAr

OSm(NO3)3

-H

+

+

SO OAr

-Sm(NO3)3-H2O

6

H+

Sm(NO3)3•6H2O+

O

HH2

4

1-(tert-Butyl)-3,5-bis[(4-fluorophenyl)sulfonyl]-1,3,5-triazinane (1). Yield 60%, white powder,

m.p. 190-191 ℃. 1H NMR (600.2 MHz, CDCl3) δ 7.82 (ddd, J ~ 8.9, 5.0, 2.5 Hz, 4Harom.), 7.23 –

7.16 (m, 4Harom.), 4.63 (s, 2H, CH2), 4.14 (s, 4H, 2CH2), 1.04 (s, 9H, CH3). 13C NMR (150.9 MHz,

CDCl3) δ 165.50 (d, J ~ 255.7 Hz, 2Cquat.), 134.55 (d, J ~ 2.9 Hz, 2Cquat.), 130.45 (d, J ~ 9.4 Hz,

4CHarom.), 116.52 (d, J ~ 22.5 Hz, 4CHarom.), 62.54 (2CH2), 60.93 (CH2), 54.14 (Cquat.), 27.28 (3CH3). 19F NMR (564.7 MHz, CDCl3) δ −104.17 (tt, J ∼ 4.4 and 8.4 Hz). IR (KBr): 3104, 3080, 3045

(HC=), 2973, 2929, 2870 (alkyl), 1333, 1153 (SO2N). MS (ESI): m/z = 460.1 [M+H]+. Anal. Calcd

for C19H23F2N3O4S2: C, 49.66; H, 5.05; N, 9.14; S, 13.95. Found: C, 49.70; H, 5.30; N, 9.19; S,

14.17.

1-(tert-Butyl)-3,5-bis[(4-chlorophenyl)sulfonyl]-1,3,5-triazinane (2). Yield 79%. White powder,

m.p. 186-187 °C. 1H NMR (600.2 MHz, CDCl3) δ 7.73 (app. d, J ~ 8.6 Hz, 4Harom.), 7.49 (app. d, J ~

8.6 Hz, 4H arom), 4.64 (s, 2H, CH2), 4.16 (s, 4H, 2CH2), 1.05 (s, 9H, 3CH3). 13C NMR (150.9 MHz,

CDCl3) δ 139.87 (2Cquat.), 137.07 (2Cquat.), 129.57 (4CHarom.), 129.09 (4CHarom.), 62.56 (2CH2), 60.89

(CH2), 54.23 (Cquat.), 27.35 (3CH3). IR (KBr): 3089, 3067 (CHarom.), 2974 (alkyl), 1347, 1161

(SO2N). MS (ESI): m/z = 494.0 [M+H, 37Cl, 37Cl]+, 493.1, [M+H, 35Cl, 37Cl]+, 492.1 [M+H, 35Cl, 35Cl]+. Anal. Calcd for C19H23Cl2N3O4S2: C, 46.34; H, 4.71; N, 8.53; S, 13.02. Found: C, 46.33; H,

4.59; N, 8.58; S, 12.94.

1,3-Bis[(4-bromophenyl)sulfonyl]-5-(tert-butyl)-1,3,5-triazinane (3). Yield 68%. White powder,

m.p. 219-220 °C. 1H NMR (600.2 MHz, CDCl3) δ 7.70–7.61 (m, 8Harom.), 4.63 (s, 2H, CH2), 4.16 (s,

4H, 2CH2), 1.05 (s, 9H, 3CH3). 13C NMR (150.9 MHz, CDCl3) δ 137.58 (2Cquat.), 132.58 (4CHarom.),

129.16 (4CHarom.), 128.40 (2Cquat.), 62.57 (2CH2), 60.89 (CH2), 54.27 (Cquat.), 27.37 (3CH3). IR

(KBr): 3086 (HC=), 2972, 2932, 2874, 2839 (Alkyl), 1346, 1160 (SO2N). MS (ESI): m/z = 583.9

[M+H, 81Br, 81Br]+, 581.9 [M+H, 79Br, 81Br]+, 579.9 [M+H, 79Br, 79Br]+. Anal. Calcd for

C19H23Br2N3O4S2: C, 39.26; H, 3.99; N, 7.23; S, 11.03. Found: C, 39.14; H, 3.76; N, 7.08; S, 11.11.

1-(tert-Butyl)-3,5-bis[(4-iodophenyl)sulfonyl]-1,3,5-triazinane 4. Yield 80%. White powder, m.p.

> 240 °C (with decomposition). 1H NMR (600.2 MHz, CDCl3) δ 7.88 (app d, J ~ 8.5 Hz, 4Harom.),

7.49 (app d, J ~ 8.5 Hz, 4Harom.), 4.62 (s, 2H, CH2), 4.16 (s, 4H, 2CH2), 1.06 (s, 9H, 3CH3).13C NMR

(150.9 MHz, CDCl3) δ 138.56 (4CHarom.), 138.21 (2Cquat.), 128.96 (4CHarom.), 100.86 (2Cquat.), 62.56

(2CH2), 60.89 (CH2), 54.32 (Cquat.), 27.43 (3CH3). IR (KBr): 3081, 3059 (HC=), 2969, 2931, 2872

(alkyl), 1346, 1159 (SO2N). MS (ESI): m/z = 675.9 [M+H]+. Anal. Calcd for C19H23I2N3O4S2: C,

33.79; H, 3.43; N, 6.22; S, 9.49. Found: C, 33.80; H, 3.43; N, 6.29; S, 9.23.

5

2. X-ray experimental part

To obtain single crystals suitable for an X-ray diffraction analysis, the powders of samples 1−4

were recrystallized at r.t from CDCl3 by a slow evaporation of the solvent from 5 mm NMR tubes.

In two cases (1·CDCl3 and 2·CDCl3) we were able to obtain solvates containing one molecule

of the solvent. All our attempts to grow similar co-crystallized solvent molecules of iodine and

bromine derivatives (3 and 4) were unsuccessful. Single crystal for substance 1 in solvate-free form

was obtained by crystallization from CH2Cl2-hexane 9:1 system, for compound 2 – from 1,2-

dichloroethane, for compound 4 – by crystallization from DMSO-d6.

X-ray diffraction experiments were performed at the Center for Shared Use of Physical

Methods of Investigation at the Frumkin Institute of Physical Chemistry and Electrochemistry, RAS.

The single-crystal X-ray diffraction data were collected on a Bruker Kappa Apex II automatic four-

circle diffractometer equipped with an area detector (Mo-Kα sealed-tube X-ray source, λ = 0.71073

Å, graphite monochromator) at 100 K for compounds 1, 2, 4, 1·CDCl3, and 2·CDCl3 and at r.t for

compounds 2−4. The data frames were collected using the program APEX2 and processed using the

program SAINT routine within APEX2. The unit cell parameters were refined over the whole dataset

[1]. The data were corrected for absorption on the multi-scan technique as implemented in SADABS

[2]. The structures were solved by direct methods using SHELXS and refined by full-matrix least-

squares on F2 using SHELXL software [3] in the anisotropic approximation for all nonhydrogen

atoms. Hydrogen atoms on carbon were calculated in ideal positions with isotropic displacement

parameters set to 1.2×Ueq (CH groups) or 1.5×Ueq (CH3 groups) of the attached atoms. Tables and

pictures for structures were generated using Olex2 [4] as GUI. Crystallographic data and structural

refinements are summarized in Table S1.

Atomic coordinates for compounds 1-4, 1·CDCl3, and 2·CDCl3 have been deposited with the

Cambridge Crystallographic Data Centre. CCDC numbers are 1969754 (1 at 100 K), 1969753 (2 at

100 K), 1969751 (2 at 296 K), 1969752 (3 at 296 K), 1969758 (4 at 100 K), 1969755 (4 at 296 K),

1969756 (1·CDCl3), 1969757 (2·CDCl3). The supplementary crystallographic data can be obtained

free of charge from the Cambridge Crystallographic Data Centre via

www.ccdc.cam.ac.uk/data_request/cif.

According to the X-ray data, Cl-, Br- and I-substituted molecules 2–4 are isostructural,

crystallize in the orthorhombic Pnma space group with half molecule in the asymmetric unit cell.

The molecule lies in special position on the mirror plane. Fluorine-substituted molecules 1 crystallize

in the monoclinic P21/c space group. In this case, the molecule lies in a general position and its

asymmetric unit contains one molecule. All compounds crystallize with four molecules in the unit

http://www.ccdc.cam.ac.uk/data_request/cif

6

cell.

Solvates (1·CDCl3 and 2·CDCl3) are isostructural, crystallize in the orthorhombic P212121

space group and have one triazinane molecule and one CDCl3 molecule in the asymmetric unit cell

(see Fig. 1 of the main part of the manuscript).

In compounds 1–4, 1·CDCl3 and 2·CDCl3 all CH2–N bond lengths and CH2–N–CH2 bond

angles are typical for 1,3,5-triazinanes and listed in corresponding Tables S2-S34. The torsion angles

CNCN in the trizacyclohexane ring are close to 60°. The orientation of the tert-butyl substituent is

almost the same for all structures with the exception of the fluorine derivative 1. In structures 2–4

N(1) atom, C(4) atom and two carbon atoms of tert-butyl substituent (C(5) and C(6)) lie in the mirror

plane (see Figs. S1, 2).

Figure S1. Mirror plane observed in compound 2 as example of isostructural compounds 2–4.

In structures 1·CDCl3 and 2·CDCl3 a crystallographic mirror plane is absent but the

orientation of the tert-butyl substituent is the same (displacement of one methyl C atom from ideal

mirror plane is 0.014(6) and 0.036(7) Å for 1·CDCl3 and 2·CDCl3, respectively). Only for 1 the tert-

butyl substituent is essentially twisted from ideal mirror plane (displacement of a methyl carbon from

ideal mirror plane is 0.554(4) Å). The orientation of phenyl rings is similar for all structures. The

angles between C6 and N3 planes are following: 1 – 70.85 and 72.78, 2 – 63.04, 3 – 60.68, 4 –

61.39, 1·CDCl3 – 76.61 and 82.37, 2·CDCl3 – 84.29 and 80.13. It should be mentioned, that the

presence of the co-crystallized solvent molecule of CDCl3 does not change much the geometry of F

and Cl substituted triazinanes (1·CDCl3 and 2·CDCl3).

[1] SAINT-Plus, Version 7.68., Bruker AXS Inc., Madison, Wisconsin, USA.

[2] SADABS, Madison, Wisconsin (USA): Bruker AXS, 2008.

[3] Sheldrick, G. M. Acta Crystallogr. Sect. C Struct. Chem. 2015, 71, 3–8.

[4] Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. J. Appl. Cryst. 2009, 42,

7

339-341.

Figure S2. X-ray packing due to C–H···O hydrogen bonds of 2 (the same packing is present in 3 and 4), (a) 2D layer in (010), view along b, (b) side view of two layers, each layer is shown by different color, view along c, (c) side view of two layers, view along c.

8

Figure S3. X-ray packing of 1 due to C–H···O hydrogen bonds (a) 1D chains along [001] direction, view along a.

9

(а)

10

(b)

Figure S4. X-ray packing of 1·CDCl3 (a) 1D channels occupied with CDCl3, view along with a, (b) alternation and interaction of 1·CDCl3 chains and CDCl3 chains, view along c.

11

Figure S5. X-ray packing of 2·CDCl3 (a) 1D column of triazinane molecules along [100], view along b (b) specific C–Cl···O interaction in 2D layer and 1D channels occupied with CDCl3, view along a.

