electronic supplementary information electronic supplementary information orthanilic acid-promoted...

S1

Electronic Supplementary Information

Orthanilic acid-Promoted Reverse turn formation in peptides.

Sangram S. Kale,a Gowri Priya,

a Amol S. Kotmale,

b Rupesh L. Gawade,

c Vedavati G

Puranik,c P. R. Rajamohanan,

b Gangadhar J. Sanjayan

a*

aDivision of Organic Chemistry, National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411 008,

India. Fax: +91-020-2590-2629; Tel+91-020-2590-2082; E-mail: [email protected] bCentral NMR Facility, National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411 008, India.

cCenter for Materials Characterization, National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411

008, India.

Contents S1

General methods S2

Synthetic schemes S3

Synthetic procedures S4-S9

Crystal data of 1-6 S10-S12

Mass spectra of 1-7 and 10 S13-S16

1H NMR spectra of 1-7 and 10 S17-S20

13C and DEPT-135 spectra of 1-7 and 10 S21-S28

Titration study of 2 -5 S29-S32

Variable temperature study of 2-5 S33-S36

2D COSY, HSQC, HMBC, and NOESY spectra of 2-5 S37-S56

Details of torsion angles and H-bonding parameters of 1-6 S57-S70

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

S2

General Methods.

Unless otherwise stated, all the chemicals and reagents were obtained commercially. Dry

solvents were prepared by the standard procedures. Analytical Thin Layer

Chromatography was done on precoated silica gel plates (Kieselgel 60F254, Merck).

Unless otherwise stated Column Chromatographic purifications were done with 230-400

mesh silica gel. NMR spectra were recorded in CDCl3 on 400MHz and 500 MHz

spectrometers. All chemical shifts are reported in δ ppm downfield to TMS and peak

multiplicities as singlet (s), doublet (d), quartet (q), broad singlet (bs), and multiplet (m).

The titration studies were done in CDCl3. IR spectra were recorded in CHCl3 using

Shimadzu FTIR-8400 spectrophotometer. Melting points were determined on a Buchi

Melting Point B-540. All the spectra have been arranged according to scheme 1 and 2.


S3

Scheme 1:

Reagent and conditions: (i) H2, Pd/C, 60 psi, 12 h; (ii) Boc-Gly-OH (for 1)/ Boc-L-Ala-

OH (for 9), ethyl chloroformate, Et3N, THF, reflux, 18 h; (ii) Methanolic CH3NH2, rt, 48

h.

Scheme 2:

Reagent and conditions: (i) H2, Pd/C, 60 psi, 12 h; (ii) Boc-Gly-OH (for 4)/ Boc-L-Pro-

OH (for 5), ethyl chloroformate, Et3N, THF, reflux, 18 h.


S4

Synthetic Procedures:

Methyl 2-methyl-2-(2-nitrophenylsulfonamido) propanoate 7:

To a solution of 2-nitrobenzenesulfonylchloride (2.6 g, 11.7 mmol) in dry DCM (30 mL)

was added 2-aminoisobutylmethyl ester hydrochloride (2.0 g, 13.0 mmol) at 0 oC

followed by the addition of Et3N (4.94 mL, 35.5 mmol). The reaction mixture was

allowed to attain room temperature and was further stirred for 12 h. Later, the reaction

mixture was washed sequentially with sat. NaHCO3, water, dil. HCl and brine. The

organic layer was dried over anhydrous Na2SO4 and evaporated under reduced pressure

to get the crude product which on purification by column chromatography (eluent: pet

ether/ethyl acetate: 50:50, Rf: 0.45) yielded 7 (1.92 g, 54%); mp: 114-115 oC; IR (CHCl3)

ν (cm-1) 3401, 3019, 1737, 1635, 1543, 1411, 1351, 1216, 1048, 769; 1H NMR (400

MHz, CDCl3) δ: 8.11-8.09 (d, J = 8 Hz, 1H), 7.90-7.88 (d, J = 8 Hz, 1H), 7.77-7.70 (m,

2H), 6.18 (s, 1H), 3.64 (s, 3H), 1.57 (s, 6H); 13C NMR (100 MHz, CDCl3) δ: 173.7,

147.5, 136.2, 133.3, 132.9, 130.1, 125.3, 60.1, 52.9, 26.3; LCMS: 325.04 (M+Na)+; Anal.

Calcd for C11H14N2O6S: C, 43.70; H, 4.67; N, 9.27; Found: C, 43.34.; H, 4.90.; N, 9.43.

General procedure for reduction of nitro compounds 7 and 10 to respective amines

8 and 11

To a solution of 7 and 10 (0.5 g, 1.59 mmol) in methanol (15 mL), 10% Pd/C (0.06 g)

was added. The reaction mixture was stirred at 60 psi for 12 h. The catalyst was filtered


S5

through celite and the filtrate was evaporated to get product 8 and 11, which was carried

forward to the next reaction without any further purification.