12

Table S1. Crystal data and structure refinement for 1-4, 1·CDCl3 and 2·CDCl3.Identification code 1 (100 K) 2 (100 K) 2 (296 K) 3 (296 K) 4 (100 K) 4 (296 K) 1·CDCl3 2·CDCl3

CCDC number 1969754 1969753 1969751 1969752 1969758 1969755 1969756 1969757

Empirical formula C19H23F2N3O4S2 C19H23Cl2N3O4S2 C19H23Cl2N3O4S2 C19H23Br2N3O4S2 C19H23I2N3O4S2 C19H23I2N3O4S2 C20H23DCl3F2N3O4S2

C20H23DCl5N3O4S2

Formula weight 459.52 492.42 492.42 581.34 675.32 675.32 579.90 612.80 Temperature/K 100(2) 100(2) 296(2) 296(2) 100(2) 296(2) 100(2) 100(2) Crystal system monoclinic orthorhombic orthorhombic orthorhombic orthorhombic orthorhombic orthorhombic orthorhombic Space group P21/c Pnma Pnma Pnma Pnma Pnma P212121 P212121 a/Å 15.0587(11) 15.0515(5) 15.0501(4) 15.1555(7) 15.4193(4) 15.4374(4) 10.4481(2) 10.5857(3) b/Å 11.9394(9) 23.4696(8) 23.9887(8) 24.3132(12) 24.5788(7) 24.9622(6) 14.3121(3) 14.0014(4) c/Å 11.6556(8) 6.1833(2) 6.1915(2) 6.1544(3) 6.1039(2) 6.1336(2) 16.4591(3) 17.5197(5) α/° 90 90 90 90 90 90 90 90 β/° 90.844(4) 90 90 90 90 90 90 90 γ/° 90 90 90 90 90 90 90 90 Volume/Å3 2095.4(3) 2184.27(13) 2235.33(12) 2267.77(19) 2313.30(12) 2363.59(11) 2461.20(8) 2596.68(13) Z 4 4 4 4 4 4 4 4 ρcalcg/cm3 1.457 1.497 1.463 1.703 1.939 1.898 1.565 1.568 μ/mm-1 0.303 0.520 0.508 3.790 2.930 2.868 0.591 0.753 F(000) 960.0 1024.0 1024.0 1168.0 1312.0 1312.0 1192.0 1256.0 Crystal size/mm3 0.360 × 0.320 ×

0.060 0.400 × 0.200 × 0.060

0.400 × 0.200 × 0.060

0.500 × 0.200 × 0.040

0.400 × 0.320 × 0.160

0.500 × 0.420 × 0.180

0.400 × 0.200 × 0.180

0.500 × 0.420 × 0.320

Radiation MoKα (λ = 0.71073)

MoKα (λ = 0.71073)

MoKα (λ = 0.71073)

MoKα (λ = 0.71073)

MoKα (λ = 0.71073)

MoKα (λ = 0.71073)

MoKα (λ = 0.71073)

MoKα (λ = 0.71073)

2Θ range for data collection/° 8.152 to 59.998 8.402 to 59.994 7.886 to 60 7.894 to 55.232 7.91 to 69.992 7.86 to 59.99 6.902 to 59.99 6.978 to 59.992

Index ranges -21 ≤ h ≤ 21, -16 ≤ k ≤ 16, -16 ≤ l ≤ 16

-21 ≤ h ≤ 21, -33 ≤ k ≤ 33, -8 ≤ l ≤ 8

-20 ≤ h ≤ 21, -33 ≤ k ≤ 33, -8 ≤ l ≤ 8

-19 ≤ h ≤ 17, -31 ≤ k ≤ 31, -7 ≤ l ≤ 8

-24 ≤ h ≤ 24, -39 ≤ k ≤ 39, -9 ≤ l ≤ 7

-21 ≤ h ≤ 21, -35 ≤ k ≤ 35, -8 ≤ l ≤ 8

-14 ≤ h ≤ 14, -20 ≤ k ≤ 19, -23 ≤ l ≤ 23

-14 ≤ h ≤ 14, -19 ≤ k ≤ 18, -24 ≤ l ≤ 24

Reflections collected 22747 22380 23321 18873 57033 28130 38251 44030 Independent reflections

6088 [Rint = 0.0557, Rsigma =

3242 [Rint = 0.0481, Rsigma =

3322 [Rint = 0.0298, Rsigma =

2670 [Rint = 0.0587, Rsigma =

5176 [Rint = 0.0325, Rsigma =

3510 [Rint = 0.0268, Rsigma =

7167 [Rint = 0.0499, Rsigma =

7555 [Rint = 0.0354, Rsigma =

13

0.0506] 0.0309] 0.0202] 0.0380] 0.0157] 0.0154] 0.0375] 0.0252] Data/restraints/parameters 6088/0/271 3242/0/142 3322/0/142 2670/0/142 5176/0/142 3510/0/142 7167/0/308 7555/0/308

Goodness-of-fit on F2 1.026 1.087 1.029 1.011 1.198 1.110 1.028 1.056 Final R indexes [I>=2σ (I)]

R1 = 0.0368, wR2 = 0.0936

R1 = 0.0395, wR2 = 0.0953

R1 = 0.0508, wR2 = 0.1212

R1 = 0.0417, wR2 = 0.0793

R1 = 0.0253, wR2 = 0.0523

R1 = 0.0383, wR2 = 0.0815

R1 = 0.0347, wR2 = 0.0796

R1 = 0.0267, wR2 = 0.0648

Final R indexes [all data]

R1 = 0.0475, wR2 = 0.1008

R1 = 0.0600, wR2 = 0.1106

R1 = 0.0771, wR2 = 0.1375

R1 = 0.0816, wR2 = 0.0931

R1 = 0.0303, wR2 = 0.0543

R1 = 0.0474, wR2 = 0.0854

R1 = 0.0417, wR2 = 0.0830

R1 = 0.0286, wR2 = 0.0658

Largest diff. peak/hole / e Å-3 0.42/-0.43 0.46/-0.44 0.55/-0.42 0.58/-0.61 0.55/-0.94 1.13/-0.78 0.43/-0.54 0.40/-0.54

Flack parameter 0.48(6) 0.48(5)

14

Table S2 Hydrogen Bonds (HB)1 (100 K)

D H A d(D-H)/Å d(H-A)/Å d(D-A)/Å D-H-A/°C(2) H(2B) O(1)1 0.99 2.43 3.0538(17) 120.9C(6) H(6B) O(3)1 0.99 2.41 3.3600(17) 161.8C(22) H(22) O(4)2 0.95 2.53 3.4670(17) 168.92 (100 K)C(2) H(2A) O(2)3 0.99 2.42 3.301(2) 148.2C(12) H(12A) O(1)4 0.95 2.40 3.297(2) 157.13 (296 K)C(2) H(2A) O(2)3 0.97 2.39 3.263(4) 149.4C(12) H(12A) O(1)4 0.93 2.48 3.357(4) 156.34 (100 K)C(2) H(2A) O(2)3 0.99 2.33 3.228(2) 149.7C(12) H(12A) O(1)4 0.95 2.42 3.331(2) 159.6

1+X,3/2-Y,-1/2+Z; 22-X,2-Y,1-Z; 3+X,+Y,1+Z; 41/2+X,+Y,1/2-Z

15

Table S3 Halogen (XBs) and hydrogen bonds (HBs) for 1·CDCl3 and 2·CDCl3

D X/H A d(D-X/H)/Å d(X/H-A)/Å d(D-A)/Å D-X/H-A/°1·CDCl3

XBs solvent - solventC(1) Cl(4) Cl(5)1 1.753 3.491 5.198 163.91

HBs solvent - triazineC(8) H(8C) Cl(3)2 0.98 2.89 3.675(3) 138.3C(1) D(1A) F(1) 1.00 2.48 3.356(4) 145.5C(23) H(23A) Cl(4)3 0.95 2.84 3.649(3) 144.0

HBs triazine - triazineC(2) H(2A) O(3)4 0.99 2.64 3.138(3) 110.9C(15) H(15A) O(4)4 0.95 2.69 3.275(3) 120.2C(25) H(25A) O(2)4 0.95 2.72 3.232(3) 114.4C(9) H(9B) O(1)4 0.98 2.82 3.435(3) 121.8C(8) H(8C) O(3)4 0.98 2.80 3.412(3) 120.8C(9) H(9C) F(2)7 0.98 2.58 3.445(3) 146.7C(15) H(15A) F(2)8 0.95 2.60 3.479(3) 153.62·CDCl3

XBs solvent - solventC(1) Cl(4) Cl(5)1 1.751 3.469 5.193 167.52

HBs solvent - triazineC(8) H(8C) Cl(3)2 0.98 2.71 3.525(3) 140.7C(1) D(1A) Cl(1) 1.00 2.83 3.631(3) 137.0C(23) H(23A) Cl(4)3 0.95 2.86 3.574(2) 132.6

HBs triazine - triazineC(15) H(15A) O(4)4 0.95 2.82 3.365(3) 117.2C(25) H(25A) O(2)4 0.95 2.75 3.302(3) 117.5C(9) H(9B) O(1)4 0.98 2.83 3.468(3) 123.6C(8) H(8C) O(3)4 0.98 2.75 3.385(3) 123.4C(6) H(6B) Cl(2)7 0.99 2.88 3.823(2) 160.2C(8) H(8A) Cl(2)9 0.98 2.94 3.553(2) 121.8C(15) H(15A) Cl(2)8 0.95 2.93 3.837(2) 159.1C(26) H(26A) Cl(2)7 0.95 2.95 3.875(2) 164.6

XBs triazine - triazineC(24) Cl(2) O(4)5 1.733 2.994 4.711 170.08C(14) Cl(1) O(2)6 1.741 3.174 4.848 160.22

11/2+X,1/2-Y,1-Z; 2+X,1+Y,+Z; 3-1/2+X,1/2-Y,1-Z; 41/2+X,3/2-Y,1-Z; 5 1-X,-1/2+Y,1/2-Z;

61-X,-1/2+Y,3/2-Z; 71-X,1/2+Y,1/2-Z; 83/2-X,1-Y,1/2+Z; 9-1/2+X,3/2-Y,1-Z

16

1 (100 K) C19H23F2N3O4S2

X-ray data for 1 at 100 K. Thermal ellipsoids are shown at the 50% probability level.

Table S4 Bond Lengths for 1 (100 K).Atom Atom Length/Å Atom Atom Length/Å

S(1) O(2) 1.4309(11) N(5) C(6) 1.5050(16)S(1) O(1) 1.4319(10) C(7) C(9) 1.5238(19)S(1) N(3) 1.6381(12) C(7) C(8) 1.533(2)S(1) C(11) 1.7619(14) C(7) C(10) 1.5344(19)S(2) O(3) 1.4346(10) C(11) C(16) 1.3891(19)S(2) O(4) 1.4379(10) C(11) C(12) 1.3961(19)S(2) N(5) 1.6295(11) C(12) C(13) 1.389(2)S(2) C(21) 1.7630(14) C(13) C(14) 1.373(2)F(1) C(14) 1.3520(16) C(14) C(15) 1.381(2)F(2) C(24) 1.3545(16) C(15) C(16) 1.389(2)N(1) C(2) 1.4362(17) C(21) C(22) 1.3930(19)N(1) C(6) 1.4381(17) C(21) C(26) 1.3969(18)N(1) C(7) 1.4984(17) C(22) C(23) 1.3865(19)N(3) C(4) 1.4650(17) C(23) C(24) 1.383(2)N(3) C(2) 1.4924(17) C(24) C(25) 1.377(2)N(5) C(4) 1.4738(16) C(25) C(26) 1.387(2)

17

Table S5 Bond Angles for 1 (100 K).Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚

O(2) S(1) O(1) 120.44(7) N(1) C(7) C(8) 113.56(11)O(2) S(1) N(3) 105.80(6) C(9) C(7) C(8) 108.94(12)O(1) S(1) N(3) 106.69(6) N(1) C(7) C(10) 106.16(11)O(2) S(1) C(11) 107.81(6) C(9) C(7) C(10) 108.29(12)O(1) S(1) C(11) 107.90(7) C(8) C(7) C(10) 110.18(12)N(3) S(1) C(11) 107.60(6) C(16) C(11) C(12) 121.16(13)O(3) S(2) O(4) 119.59(6) C(16) C(11) S(1) 119.43(10)O(3) S(2) N(5) 107.32(6) C(12) C(11) S(1) 119.40(11)O(4) S(2) N(5) 106.33(6) C(13) C(12) C(11) 119.24(13)O(3) S(2) C(21) 108.21(6) C(14) C(13) C(12) 118.58(13)O(4) S(2) C(21) 107.46(6) F(1) C(14) C(13) 118.53(14)N(5) S(2) C(21) 107.38(6) F(1) C(14) C(15) 118.28(14)C(2) N(1) C(6) 109.48(10) C(13) C(14) C(15) 123.20(13)C(2) N(1) C(7) 119.58(11) C(14) C(15) C(16) 118.35(14)C(6) N(1) C(7) 116.89(11) C(15) C(16) C(11) 119.46(13)C(4) N(3) C(2) 110.59(10) C(22) C(21) C(26) 121.14(13)C(4) N(3) S(1) 119.19(9) C(22) C(21) S(2) 118.46(10)C(2) N(3) S(1) 116.69(9) C(26) C(21) S(2) 120.38(11)C(4) N(5) C(6) 112.32(10) C(23) C(22) C(21) 119.70(13)C(4) N(5) S(2) 117.40(9) C(24) C(23) C(22) 117.88(13)C(6) N(5) S(2) 117.88(9) F(2) C(24) C(25) 118.48(13)N(1) C(2) N(3) 111.05(10) F(2) C(24) C(23) 117.87(14)N(3) C(4) N(5) 105.16(10) C(25) C(24) C(23) 123.66(14)N(1) C(6) N(5) 110.89(10) C(24) C(25) C(26) 118.35(13)N(1) C(7) C(9) 109.57(11) C(25) C(26) C(21) 119.27(13)

Table S6 Hydrogen Bonds for 1 (100 K).D H A d(D-H)/Å d(H-A)/Å d(D-A)/Å D-H-A/°

C(2) H(2B) O(1)1 0.99 2.43 3.0538(17) 120.9C(6) H(6B) O(3)1 0.99 2.41 3.3600(17) 161.8C(22) H(22) O(4)2 0.95 2.53 3.4670(17) 168.9

1+X,3/2-Y,-1/2+Z; 22-X,2-Y,1-Z

Table S7 Torsion Angles for 1 (100 K).A B C D Angle/˚ A B C D Angle/˚

O(2) S(1) N(3) C(4) 168.81(10) O(1) S(1) C(11) C(16) -18.23(13)O(1) S(1) N(3) C(4) 39.43(12) N(3) S(1) C(11) C(16) 96.54(12)C(11) S(1) N(3) C(4) -76.15(11) O(2) S(1) C(11) C(12) 31.26(13)O(2) S(1) N(3) C(2) -54.16(11) O(1) S(1) C(11) C(12) 162.79(11)O(1) S(1) N(3) C(2) 176.46(10) N(3) S(1) C(11) C(12) -82.44(12)C(11) S(1) N(3) C(2) 60.88(11) C(16) C(11) C(12) C(13) -0.9(2)O(3) S(2) N(5) C(4) -44.91(11) S(1) C(11) C(12) C(13) 178.02(10)

18

O(4) S(2) N(5) C(4) -173.98(9) C(11) C(12) C(13) C(14) 1.1(2)C(21) S(2) N(5) C(4) 71.23(11) C(12) C(13) C(14) F(1) 179.19(13)O(3) S(2) N(5) C(6) 175.79(9) C(12) C(13) C(14) C(15) -0.3(2)O(4) S(2) N(5) C(6) 46.72(11) F(1) C(14) C(15) C(16) 179.92(13)C(21) S(2) N(5) C(6) -68.06(11) C(13) C(14) C(15) C(16) -0.5(2)C(6) N(1) C(2) N(3) 58.01(14) C(14) C(15) C(16) C(11) 0.7(2)C(7) N(1) C(2) N(3) -80.79(14) C(12) C(11) C(16) C(15) 0.0(2)C(4) N(3) C(2) N(1) -62.81(14) S(1) C(11) C(16) C(15) -178.92(11)S(1) N(3) C(2) N(1) 156.66(9) O(3) S(2) C(21) C(22) -172.59(10)C(2) N(3) C(4) N(5) 60.42(13) O(4) S(2) C(21) C(22) -42.18(12)S(1) N(3) C(4) N(5) -160.16(9) N(5) S(2) C(21) C(22) 71.85(12)C(6) N(5) C(4) N(3) -58.70(13) O(3) S(2) C(21) C(26) 8.96(13)S(2) N(5) C(4) N(3) 159.85(9) O(4) S(2) C(21) C(26) 139.37(11)C(2) N(1) C(6) N(5) -55.14(14) N(5) S(2) C(21) C(26) -106.60(12)C(7) N(1) C(6) N(5) 84.90(13) C(26) C(21) C(22) C(23) 1.1(2)C(4) N(5) C(6) N(1) 57.98(14) S(2) C(21) C(22) C(23) -177.35(10)S(2) N(5) C(6) N(1) -160.76(9) C(21) C(22) C(23) C(24) -1.0(2)C(2) N(1) C(7) C(9) -31.35(16) C(22) C(23) C(24) F(2) 179.23(13)C(6) N(1) C(7) C(9) -167.22(11) C(22) C(23) C(24) C(25) -0.3(2)C(2) N(1) C(7) C(8) 90.71(14) F(2) C(24) C(25) C(26) -178.12(13)C(6) N(1) C(7) C(8) -45.16(16) C(23) C(24) C(25) C(26) 1.4(2)C(2) N(1) C(7) C(10) -148.07(11) C(24) C(25) C(26) C(21) -1.2(2)C(6) N(1) C(7) C(10) 76.05(14) C(22) C(21) C(26) C(25) 0.0(2)O(2) S(1) C(11) C(16) -149.76(11) S(2) C(21) C(26) C(25) 178.44(11)

19

2 (100 K) C19H23Cl2N3O4S2



Cl(1) C(11) 1.7411(18) C(5) C(7) 1.525(2)S(1) O(1) 1.4291(15) C(5) C(7)1 1.525(2)S(1) O(2) 1.4349(14) C(5) C(6) 1.541(3)S(1) N(3) 1.6218(16) C(8) C(13) 1.388(2)S(1) C(8) 1.7655(17) C(8) C(9) 1.392(2)N(1) C(2) 1.437(2) C(9) C(10) 1.381(2)N(1) C(2)1 1.437(2) C(10) C(11) 1.384(3)N(1) C(5) 1.493(3) C(11) C(12) 1.389(3)N(3) C(4) 1.458(2) C(12) C(13) 1.388(2)N(3) C(2) 1.496(2)

1+X,1/2-Y,+Z

20

Table S9 Bond Angles for 2 (100 K).Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚

O(1) S(1) O(2) 120.82(9) N(1) C(5) C(7)1 107.78(14)O(1) S(1) N(3) 105.87(9) C(7) C(5) C(7)1 107.8(2)O(2) S(1) N(3) 106.90(8) N(1) C(5) C(6) 114.38(19)O(1) S(1) C(8) 107.60(8) C(7) C(5) C(6) 109.46(14)O(2) S(1) C(8) 107.27(8) C(7)1 C(5) C(6) 109.46(14)N(3) S(1) C(8) 107.81(8) C(13) C(8) C(9) 120.97(16)C(2) N(1) C(2)1 109.1(2) C(13) C(8) S(1) 119.73(13)C(2) N(1) C(5) 118.22(12) C(9) C(8) S(1) 119.27(13)C(2)1 N(1) C(5) 118.22(12) C(10) C(9) C(8) 119.38(17)C(4) N(3) C(2) 112.69(16) C(9) C(10) C(11) 119.33(16)C(4) N(3) S(1) 120.83(13) C(10) C(11) C(12) 121.91(16)C(2) N(3) S(1) 120.36(13) C(10) C(11) Cl(1) 119.12(14)N(1) C(2) N(3) 111.02(15) C(12) C(11) Cl(1) 118.95(14)N(3)1 C(4) N(3) 105.77(19) C(13) C(12) C(11) 118.52(16)N(1) C(5) C(7) 107.78(14) C(8) C(13) C(12) 119.86(16)

1+X,1/2-Y,+Z


C(2) H(2A) O(2)1 0.99 2.42 3.301(2) 148.2C(12) H(12A) O(1)2 0.95 2.40 3.297(2) 157.1

1+X,+Y,1+Z; 21/2+X,+Y,1/2-Z


O(1) S(1) N(3) C(4) 166.40(15) C(2)1 N(1) C(5) C(6) -67.60(15)O(2) S(1) N(3) C(4) 36.38(17) O(1) S(1) C(8) C(13) -140.65(15)C(8) S(1) N(3) C(4) -78.68(16) O(2) S(1) C(8) C(13) -9.24(17)O(1) S(1) N(3) C(2) -43.11(16) N(3) S(1) C(8) C(13) 105.57(15)O(2) S(1) N(3) C(2) -173.13(13) O(1) S(1) C(8) C(9) 41.13(16)C(8) S(1) N(3) C(2) 71.81(15) O(2) S(1) C(8) C(9) 172.54(14)C(2)1 N(1) C(2) N(3) 56.7(2) N(3) S(1) C(8) C(9) -72.64(15)C(5) N(1) C(2) N(3) -82.3(2) C(13) C(8) C(9) C(10) -1.5(3)C(4) N(3) C(2) N(1) -59.4(2) S(1) C(8) C(9) C(10) 176.69(14)S(1) N(3) C(2) N(1) 147.86(14) C(8) C(9) C(10) C(11) 1.0(3)C(2) N(3) C(4) N(3)1 57.1(2) C(9) C(10) C(11) C(12) 0.5(3)S(1) N(3) C(4) N(3)1 -150.31(10) C(9) C(10) C(11) Cl(1) -178.34(14)C(2) N(1) C(5) C(7) -54.4(2) C(10) C(11) C(12) C(13) -1.5(3)C(2)1 N(1) C(5) C(7) 170.44(16) Cl(1) C(11) C(12) C(13) 177.32(14)C(2) N(1) C(5) C(7)1 -170.44(16) C(9) C(8) C(13) C(12) 0.5(3)C(2)1 N(1) C(5) C(7)1 54.4(2) S(1) C(8) C(13) C(12) -177.71(14)C(2) N(1) C(5) C(6) 67.59(15) C(11) C(12) C(13) C(8) 1.0(3)

1+X,1/2-Y,+Z

21

2 (296 K) C19H23Cl2N3O4S2



Cl(1) C(11) 1.743(2) C(5) C(7) 1.518(3)S(1) O(1) 1.4241(19) C(5) C(7)1 1.519(3)S(1) O(2) 1.4275(19) C(5) C(6) 1.524(4)S(1) N(3) 1.614(2) C(8) C(13) 1.377(3)S(1) C(8) 1.765(2) C(8) C(9) 1.384(3)N(1) C(2)1 1.433(3) C(9) C(10) 1.378(3)N(1) C(2) 1.433(3) C(10) C(11) 1.368(3)N(1) C(5) 1.500(4) C(11) C(12) 1.368(4)N(3) C(4) 1.458(3) C(12) C(13) 1.390(3)N(3) C(2) 1.491(3)

1+X,1/2-Y,+Z

Table S12 Bond Angles for 2 (296 K).Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚O(1) S(1) O(2) 120.92(13) N(1) C(5) C(7)1 107.89(18)O(1) S(1) N(3) 106.05(11) C(7) C(5) C(7)1 107.4(3)O(2) S(1) N(3) 106.71(11) N(1) C(5) C(6) 114.2(2)

22

O(1) S(1) C(8) 107.46(10) C(7) C(5) C(6) 109.59(19)O(2) S(1) C(8) 107.31(11) C(7)1 C(5) C(6) 109.59(19)N(3) S(1) C(8) 107.81(10) C(13) C(8) C(9) 120.61(19)C(2)1 N(1) C(2) 109.3(3) C(13) C(8) S(1) 119.87(17)C(2)1 N(1) C(5) 118.21(15) C(9) C(8) S(1) 119.50(16)C(2) N(1) C(5) 118.21(15) C(10) C(9) C(8) 119.4(2)C(4) N(3) C(2) 112.7(2) C(11) C(10) C(9) 119.7(2)C(4) N(3) S(1) 121.19(16) C(12) C(11) C(10) 121.7(2)C(2) N(3) S(1) 120.83(16) C(12) C(11) Cl(1) 119.36(19)N(1) C(2) N(3) 111.36(18) C(10) C(11) Cl(1) 119.0(2)N(3) C(4) N(3)1 106.2(2) C(11) C(12) C(13) 119.0(2)N(1) C(5) C(7) 107.89(18) C(8) C(13) C(12) 119.6(2)

1+X,1/2-Y,+Z


C(2) H(2A) O(2)1 0.97 2.43 3.294(3) 148.7C(12) H(12A) O(1)2 0.93 2.49 3.358(3) 155.0

1+X,+Y,1+Z; 21/2+X,+Y,1/2-Z


O(1) S(1) N(3) C(4) 164.5(2) C(2) N(1) C(5) C(6) 67.79(18)O(2) S(1) N(3) C(4) 34.4(2) O(1) S(1) C(8) C(13) -141.23(19)C(8) S(1) N(3) C(4) -80.6(2) O(2) S(1) C(8) C(13) -9.8(2)O(1) S(1) N(3) C(2) -42.9(2) N(3) S(1) C(8) C(13) 104.85(19)O(2) S(1) N(3) C(2) -173.03(17) O(1) S(1) C(8) C(9) 40.3(2)C(8) S(1) N(3) C(2) 71.96(19) O(2) S(1) C(8) C(9) 171.81(18)C(2)1 N(1) C(2) N(3) 56.2(3) N(3) S(1) C(8) C(9) -73.58(19)C(5) N(1) C(2) N(3) -83.0(3) C(13) C(8) C(9) C(10) -1.2(3)C(4) N(3) C(2) N(1) -58.7(3) S(1) C(8) C(9) C(10) 177.26(18)S(1) N(3) C(2) N(1) 146.56(18) C(8) C(9) C(10) C(11) 0.8(4)C(2) N(3) C(4) N(3)1 56.4(3) C(9) C(10) C(11) C(12) 0.5(4)S(1) N(3) C(4) N(3)1 -149.02(13) C(9) C(10) C(11) Cl(1) -178.38(18)C(2)1 N(1) C(5) C(7) 170.1(2) C(10) C(11) C(12) C(13) -1.4(4)C(2) N(1) C(5) C(7) -54.3(3) Cl(1) C(11) C(12) C(13) 177.49(18)C(2)1 N(1) C(5) C(7)1 54.3(3) C(9) C(8) C(13) C(12) 0.3(3)C(2) N(1) C(5) C(7)1 -170.1(2) S(1) C(8) C(13) C(12) -178.14(17)C(2)1 N(1) C(5) C(6) -67.79(18) C(11) C(12) C(13) C(8) 1.0(4)

1+X,1/2-Y,+Z

23

3 (296 K) C19H23Br2N3O4S2



Br(1) C(11) 1.893(3) C(5) C(7)1 1.515(4)S(1) O(1) 1.424(3) C(5) C(7) 1.515(4)S(1) O(2) 1.430(3) C(5) C(6) 1.528(6)S(1) N(3) 1.607(3) C(8) C(13) 1.372(4)S(1) C(8) 1.770(3) C(8) C(9) 1.377(4)N(1) C(2) 1.434(4) C(9) C(10) 1.377(4)N(1) C(2)1 1.434(4) C(10) C(11) 1.373(5)N(1) C(5) 1.490(5) C(11) C(12) 1.373(5)N(3) C(4) 1.457(4) C(12) C(13) 1.380(4)N(3) C(2) 1.494(4)

1+X,1/2-Y,+Z

Table S16 Bond Angles for 3 (296 K).Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚O(1) S(1) O(2) 121.27(18) N(1) C(5) C(7) 107.8(3)O(1) S(1) N(3) 105.91(16) C(7)1 C(5) C(7) 107.4(4)O(2) S(1) N(3) 106.69(16) N(1) C(5) C(6) 113.9(4)

24

O(1) S(1) C(8) 107.38(15) C(7)1 C(5) C(6) 109.9(3)O(2) S(1) C(8) 107.22(16) C(7) C(5) C(6) 109.9(3)N(3) S(1) C(8) 107.74(15) C(13) C(8) C(9) 120.4(3)C(2) N(1) C(2)1 109.0(4) C(13) C(8) S(1) 119.9(2)C(2) N(1) C(5) 118.6(2) C(9) C(8) S(1) 119.6(2)C(2)1 N(1) C(5) 118.6(2) C(8) C(9) C(10) 119.6(3)C(4) N(3) C(2) 112.3(3) C(11) C(10) C(9) 119.3(3)C(4) N(3) S(1) 121.5(2) C(10) C(11) C(12) 121.8(3)C(2) N(3) S(1) 121.2(2) C(10) C(11) Br(1) 118.9(3)N(1) C(2) N(3) 111.7(3) C(12) C(11) Br(1) 119.3(3)N(3)1 C(4) N(3) 106.4(4) C(11) C(12) C(13) 118.3(3)N(1) C(5) C(7)1 107.8(3) C(8) C(13) C(12) 120.6(3)

1+X,1/2-Y,+Z


C(2) H(2A) O(2)1 0.97 2.39 3.263(4) 149.4C(12) H(12A) O(1)2 0.93 2.48 3.357(4) 156.3

1+X,+Y,1+Z; 21/2+X,+Y,1/2-Z


O(1) S(1) N(3) C(4) 164.4(3) C(2)1 N(1) C(5) C(6) -68.0(3)O(2) S(1) N(3) C(4) 33.9(3) O(1) S(1) C(8) C(13) -141.5(3)C(8) S(1) N(3) C(4) -81.0(3) O(2) S(1) C(8) C(13) -9.7(3)O(1) S(1) N(3) C(2) -42.6(3) N(3) S(1) C(8) C(13) 104.8(3)O(2) S(1) N(3) C(2) -173.1(2) O(1) S(1) C(8) C(9) 39.9(3)C(8) S(1) N(3) C(2) 72.0(3) O(2) S(1) C(8) C(9) 171.7(3)C(2)1 N(1) C(2) N(3) 56.0(5) N(3) S(1) C(8) C(9) -73.8(3)C(5) N(1) C(2) N(3) -83.8(4) C(13) C(8) C(9) C(10) -1.4(5)C(4) N(3) C(2) N(1) -58.8(4) S(1) C(8) C(9) C(10) 177.2(3)S(1) N(3) C(2) N(1) 145.9(3) C(8) C(9) C(10) C(11) 0.8(5)C(2) N(3) C(4) N(3)1 56.8(4) C(9) C(10) C(11) C(12) 0.6(5)S(1) N(3) C(4) N(3)1 -148.1(2) C(9) C(10) C(11) Br(1) -178.1(2)C(2) N(1) C(5) C(7)1 -169.8(3) C(10) C(11) C(12) C(13) -1.2(5)C(2)1 N(1) C(5) C(7)1 54.2(4) Br(1) C(11) C(12) C(13) 177.5(2)C(2) N(1) C(5) C(7) -54.2(4) C(9) C(8) C(13) C(12) 0.7(5)C(2)1 N(1) C(5) C(7) 169.8(3) S(1) C(8) C(13) C(12) -177.9(3)C(2) N(1) C(5) C(6) 68.0(3) C(11) C(12) C(13) C(8) 0.6(5)

1+X,1/2-Y,+Z

25

4 (100 K) C19H23I2N3O4S2



I(1) C(11) 2.0939(14) C(5) C(7) 1.527(2)S(1) O(2) 1.4338(15) C(5) C(7)1 1.527(2)S(1) O(1) 1.4338(14) C(5) C(6) 1.531(3)S(1) N(3) 1.6178(15) C(8) C(13) 1.387(2)S(1) C(8) 1.7704(15) C(8) C(9) 1.388(2)N(1) C(2)1 1.438(2) C(9) C(10) 1.388(2)N(1) C(2) 1.438(2) C(10) C(11) 1.390(2)N(1) C(5) 1.497(3) C(11) C(12) 1.387(2)N(3) C(4) 1.4609(19) C(12) C(13) 1.393(2)N(3) C(2) 1.496(2)

1+X,1/2-Y,+Z


26

O(2) S(1) C(8) 107.07(8) C(7) C(5) C(6) 109.79(13)O(1) S(1) C(8) 107.67(8) C(7)1 C(5) C(6) 109.79(13)N(3) S(1) C(8) 107.97(8) C(13) C(8) C(9) 121.11(14)C(2)1 N(1) C(2) 109.6(2) C(13) C(8) S(1) 119.20(12)C(2)1 N(1) C(5) 118.32(12) C(9) C(8) S(1) 119.67(11)C(2) N(1) C(5) 118.32(12) C(10) C(9) C(8) 119.37(14)C(4) N(3) C(2) 112.34(17) C(9) C(10) C(11) 119.35(14)C(4) N(3) S(1) 120.62(12) C(12) C(11) C(10) 121.56(13)C(2) N(3) S(1) 120.81(12) C(12) C(11) I(1) 119.40(10)N(1) C(2) N(3) 111.37(14) C(10) C(11) I(1) 119.03(11)N(3)1 C(4) N(3) 105.23(17) C(11) C(12) C(13) 118.81(14)N(1) C(5) C(7) 107.73(13) C(8) C(13) C(12) 119.78(14)

1+X,1/2-Y,+Z


C(2) H(2A) O(2)1 0.99 2.33 3.228(2) 149.7C(12) H(12A) O(1)2 0.95 2.42 3.331(2) 159.6

1+X,+Y,1+Z; 21/2+X,+Y,1/2-Z


O(2) S(1) N(3) C(4) 35.47(17) C(2) N(1) C(5) C(6) 68.13(15)O(1) S(1) N(3) C(4) 165.51(15) O(2) S(1) C(8) C(13) -9.38(15)C(8) S(1) N(3) C(4) -79.43(16) O(1) S(1) C(8) C(13) -140.74(14)O(2) S(1) N(3) C(2) -174.40(13) N(3) S(1) C(8) C(13) 105.42(14)O(1) S(1) N(3) C(2) -44.37(15) O(2) S(1) C(8) C(9) 171.86(13)C(8) S(1) N(3) C(2) 70.70(14) O(1) S(1) C(8) C(9) 40.50(16)C(2)1 N(1) C(2) N(3) 55.1(3) N(3) S(1) C(8) C(9) -73.35(14)C(5) N(1) C(2) N(3) -84.6(2) C(13) C(8) C(9) C(10) -1.1(2)C(4) N(3) C(2) N(1) -59.5(2) S(1) C(8) C(9) C(10) 177.69(13)S(1) N(3) C(2) N(1) 148.15(14) C(8) C(9) C(10) C(11) 0.5(2)C(2) N(3) C(4) N(3)1 58.6(2) C(9) C(10) C(11) C(12) 0.7(2)S(1) N(3) C(4) N(3)1 -148.95(10) C(9) C(10) C(11) I(1) -177.88(12)C(2)1 N(1) C(5) C(7) 169.65(16) C(10) C(11) C(12) C(13) -1.3(2)C(2) N(1) C(5) C(7) -54.1(2) I(1) C(11) C(12) C(13) 177.26(12)C(2)1 N(1) C(5) C(7)1 54.1(2) C(9) C(8) C(13) C(12) 0.4(2)C(2) N(1) C(5) C(7)1 -169.65(16) S(1) C(8) C(13) C(12) -178.31(12)C(2)1 N(1) C(5) C(6) -68.13(15) C(11) C(12) C(13) C(8) 0.8(2)

1+X,1/2-Y,+Z

27

4 (296 K) C19H23I2N3O4S2



I(1) C(11) 2.093(3) C(5) C(7) 1.524(4)S(1) O(1) 1.430(3) C(5) C(7)1 1.524(4)S(1) O(2) 1.430(3) C(5) C(6) 1.528(6)S(1) N(3) 1.614(3) C(8) C(13) 1.373(4)S(1) C(8) 1.769(3) C(8) C(9) 1.380(4)N(1) C(2) 1.437(4) C(9) C(10) 1.377(4)N(1) C(2)1 1.437(4) C(10) C(11) 1.382(4)N(1) C(5) 1.494(6) C(11) C(12) 1.377(4)N(3) C(4) 1.457(4) C(12) C(13) 1.383(4)N(3) C(2) 1.493(5)

1+X,1/2-Y,+Z


28

O(1) S(1) C(8) 107.34(15) C(7) C(5) C(6) 109.6(3)O(2) S(1) C(8) 107.06(16) C(7)1 C(5) C(6) 109.6(3)N(3) S(1) C(8) 108.02(15) C(13) C(8) C(9) 120.4(3)C(2) N(1) C(2)1 109.5(4) C(13) C(8) S(1) 119.6(2)C(2) N(1) C(5) 118.6(2) C(9) C(8) S(1) 120.0(2)C(2)1 N(1) C(5) 118.6(2) C(10) C(9) C(8) 119.9(3)C(4) N(3) C(2) 112.4(3) C(9) C(10) C(11) 119.4(3)C(4) N(3) S(1) 120.8(3) C(12) C(11) C(10) 121.0(3)C(2) N(3) S(1) 121.0(2) C(12) C(11) I(1) 119.9(2)N(1) C(2) N(3) 111.4(3) C(10) C(11) I(1) 119.1(2)N(3)1 C(4) N(3) 105.6(4) C(11) C(12) C(13) 119.1(3)N(1) C(5) C(7) 108.1(3) C(8) C(13) C(12) 120.2(3)

1+X,1/2-Y,+Z


C(2) H(2A) O(2)1 0.97 2.37 3.246(4) 149.9C(12) H(12A) O(1)2 0.93 2.51 3.394(4) 159.2

1+X,+Y,1+Z; 21/2+X,+Y,1/2-Z


O(1) S(1) N(3) C(4) 165.0(3) C(2)1 N(1) C(5) C(6) -68.4(3)O(2) S(1) N(3) C(4) 34.6(3) O(1) S(1) C(8) C(13) -141.0(3)C(8) S(1) N(3) C(4) -80.2(3) O(2) S(1) C(8) C(13) -9.5(3)O(1) S(1) N(3) C(2) -43.8(3) N(3) S(1) C(8) C(13) 105.0(3)O(2) S(1) N(3) C(2) -174.2(3) O(1) S(1) C(8) C(9) 39.9(3)C(8) S(1) N(3) C(2) 71.0(3) O(2) S(1) C(8) C(9) 171.4(3)C(2)1 N(1) C(2) N(3) 55.3(5) N(3) S(1) C(8) C(9) -74.1(3)C(5) N(1) C(2) N(3) -85.0(4) C(13) C(8) C(9) C(10) -0.5(5)C(4) N(3) C(2) N(1) -59.3(4) S(1) C(8) C(9) C(10) 178.7(3)S(1) N(3) C(2) N(1) 147.3(3) C(8) C(9) C(10) C(11) -0.4(5)C(2) N(3) C(4) N(3)1 58.2(5) C(9) C(10) C(11) C(12) 1.6(5)S(1) N(3) C(4) N(3)1 -148.3(2) C(9) C(10) C(11) I(1) -177.8(3)C(2) N(1) C(5) C(7) -53.7(5) C(10) C(11) C(12) C(13) -1.8(5)C(2)1 N(1) C(5) C(7) 169.5(3) I(1) C(11) C(12) C(13) 177.5(3)C(2) N(1) C(5) C(7)1 -169.5(3) C(9) C(8) C(13) C(12) 0.2(5)C(2)1 N(1) C(5) C(7)1 53.7(5) S(1) C(8) C(13) C(12) -178.9(3)C(2) N(1) C(5) C(6) 68.4(3) C(11) C(12) C(13) C(8) 0.9(5)

1+X,1/2-Y,+Z

29

1·CDCl3 C19H23F2N3O4S2CDCl3

X-ray data for 1·CDCl3 at 100 K. Thermal ellipsoids are shown at the 50% probability level.

Table S27 Bond Lengths for 1·CDCl3.Atom Atom Length/Å Atom Atom Length/Å

F(1) C(14) 1.355(3) N(5) C(4) 1.477(3)F(2) C(24) 1.354(3) N(5) C(6) 1.504(3)Cl(3) C(1) 1.748(3) C(1) D(1A) 1.0000Cl(4) C(1) 1.752(3) C(7) C(9) 1.530(3)Cl(5) C(1) 1.757(3) C(7) C(8) 1.529(4)S(1) O(1) 1.430(2) C(7) C(10) 1.541(4)S(1) O(2) 1.4321(19) C(11) C(12) 1.392(4)S(1) N(3) 1.644(2) C(11) C(16) 1.391(4)S(1) C(11) 1.769(3) C(12) C(13) 1.383(4)

30

S(2) O(3) 1.429(2) C(13) C(14) 1.385(4)S(2) O(4) 1.431(2) C(14) C(15) 1.383(4)S(2) N(5) 1.647(2) C(15) C(16) 1.385(4)S(2) C(21) 1.758(3) C(21) C(26) 1.396(4)N(1) C(6) 1.435(3) C(21) C(22) 1.397(4)N(1) C(2) 1.437(3) C(22) C(23) 1.379(4)N(1) C(7) 1.493(3) C(23) C(24) 1.380(4)N(3) C(4) 1.466(3) C(24) C(25) 1.374(4)N(3) C(2) 1.497(3) C(25) C(26) 1.390(4)

Table S28 Bond Angles for 1·CDCl3.Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚O(1) S(1) O(2) 120.59(12) N(3) C(4) N(5) 106.4(2)O(1) S(1) N(3) 106.76(11) N(1) C(6) N(5) 111.36(19)O(2) S(1) N(3) 106.17(11) N(1) C(7) C(9) 107.4(2)O(1) S(1) C(11) 107.64(12) N(1) C(7) C(8) 107.9(2)O(2) S(1) C(11) 107.67(12) C(9) C(7) C(8) 108.5(2)N(3) S(1) C(11) 107.38(11) N(1) C(7) C(10) 114.5(2)O(3) S(2) O(4) 120.42(12) C(9) C(7) C(10) 109.0(2)O(3) S(2) N(5) 106.55(11) C(8) C(7) C(10) 109.4(2)O(4) S(2) N(5) 106.44(11) C(12) C(11) C(16) 121.6(2)O(3) S(2) C(21) 108.14(12) C(12) C(11) S(1) 119.2(2)O(4) S(2) C(21) 108.16(12) C(16) C(11) S(1) 119.3(2)N(5) S(2) C(21) 106.33(11) C(13) C(12) C(11) 119.5(2)C(6) N(1) C(2) 109.3(2) C(12) C(13) C(14) 118.1(3)C(6) N(1) C(7) 119.12(19) F(1) C(14) C(15) 118.6(3)C(2) N(1) C(7) 118.26(19) F(1) C(14) C(13) 118.1(3)C(4) N(3) C(2) 111.94(19) C(15) C(14) C(13) 123.3(3)C(4) N(3) S(1) 114.93(16) C(14) C(15) C(16) 118.4(3)C(2) N(3) S(1) 116.56(16) C(15) C(16) C(11) 119.2(3)C(4) N(5) C(6) 111.61(19) C(26) C(21) C(22) 120.8(2)C(4) N(5) S(2) 114.23(17) C(26) C(21) S(2) 120.0(2)C(6) N(5) S(2) 115.55(15) C(22) C(21) S(2) 119.2(2)Cl(3) C(1) Cl(4) 111.04(18) C(23) C(22) C(21) 119.5(3)Cl(3) C(1) Cl(5) 111.44(18) C(22) C(23) C(24) 118.6(3)Cl(4) C(1) Cl(5) 109.92(17) F(2) C(24) C(25) 118.6(3)Cl(3) C(1) D(1A) 108.1 F(2) C(24) C(23) 118.1(3)Cl(4) C(1) D(1A) 108.1 C(25) C(24) C(23) 123.3(3)Cl(5) C(1) D(1A) 108.1 C(24) C(25) C(26) 118.3(3)N(1) C(2) N(3) 110.82(19) C(25) C(26) C(21) 119.5(3)

Table S29 Hydrogen Bonds for 1·CDCl3.D H A d(D-H)/Å d(H-A)/Å d(D-A)/Å D-H-A/°

C(1) D(1A) F(1) 1.00 2.48 3.356(4) 145.5C(2) H(2A) O(3)1 0.99 2.64 3.138(3) 110.9

31

C(8) H(8C) Cl(3)2 0.98 2.89 3.675(3) 138.3C(9) H(9C) F(2)3 0.98 2.58 3.445(3) 146.7C(10) H(10B) N(5) 0.98 2.68 3.211(4) 114.2C(10) H(10C) N(3) 0.98 2.66 3.198(4) 115.0C(15) H(15A) F(2)4 0.95 2.60 3.479(3) 153.6C(23) H(23A) Cl(4)5 0.95 2.84 3.649(3) 144.0

11/2+X,3/2-Y,1-Z; 2+X,1+Y,+Z; 31-X,1/2+Y,1/2-Z; 43/2-X,1-Y,1/2+Z; 5-1/2+X,1/2-Y,1-Z

Table S30 Torsion Angles for 1·CDCl3.A B C D Angle/˚ A B C D Angle/˚

O(1) S(1) N(3) C(4) -46.6(2) O(2) S(1) C(11) C(12) 149.6(2)O(2) S(1) N(3) C(4) -176.41(18) N(3) S(1) C(11) C(12) -96.4(2)C(11) S(1) N(3) C(4) 68.6(2) O(1) S(1) C(11) C(16) -162.30(19)O(1) S(1) N(3) C(2) 179.56(18) O(2) S(1) C(11) C(16) -30.9(2)O(2) S(1) N(3) C(2) 49.7(2) N(3) S(1) C(11) C(16) 83.1(2)C(11) S(1) N(3) C(2) -65.2(2) C(16) C(11) C(12) C(13) 0.6(4)O(3) S(2) N(5) C(4) 48.6(2) S(1) C(11) C(12) C(13) -179.9(2)O(4) S(2) N(5) C(4) 178.28(17) C(11) C(12) C(13) C(14) -0.4(4)C(21) S(2) N(5) C(4) -66.57(19) C(12) C(13) C(14) F(1) 179.4(2)O(3) S(2) N(5) C(6) -179.88(17) C(12) C(13) C(14) C(15) -0.4(4)O(4) S(2) N(5) C(6) -50.2(2) F(1) C(14) C(15) C(16) -178.8(2)C(21) S(2) N(5) C(6) 64.9(2) C(13) C(14) C(15) C(16) 1.0(4)C(6) N(1) C(2) N(3) -57.9(3) C(14) C(15) C(16) C(11) -0.8(4)C(7) N(1) C(2) N(3) 82.8(3) C(12) C(11) C(16) C(15) 0.0(4)C(4) N(3) C(2) N(1) 60.2(3) S(1) C(11) C(16) C(15) -179.44(19)S(1) N(3) C(2) N(1) -164.60(17) O(3) S(2) C(21) C(26) 157.7(2)C(2) N(3) C(4) N(5) -57.6(2) O(4) S(2) C(21) C(26) 25.8(2)S(1) N(3) C(4) N(5) 166.43(16) N(5) S(2) C(21) C(26) -88.2(2)C(6) N(5) C(4) N(3) 56.6(2) O(3) S(2) C(21) C(22) -24.7(2)S(2) N(5) C(4) N(3) -169.98(16) O(4) S(2) C(21) C(22) -156.6(2)C(2) N(1) C(6) N(5) 57.4(3) N(5) S(2) C(21) C(22) 89.4(2)C(7) N(1) C(6) N(5) -82.9(3) C(26) C(21) C(22) C(23) -0.6(4)C(4) N(5) C(6) N(1) -58.7(3) S(2) C(21) C(22) C(23) -178.2(2)S(2) N(5) C(6) N(1) 168.56(16) C(21) C(22) C(23) C(24) -0.5(4)C(6) N(1) C(7) C(9) -53.8(3) C(22) C(23) C(24) F(2) -178.9(2)C(2) N(1) C(7) C(9) 169.4(2) C(22) C(23) C(24) C(25) 1.0(4)C(6) N(1) C(7) C(8) -170.6(2) F(2) C(24) C(25) C(26) 179.5(2)C(2) N(1) C(7) C(8) 52.6(3) C(23) C(24) C(25) C(26) -0.4(4)C(6) N(1) C(7) C(10) 67.4(3) C(24) C(25) C(26) C(21) -0.7(4)C(2) N(1) C(7) C(10) -69.5(3) C(22) C(21) C(26) C(25) 1.2(4)O(1) S(1) C(11) C(12) 18.2(2) S(2) C(21) C(26) C(25) 178.77(19)

32

2·CDCl3 C19H23Cl2N3O4S2CDCl3

X-ray data for 2·CDCl3 at 100 K. Thermal ellipsoids are shown at the 50% probability level.

Table S31 Bond Lengths for 2·CDCl3.Atom Atom Length/Å Atom Atom Length/Å

Cl(1) C(14) 1.741(2) N(5) C(4) 1.470(3)Cl(2) C(24) 1.733(2) N(5) C(6) 1.504(3)Cl(3) C(1) 1.749(3) C(1) D(1A) 1.0000Cl(4) C(1) 1.751(3) C(7) C(8) 1.528(3)Cl(5) C(1) 1.760(3) C(7) C(9) 1.528(3)S(1) O(1) 1.4313(16) C(7) C(10) 1.543(3)S(1) O(2) 1.4352(16) C(11) C(16) 1.392(3)S(1) N(3) 1.6389(17) C(11) C(12) 1.396(3)S(1) C(11) 1.768(2) C(12) C(13) 1.395(3)S(2) O(3) 1.4303(16) C(13) C(14) 1.383(3)

33

S(2) O(4) 1.4359(16) C(14) C(15) 1.392(3)S(2) N(5) 1.6409(18) C(15) C(16) 1.387(3)S(2) C(21) 1.762(2) C(21) C(26) 1.398(3)N(1) C(6) 1.438(3) C(21) C(22) 1.398(3)N(1) C(2) 1.440(3) C(22) C(23) 1.387(3)N(1) C(7) 1.491(3) C(23) C(24) 1.385(3)N(3) C(4) 1.465(3) C(24) C(25) 1.388(3)N(3) C(2) 1.500(3) C(25) C(26) 1.390(3)

Table S32 Bond Angles for 2·CDCl3.Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚O(1) S(1) O(2) 120.72(10) N(3) C(4) N(5) 106.59(17)O(1) S(1) N(3) 106.68(9) N(1) C(6) N(5) 111.08(16)O(2) S(1) N(3) 105.97(9) N(1) C(7) C(8) 107.58(17)O(1) S(1) C(11) 107.61(10) N(1) C(7) C(9) 107.86(17)O(2) S(1) C(11) 107.82(10) C(8) C(7) C(9) 108.72(19)N(3) S(1) C(11) 107.40(9) N(1) C(7) C(10) 114.46(19)O(3) S(2) O(4) 120.39(10) C(8) C(7) C(10) 109.21(19)O(3) S(2) N(5) 106.69(9) C(9) C(7) C(10) 108.9(2)O(4) S(2) N(5) 106.33(9) C(16) C(11) C(12) 121.1(2)O(3) S(2) C(21) 107.79(10) C(16) C(11) S(1) 119.90(17)O(4) S(2) C(21) 108.40(10) C(12) C(11) S(1) 119.01(16)N(5) S(2) C(21) 106.44(9) C(13) C(12) C(11) 119.3(2)C(6) N(1) C(2) 109.25(17) C(14) C(13) C(12) 118.9(2)C(6) N(1) C(7) 118.85(16) C(13) C(14) C(15) 122.2(2)C(2) N(1) C(7) 118.70(16) C(13) C(14) Cl(1) 118.88(18)C(4) N(3) C(2) 112.05(16) C(15) C(14) Cl(1) 118.91(17)C(4) N(3) S(1) 115.87(14) C(16) C(15) C(14) 118.8(2)C(2) N(3) S(1) 117.42(13) C(15) C(16) C(11) 119.7(2)C(4) N(5) C(6) 111.59(16) C(26) C(21) C(22) 120.8(2)C(4) N(5) S(2) 115.20(14) C(26) C(21) S(2) 120.36(16)C(6) N(5) S(2) 116.66(13) C(22) C(21) S(2) 118.77(17)Cl(3) C(1) Cl(4) 110.64(15) C(23) C(22) C(21) 119.3(2)Cl(3) C(1) Cl(5) 111.53(15) C(24) C(23) C(22) 119.3(2)Cl(4) C(1) Cl(5) 110.24(15) C(23) C(24) C(25) 122.1(2)Cl(3) C(1) D(1A) 108.1 C(23) C(24) Cl(2) 118.37(17)Cl(4) C(1) D(1A) 108.1 C(25) C(24) Cl(2) 119.54(17)Cl(5) C(1) D(1A) 108.1 C(24) C(25) C(26) 118.8(2)N(1) C(2) N(3) 110.68(16) C(25) C(26) C(21) 119.7(2)

Table S33 Hydrogen Bonds for 2·CDCl3.D H A d(D-H)/Å d(H-A)/Å d(D-A)/Å D-H-A/°

C(1) D(1A) Cl(1) 1.00 2.83 3.631(3) 137.0C(6) H(6B) Cl(2)1 0.99 2.88 3.823(2) 160.2C(8) H(8A) Cl(2)2 0.98 2.94 3.553(2) 121.8

34

C(8) H(8C) Cl(3)3 0.98 2.71 3.525(3) 140.7C(10) H(10B) N(5) 0.98 2.67 3.205(3) 114.4C(10) H(10C) N(3) 0.98 2.67 3.205(3) 114.7C(15) H(15A) Cl(2)4 0.95 2.93 3.837(2) 159.1C(23) H(23A) Cl(4)5 0.95 2.86 3.574(2) 132.6C(26) H(26A) Cl(2)1 0.95 2.95 3.875(2) 164.6

11-X,1/2+Y,1/2-Z; 2-1/2+X,3/2-Y,1-Z; 3+X,1+Y,+Z; 43/2-X,1-Y,1/2+Z; 5-1/2+X,1/2-Y,1-Z

Table S34 Torsion Angles for 2·CDCl3.A B C D Angle/˚ A B C D Angle/˚

O(1) S(1) N(3) C(4) -45.44(17) O(2) S(1) C(11) C(16) -31.3(2)O(2) S(1) N(3) C(4) -175.27(15) N(3) S(1) C(11) C(16) 82.48(18)C(11) S(1) N(3) C(4) 69.70(17) O(1) S(1) C(11) C(12) 17.09(19)O(1) S(1) N(3) C(2) 178.38(15) O(2) S(1) C(11) C(12) 148.77(17)O(2) S(1) N(3) C(2) 48.55(17) N(3) S(1) C(11) C(12) -97.43(18)C(11) S(1) N(3) C(2) -66.48(17) C(16) C(11) C(12) C(13) 0.0(3)O(3) S(2) N(5) C(4) 46.23(17) S(1) C(11) C(12) C(13) 179.95(17)O(4) S(2) N(5) C(4) 175.89(14) C(11) C(12) C(13) C(14) -0.1(3)C(21) S(2) N(5) C(4) -68.67(16) C(12) C(13) C(14) C(15) -0.1(3)O(3) S(2) N(5) C(6) 179.97(14) C(12) C(13) C(14) Cl(1) 179.09(17)O(4) S(2) N(5) C(6) -50.37(17) C(13) C(14) C(15) C(16) 0.5(3)C(21) S(2) N(5) C(6) 65.06(17) Cl(1) C(14) C(15) C(16) -178.73(17)C(6) N(1) C(2) N(3) -57.7(2) C(14) C(15) C(16) C(11) -0.6(3)C(7) N(1) C(2) N(3) 83.0(2) C(12) C(11) C(16) C(15) 0.3(3)C(4) N(3) C(2) N(1) 59.7(2) S(1) C(11) C(16) C(15) -179.58(17)S(1) N(3) C(2) N(1) -162.49(14) O(3) S(2) C(21) C(26) 161.29(16)C(2) N(3) C(4) N(5) -57.5(2) O(4) S(2) C(21) C(26) 29.47(19)S(1) N(3) C(4) N(5) 163.99(13) N(5) S(2) C(21) C(26) -84.56(18)C(6) N(5) C(4) N(3) 57.0(2) O(3) S(2) C(21) C(22) -21.58(19)S(2) N(5) C(4) N(3) -166.96(13) O(4) S(2) C(21) C(22) -153.40(16)C(2) N(1) C(6) N(5) 57.7(2) N(5) S(2) C(21) C(22) 92.57(18)C(7) N(1) C(6) N(5) -82.9(2) C(26) C(21) C(22) C(23) -0.4(3)C(4) N(5) C(6) N(1) -59.3(2) S(2) C(21) C(22) C(23) -177.53(16)S(2) N(5) C(6) N(1) 165.43(14) C(21) C(22) C(23) C(24) 0.1(3)C(6) N(1) C(7) C(8) -170.49(18) C(22) C(23) C(24) C(25) 0.2(3)C(2) N(1) C(7) C(8) 52.6(2) C(22) C(23) C(24) Cl(2) -179.39(16)C(6) N(1) C(7) C(9) -53.4(2) C(23) C(24) C(25) C(26) -0.2(3)C(2) N(1) C(7) C(9) 169.68(18) Cl(2) C(24) C(25) C(26) 179.32(16)C(6) N(1) C(7) C(10) 68.0(2) C(24) C(25) C(26) C(21) 0.0(3)C(2) N(1) C(7) C(10) -69.0(2) C(22) C(21) C(26) C(25) 0.3(3)O(1) S(1) C(11) C(16) -162.99(16) S(2) C(21) C(26) C(25) 177.42(16)

35

3. Copies of NMR spectra of synthesised compounds 1-4 (in CDCl3, r.t, 1H/13C, 600/125 MHz).

36

1H NMR spectrum of compound 1

37


7.207.257.307.357.407.457.507.557.607.657.707.757.807.85f1 (мд)

D (ddd)7.82

E (m)7.20

4.02

3.96

7.18

7.18

7.19

7.19

7.19

7.20

7.20

7.20

7.21

7.21

7.22

7.26

CD

Cl3

7.80

7.81

7.81

7.81

7.82

7.82

7.82

7.83

7.83

N

F

S

O

ON

F

S

O

O

N

CH3 CH3CH3

38

13С NMR spectrum of compound 1

39

13С NMR spectrum of compound 1

40

19F NMR spectrum of compound 1

41

COSY spectrum of compound

42

HMQC spectrum of compound 1

43


44

13C NMR spectrum of compound 2

45


46


47


48


49

4. Experimental details for 2D low temperature NMR.

1H, 13C, 19F, and corresponding 2D NMR spectra for the temperature/dynamic experiments of

triazinanes 1-4 were recorded on a «Bruker AVANCE-III-HD 300» (300.1, 75.5, and 282.4 MHz,

respectively) and «Bruker AVANCE-III 400» (400.1, 100.6, and 376.5 MHz, respectively)

spectrometers equipped with BBF probes in CD2Cl2, THF-d8/CD2Cl2 (v/v, 1:1), i-PrCl-d7, and i-

PrCl-h7. Chemical shifts were automated referenced by “Bruker Topspin 3.2” software to 2H signals

of the corresponding deuterated solvent.

Temperature/dynamic NMR experiments of triazinane 1 were made at temperatures beginning

with +20 °C and subsequent cooling to –135 °C (in CD2Cl2 to –100 °C; in THF-d8/CD2Cl2 1:1 to –

135 °C) with 10 °C step (or smaller if necessary) and enough time to equalize the temperature.

Determinations of structures and stereochemistry of the conformers A−C of triazinanes 1−4 and

assignments of 1H, 13C, and 19F signals were made with the aid of 2D TOCSY, NOESY, edited-

HSQC, and 1H–19F HMBC techniques with Z-gradient selection in temperature interval –90 ÷ –120

°C in both CD2Cl2 and THF-d8/CD2Cl2 solvents. A used BBF probe was specially calibrated on each

nuclei 1H/13C/19F at each low temperature (tuning/matching); as well as, 90° pulses were also

partially adjusted for temperatures lower than –60 °C for the proper implementation of 2D

experiments. Exchange between conformers of triazinane 1 and their configurations were studied

using a set of 2D EXSY / NOESY spectra with variable mixing times (from 50 to 600 msec) at

temperature interval –100 ÷ –110 °C and in CD2Cl2 and THF-d8/CD2Cl2 (v/v, 1:1) as solvents.

“MestreNova” and “Bruker Topspin 3.6” software were used for the deconvolution and line

fitting of the 19F NMR spectra obtained in the temperature interval –90 ÷ –120 °C.

50

Assignments of 19F NMR spectra of fluoro-triazinane 1in CD2Cl2 and THF-d8/CD2Cl2 (1/1) at –100 °C and –110 °C

51

Assignments of 1H and 2D EXSY/NOESY (100 msec) NMR spectraof fluoro derivative 1 in THF-d8/CD2Cl2 (v/v, 1/1) at –110 °C

52

A set of 1H NMR spectra of fluoro-triazinane 1 in THF-d8/CD2Cl2 (1/1)at various temperatures from +20 °C to –130 °C

53

5. Copies of 1D and 2D dynamic NMR spectra at various temperatures for triazinane 1.

(1)

54

1H NMR spectrum of fluoro-triazinane 1 in CD2Cl2 at +20 °C

55

19F NMR spectrum of fluoro-triazinane 1 in CD2Cl2 at +20 °C

56

A set of 1H NMR spectra of fluoro-triazinane 1 in CD2Cl2 at various temperatures(from the bottom to the top): +20 °C; –20 °C; –50 °C; –60 °C; –90 °C; –100 °C

57

A set of 19F NMR spectra of fluoro-triazinane 1 in CD2Cl2 at various temperatures(from the bottom to the top): +20 °C; –20 °C; –50 °C; –60 °C; –90 °C; –100 °C

58

1H NMR spectrum of fluoro-triazinane 1 in CD2Cl2 at –100 °C

59

19F NMR spectrum of fluoro-triazinane 1 in CD2Cl2 at –100 °C

60

19F NMR spectrum (deconvolution) of fluoro-triazinane 1 in CD2Cl2 at –100 °C

61

13C{1H} NMR spectrum of fluoro-triazinane 1 in CD2Cl2 at –100 °C

62

2D 1H–1H EXSY (mixing time = 100 msec) NMR spectrum of fluoro-triazinane 1 in CD2Cl2 at –100 °C

63

2D 1H–1H NOESY (mixing time = 500 msec) NMR spectrum of fluoro-triazinane 1 in CD2Cl2 at –100 °C

64

2D 1H–1H TOCSY (mixing time = 85 msec) NMR spectrum of fluoro-triazinane 1 in CD2Cl2 at –100 °C

65

2D 1H–13C edited-HSQC NMR spectrum of fluoro-triazinane 1 in CD2Cl2 at –100 °C

66

2D 1H–13C edited-HSQC NMR spectrum (expanded region) of fluoro-triazinane 1 in CD2Cl2 at –100 °C

67

2D 1H–19F HMBC NMR spectrum of fluoro-triazinane 1 in CD2Cl2 at –100 °C

68

2D 1H–19F HMBC NMR spectrum (expanded region) of fluoro-triazinane 1 in CD2Cl2 at –100 °C

69

1H NMR spectrum of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at +20 °C

70

19F NMR spectrum of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at +20 °C

71

A set of 1H NMR spectra of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at various temperatures(from bottom to top): +20 °C; –50 °C; –80 °C; –90 °C; –100 °C; –110 °C

72

A set of 1H NMR spectra of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at various temperatures(from bottom to top): –100 °C; –110 °C; –120 °C; –128 °C; –130 °C; –135 °C

73

A set of 19F NMR spectra of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at various temperatures(from bottom to top): +20 °C; –50 °C; –80 °C; –90 °C; –100 °C; –110 °C

74

A set of 19F NMR spectra of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at various temperatures(from bottom to top): –100 °C; –110 °C; –120 °C; –128 °C; –130 °C; –135 °C

75

1H NMR spectrum of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at –110 °C

76

19F NMR spectrum of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at –110 °C

77

19F NMR spectrum (deconvolution) of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at –110 °C

78

19F NMR spectrum (deconvolution with minor component) of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at –110 °C

79

13C{1H} NMR spectrum of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at –110 °C

80

2D 1H–1H EXSY (mixing time = 100 msec) NMR spectrum of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at –110 °C

81

2D 1H–1H EXSY (mixing time = 100 msec) NMR spectrum (expanded region) of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at –110 °C

82

2D 1H–1H NOESY (mixing time = 500 msec) NMR spectrum of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at –110 °C

83

2D 1H–1H TOCSY (mixing time = 85 msec) NMR spectrum of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at –110 °C

84

2D 1H–13C edited-HSQC NMR spectrum of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at –110 °C

85

2D 1H–13C edited-HSQC NMR spectrum (expanded region) of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at –110 °C

86

1H NMR spectrum of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at –128 °C

87

19F NMR spectrum of fluoro-triazinane 1 in THF-d8/CD2Cl2 (v/v, 1:1) at –128 °C

88

6. Copies of 1D and 2D dynamic NMR spectra at various temperatures for triazinane 3.

(3)

N

Br

SO

O

N

Br

SO

O N

89

1H NMR spectrum of bromo-triazinane 3 in THF-d8/CD2Cl2 at +20 °C

90

1H NMR spectrum of bromo-triazinane 3 in THF-d8/CD2Cl2 at -110 °C

91

A set of 1H NMR spectra of bromo-triazinane 3 in in THF-d8/CD2Cl2 at various temperatures (part 1)(from the bottom to the top): +20 °C; –20 °C; –50 °C; –80 °C; –90 °C

92

A set of 1H NMR spectra of bromo-triazinane 3 in in THF-d8/CD2Cl2 at various temperatures (part 2)(from the bottom to the top): –90 °C; –100 °C; –110 °C; –120 °C; –130 °C

93

A set of 1H NMR spectra of bromo-triazinane 3 in in THF-d8/CD2Cl2 at various temperatures (FULL)

94

2D 1H–1H EXSY (mixing time = 100 msec) NMR spectrum of bromo-triazinane 3 in THF-d8/CD2Cl2 (v/v, 1:1) at –110 °C

95

2D 1H–1H EXSY (mixing time = 100 msec) NMR spectrum (expanded region) of bromo-triazinane 3 in THF-d8/CD2Cl2 (v/v, 1:1) at –110 °C

96

2D 1H–13C edited-HSQC NMR spectrum of bromo-triazinane 3 in THF-d8/CD2Cl2 (v/v, 1:1) at –110 °C

97

7. Conformational study of the hypothetical N-methyl derivative

Fig. S6 shows the optimized geometries (PBE1PBE-D3/def2-TZVP level of theory) of conformers A-C of compound 1 where the t-Bu group has been replaced by a Me group. It can be observed that isomer B is slightly more favored than C (0.5 kcal/mol) due to the formation of an intramolecular C–H···O bond. The all-e isomer (A) is the least favored. Although isomer B is the most stable thermodynamically, it is not likely to occur in the solid state since the orientation of one of the arenes would hinder a close packing. It should be also emphasized that the existence of the different conformers in solution would be highly dependent of the first solvation sphere, as demonstrated for compound 1 (see the main text).

Figure S6. PBE1PBE-D3/def2-TZVP optimized geometries and energies of isomers A-C.

Cartesian coordinates and energies of the compounds:

Compound A:Energy -2081.703099X-ray coordinatesNImag=0Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 -2.617465 -1.346167 -0.889887 2 8 0 -3.593243 -2.218791 -0.301741 3 8 0 -2.341672 -1.335973 -2.297556 4 7 0 -0.000023 -2.590814 1.708426 5 7 0 -1.178070 -1.679495 -0.132943 6 6 0 -1.196255 -1.872077 1.316219 7 1 0 -1.260408 -0.887284 1.827703 8 1 0 -2.071702 -2.461040 1.576413 9 6 0 -0.000022 -0.961377 -0.606422 10 1 0 -0.000012 -0.950078 -1.691042 11 1 0 -0.000011 0.072503 -0.217849 12 6 0 0.000057 -2.899080 3.129040 13 6 0 -3.019150 0.320297 -0.409312 14 6 0 -3.753743 0.543955 0.752952 15 1 0 -4.135994 -0.295858 1.316134 16 6 0 -4.014009 1.843953 1.162854 17 1 0 -4.588830 2.055008 2.053839 18 6 0 -3.529160 2.890508 0.395316 19 6 0 -2.804653 2.688660 -0.768212 20 1 0 -2.463846 3.539868 -1.341023 21 6 0 -2.548385 1.386273 -1.172980 22 1 0 -2.007028 1.192264 -2.088436 23 16 0 2.617426 -1.346200 -0.889854 24 8 0 3.593189 -2.218832 -0.301695 25 8 0 2.341648 -1.336026 -2.297525 26 7 0 1.178017 -1.679493 -0.132921 27 6 0 1.196185 -1.872037 1.316239 28 1 0 1.260293 -0.887230 1.827702 29 1 0 2.071659 -2.460950 1.576458 30 6 0 3.019157 0.320265 -0.409318 31 6 0 3.753743 0.543930 0.752949 32 1 0 4.135963 -0.295879 1.316158 33 6 0 4.014023 1.843931 1.162833

98

34 1 0 4.588829 2.054992 2.053827 35 6 0 3.529207 2.890481 0.395268 36 6 0 2.804718 2.688625 -0.768269 37 1 0 2.463935 3.539829 -1.341099 38 6 0 2.548435 1.386236 -1.173020 39 1 0 2.007084 1.192219 -2.088478 40 9 0 -3.779579 4.151330 0.789890 41 9 0 3.779647 4.151305 0.789822 42 1 0 -0.882395 -3.491895 3.371177 43 1 0 -0.000026 -2.000371 3.769253 44 1 0 0.882765 -3.491596 3.371099---------------------------------------------------------------------

Compound BEnergy: -2081.712342NImag=0X-ray coordinates--------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 2.459602 -1.334985 -0.040756 2 8 0 3.272709 -2.225873 -0.826597 3 8 0 2.118836 -1.664830 1.317320 4 7 0 -0.439247 -2.947874 -1.200555 5 7 0 1.098014 -1.047336 -0.967096 6 6 0 0.560202 -2.123436 -1.838635 7 1 0 0.099813 -1.612796 -2.688712 8 1 0 1.389391 -2.727298 -2.192447 9 6 0 0.041948 -0.251174 -0.365530 10 1 0 0.447512 0.435169 0.371422 11 1 0 -0.426307 0.331136 -1.171028 12 6 0 0.090439 -3.928751 -0.248051 13 6 0 3.205203 0.276803 -0.012430 14 6 0 3.895751 0.726831 -1.135341 15 1 0 3.981305 0.090438 -2.005350 16 6 0 4.481997 1.982041 -1.119367 17 1 0 5.033207 2.364311 -1.967184 18 6 0 4.356453 2.757736 0.024221 19 6 0 3.677095 2.324999 1.149576 20 1 0 3.614634 2.964651 2.018795 21 6 0 3.096361 1.062999 1.130192 22 1 0 2.568216 0.684067 1.994227 23 16 0 -1.920884 -0.468729 1.439779 24 8 0 -2.660752 -1.559256 2.009956 25 8 0 -1.093615 0.397308 2.234335 26 7 0 -0.948402 -1.118138 0.278772 27 6 0 -1.496654 -2.134410 -0.655062 28 1 0 -2.015835 -1.627551 -1.479236 29 1 0 -2.204691 -2.750316 -0.108026 30 6 0 -3.077092 0.560638 0.557529 31 6 0 -4.266816 0.010811 0.085505 32 1 0 -4.513237 -1.015521 0.319252 33 6 0 -5.140176 0.793017 -0.657152 34 1 0 -6.076069 0.401729 -1.031146 35 6 0 -4.798155 2.111633 -0.909134 36 6 0 -3.624208 2.679472 -0.441603 37 1 0 -3.411166 3.718399 -0.651696 38 6 0 -2.755482 1.891583 0.300625 39 1 0 -1.842476 2.309880 0.700934 40 9 0 4.922728 3.977666 0.038653 41 9 0 -5.642750 2.872706 -1.627984 42 1 0 0.496063 -3.473594 0.660606 43 1 0 0.879675 -4.502880 -0.732191 44 1 0 -0.710507 -4.613856 0.031366 ---------------------------------------------------------------------Compound CEnergy: -2081.711501NImag=0X-ray coordinates--------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 2.616435 -1.327024 0.760874 2 8 0 3.579184 -2.192247 0.138938 3 8 0 2.342241 -1.371120 2.169176 4 7 0 0.000032 -2.439470 -1.933839 5 7 0 1.181815 -1.604400 -0.016368 6 6 0 1.183397 -1.745201 -1.493774 7 1 0 1.201761 -0.751261 -1.959523 8 1 0 2.075048 -2.294826 -1.779670 9 6 0 -0.000009 -0.905974 0.484758 10 1 0 -0.000027 -0.933894 1.569637 11 1 0 -0.000000 0.142247 0.137309 12 6 0 -0.000001 -3.867462 -1.603895 13 6 0 3.047860 0.350586 0.349420

99

14 6 0 3.776570 0.609489 -0.809301 15 1 0 4.137900 -0.212567 -1.411307 16 6 0 4.058170 1.920575 -1.166489 17 1 0 4.629040 2.158284 -2.053300 18 6 0 3.600676 2.942607 -0.350543 19 6 0 2.882376 2.705236 0.810080 20 1 0 2.562904 3.537647 1.421531 21 6 0 2.604105 1.391875 1.161674 22 1 0 2.066265 1.169272 2.072714 23 16 0 -2.616454 -1.327044 0.760803 24 8 0 -3.579189 -2.192244 0.138814 25 8 0 -2.342303 -1.371184 2.169112 26 7 0 -1.181820 -1.604394 -0.016406 27 6 0 -1.183357 -1.745212 -1.493824 28 1 0 -1.201746 -0.751273 -1.959571 29 1 0 -2.074996 -2.294857 -1.779725 30 6 0 -3.047866 0.350583 0.349397 31 6 0 -3.776513 0.609528 -0.809355 32 1 0 -4.137806 -0.212506 -1.411413 33 6 0 -4.058101 1.920626 -1.166506 34 1 0 -4.628924 2.158368 -2.053339 35 6 0 -3.600660 2.942627 -0.350493 36 6 0 -2.882423 2.705214 0.810161 37 1 0 -2.562990 3.537603 1.421663 38 6 0 -2.604162 1.391841 1.161717 39 1 0 -2.066369 1.169204 2.072777 40 9 0 3.872272 4.214101 -0.693628 41 9 0 -3.872246 4.214135 -0.693541 42 1 0 -0.000135 -4.058119 -0.526058 43 1 0 0.883818 -4.330887 -2.041994 44 1 0 -0.883695 -4.330886 -2.042252 ---------------------------------------------------------------------

COMPOUNDS OF FIGURE 9(a)NImag=0Energy: -2199.706783Cartesian coordinates--------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 -0.690347 1.105019 2.615352 2 8 0 -1.676942 0.646886 3.554511 3 8 0 -0.482730 2.499604 2.344322 4 7 0 -2.217417 -1.377731 -0.000000 5 7 0 -1.062609 0.386033 1.177535 6 6 0 -1.453601 -1.048369 1.172265 7 1 0 -0.542864 -1.663069 1.172998 8 1 0 -2.007992 -1.246013 2.079688 9 6 0 -0.291131 0.771615 -0.000000 10 1 0 -0.143801 1.846704 -0.000000 11 1 0 0.687305 0.259223 0.000000 12 6 0 -3.688541 -1.079473 -0.000000 13 6 0 -4.026811 0.422358 -0.000000 14 1 0 -5.111505 0.549825 -0.000000 15 1 0 -3.625835 0.919300 0.881670 16 6 0 -4.304696 -1.737522 1.243648 17 1 0 -5.391768 -1.690275 1.176800 18 1 0 -4.009052 -2.785906 1.314922 19 1 0 -4.023191 -1.226533 2.164844 20 6 0 0.877238 0.410726 3.094888 21 6 0 0.910861 -0.771340 3.831240 22 1 0 -0.012769 -1.218496 4.171273 23 6 0 2.131620 -1.350901 4.146889 24 1 0 2.195942 -2.262521 4.724498 25 6 0 3.291904 -0.729125 3.714829 26 6 0 3.279599 0.450954 2.989260 27 1 0 4.213955 0.905314 2.690303 28 6 0 2.055484 1.025513 2.676965 29 1 0 2.009480 1.958255 2.132263 30 16 0 -0.690347 1.105019 -2.615352 31 8 0 -1.676942 0.646886 -3.554511 32 8 0 -0.482730 2.499604 -2.344322 33 7 0 -1.062609 0.386033 -1.177535 34 6 0 -1.453601 -1.048369 -1.172265 35 1 0 -0.542864 -1.663069 -1.172998 36 1 0 -2.007992 -1.246013 -2.079688 37 1 0 -3.625835 0.919300 -0.881670 38 6 0 -4.304696 -1.737522 -1.243648 39 1 0 -5.391768 -1.690275 -1.176800 40 1 0 -4.009052 -2.785906 -1.314922 41 1 0 -4.023191 -1.226533 -2.164844 42 6 0 0.877238 0.410726 -3.094888 43 6 0 0.910861 -0.771340 -3.831240 44 1 0 -0.012769 -1.218496 -4.171273 45 6 0 2.131620 -1.350901 -4.146889

100

46 1 0 2.195942 -2.262521 -4.724498 47 6 0 3.291904 -0.729125 -3.714829 48 6 0 3.279599 0.450954 -2.989260 49 1 0 4.213955 0.905314 -2.690303 50 6 0 2.055484 1.025513 -2.676965 51 1 0 2.009480 1.958255 -2.132263 52 9 0 4.476581 -1.288161 4.019454 53 9 0 4.476581 -1.288161 -4.019454 ---------------------------------------------------------------------(b)NImag=0Energy: -2662.358703Cartesian coordinates:--------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 1.058425 2.457061 -1.446002 2 8 0 1.957803 3.457135 -0.861998 3 8 0 1.227361 1.999002 -2.829459 4 7 0 1.692097 0.126006 1.610016 5 7 0 1.167213 1.094451 -0.478138 6 6 0 1.132907 1.304406 0.985219 7 1 0 0.088005 1.506943 1.297710 8 1 0 1.751627 2.180078 1.193254 9 6 0 0.439168 -0.087167 -0.938899 10 1 0 0.628696 -0.234082 -2.007584 11 1 0 -0.645325 0.031008 -0.757381 12 6 0 2.170673 0.210019 3.016642 13 6 0 1.003953 0.097370 4.022447 14 1 0 1.367484 0.214245 5.055339 15 1 0 0.504719 -0.882105 3.956597 16 6 0 3.189361 -0.925596 3.237965 17 1 0 3.983678 -0.866254 2.478363 18 1 0 2.724918 -1.921377 3.174517 19 1 0 3.634012 -0.844483 4.241746 20 6 0 -0.628983 3.012682 -1.233212 21 6 0 -0.936434 3.847202 -0.152451 22 1 0 -0.137426 4.268489 0.459131 23 6 0 -2.271766 4.128051 0.132221 24 1 0 -2.557339 4.768038 0.968397 25 6 0 -3.261026 3.561122 -0.669475 26 6 0 -2.964993 2.757520 -1.768761 27 1 0 -3.776819 2.356658 -2.377378 28 6 0 -1.628876 2.476907 -2.052641 29 1 0 -1.361679 1.845092 -2.900849 30 16 0 0.842525 -2.743573 -0.842879 31 8 0 1.612722 -3.632428 0.034350 32 8 0 1.154903 -2.616268 -2.270053 33 7 0 0.969113 -1.216023 -0.188678 34 6 0 0.910144 -1.043377 1.269233 35 1 0 -0.153897 -0.944917 1.575509 36 1 0 1.339928 -1.936222 1.731338 37 1 0 0.248447 0.878186 3.837177 38 6 0 2.900469 1.545386 3.240142 39 1 0 3.379648 1.532895 4.229859 40 1 0 3.683892 1.699194 2.483357 41 1 0 2.217161 2.407885 3.224225 42 6 0 -0.884350 -3.201925 -0.703638 43 6 0 -1.362080 -3.702676 0.514514 44 1 0 -0.676734 -3.878371 1.345012 45 6 0 -2.720744 -3.985936 0.649762 46 1 0 -3.134102 -4.376073 1.581085 47 6 0 -3.565646 -3.767188 -0.439537 48 6 0 -3.096756 -3.284083 -1.660871 49 1 0 -3.795271 -3.139266 -2.486471 50 6 0 -1.737685 -2.996587 -1.793646 51 1 0 -1.337356 -2.621804 -2.736581 52 9 0 -4.547286 3.792717 -0.366375 53 9 0 -4.870149 -4.030334 -0.306150 54 6 0 -3.130284 -0.159552 0.385794 55 8 0 -2.153580 0.684879 1.009677 56 6 0 -2.690133 1.266786 2.200580 57 6 0 -4.206955 1.152445 2.056251 58 6 0 -4.335519 -0.194186 1.331324 59 1 0 -2.693475 -1.154150 0.215080 60 1 0 -3.395409 0.269826 -0.596373 61 1 0 -2.328989 2.303912 2.275762 62 1 0 -2.330051 0.710862 3.088474 63 1 0 -4.588783 1.968980 1.422395 64 1 0 -4.734295 1.187254 3.020833 65 1 0 -5.288037 -0.321271 0.796583 66 1 0 -4.235885 -1.025965 2.048200 67 6 0 4.723709 0.751777 -0.199050 68 8 0 5.120762 -0.560835 0.198934 69 6 0 4.644159 -1.512626 -0.760121 70 6 0 4.062920 -0.709629 -1.940969

101

71 6 0 4.629364 0.700558 -1.722516 72 1 0 5.470296 1.468565 0.179860 73 1 0 3.740225 0.996946 0.233510 74 1 0 3.878728 -2.165845 -0.305647 75 1 0 5.495383 -2.147850 -1.065225 76 1 0 2.969066 -0.691963 -1.875358 77 1 0 4.331000 -1.142175 -2.916184 78 1 0 3.978962 1.488080 -2.130880 79 1 0 5.630387 0.800641 -2.174423 ---------------------------------------------------------------------

triazinanes with an axial tert-butyl group esi for

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