2-(2-aminophenylsulfonamido)-N, 2-dimethylpropanamide 6:

Compound 8 was dissolved in MeOH (2 mL) followed by addition of methanolic methyl

amine solution (2 mL) at 0 oC. Progress of the reaction was monitored by TLC and after

completion of reaction (48 h), the solvent was stripped off and crude product was purified

by column chromatography (eluent: pet ether/ethyl acetate: 50:50, Rf: 0.4) to yield 6

(0.04 g, 90%); mp: 136-138 oC. IR(CHCl3) ν (cm-1) 3685, 3448, 3365, 3020, 2400, 1671,

1524, 1416, 1329, 1216, 1155, 1020, 928, 851, 770, 668. 1H NMR (500 MHz, CDCl3) δ:

7.72-7.70- (dd, J = 8.2, 1.5 Hz, 1H), 7.35-7.33 (t, J = 7 Hz, 2H), 6.85-6.83 (d, J = 7.3 Hz,

1H), 6.80-6.78 (d, J = 8.2 Hz, 1H), 5.66 (s, 1H), 4.86 (s, 2H), 2.75-2.74 (d, J = 4.9 Hz,

3H), 1.38 (s, 6H); 13C NMR (100 MHz, CDCl3) δ: 174.5, 144.6, 134.3, 129.2, 124.2,

118.4, 117.9, 60.1, 28.5, 25.6; HRMS: C11H18O3N3S, Calcd: 272.1063 Found: 272.1064

Methyl-2-(2-(2-((tert-butoxycarbonyl)amino)acetamido)phenylsulfonamido)-2-

methylpropanoate 1:

To a two necked round-bottomed flask containing Boc-Glycine (0.11 g, 0.66 mmol) in 10

mL dry THF, dry Et3N (0.13 mL, 0.99 mmol) was added under N2 atmosphere. The

resultant solution was cooled to 0°C. Subsequently, ethyl chloroformate (0.07 mL, 0.79

mmol) was added drop wise. The solution was stirred at 0 oC for 1 h, amine 8 (0.18 g,

0.66 mmol) in 10 mL dry THF was added, the reaction mixture was allowed to stir for 2 h

at room temperature, and finally refluxed for 48 h. Later, the reaction mixture was cooled


S6

to room temperature and filtered. The filtrate was concentrated to get the crude product,

which was dissolved in DCM (10 mL) and washed with sat. NaHCO3 followed by brine.

The organic layer was dried over anhydrous Na2SO4 and evaporated under reduced

pressure to get the crude product which was further purified by column chromatography

(eluent: pet ether/ethyl acetate: 50:50, Rf: 0.5) to furnish 1 (0.19 g, 70%) as a white solid;

mp: 149-152 oC. IR(CHCl3) ν (cm-1) 3684, 3447, 3237, 3020, 2400, 1736, 1700, 1584,

1523, 1497, 1439, 1331, 1215, 1161, 1024, 929, 851, 762, 669, 481. 1H NMR (400 MHz,

CDCl3) δ: 9.55 (s, 1H), 8.1-8.08 (d, J = 8Hz, 1H), 7.88-7.86 (dd, J = 7.9, 1.3 Hz, 1H),

7.58-7.54 (t, J = 7Hz, 1H), 7.26-7.22 (t, J = 7.3Hz, 1H), 6.54 (s, 1H), 5.31-5.29 (m, 1H),

3.96-3.94 (d, J = 6 Hz, 2H), 3.49 (s, 3H), 1.57 (s, 9H), 1.40 (s, 6H); 13C NMR (100 MHz,

CDCl3) δ: 173.8, 167.9, 157.9, 134.4, 133.3, 131.6, 128.7, 124.5, 82.1, 58.4, 52.6, 45.7,

28.5, 25.6; HRMS: C18H28O7N3S, Calcd: 430.1642 Found: 430.1637.

tert-butyl-(2-((2-(N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)sulfamoyl)phenyl)

amino)-2-oxoethyl) carbamate 2:

Compound 1 was dissolved in MeOH (2 mL) followed by the addition of methanolic

methyl amine solution (2 mL) at 0 oC. The reaction was monitored by TLC and after

completion of reaction (48 h), the solvent was stripped off and the crude product was

purified by column chromatography (eluent: pet ether/ethyl acetate: 50:50, Rf: 0.3) to

yield 2 (0.09 g, 50%); mp: 170-172 oC. IR(CHCl3) ν (cm-1) 3683, 3582, 3447, 3020,

2400, 1696, 1520, 1426, 1370, 1284, 1215, 1022, 760, 669; 1H NMR (400 MHz, CDCl3)

δ: 9.31 (s, 1H), 7.98-7.96 (d, J = 8 Hz, 1H), 7.93-7.90 (dd, J = 8, 1.3 Hz, 1H), 7.62-7.58 (

t, J = 7 Hz, 1H), 7.31-7.29 (t, J = 7.3 Hz, 1H), 6.57 (s, 2H), 5.48-5.45 (m, 1H), 3.93-3.91


S7

(d, J = 5.8 Hz, 2H), 2.72-2.71 (d, J = 4.8 Hz, 3H), 1.54 (s, 9H) 1.31 (s, 6H); 13C NMR

(100 MHz, CDCl3) δ: 174.2, 168.0, 158.1, 133.6, 132.8, 129, 125.6, 125.3, 82.2, 60.3,

45.7, 28.4, 26.5, 25.5; HRMS: C18H29O6N4S, Calcd: 429.1802 Found: 430.1797.

(S)-tert-butyl-1-(2-(N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)sulfamoyl)

phenylamino)-1-oxopropan-2-ylcarbamate 3:

To a two-necked round-bottomed flask containing Boc-L-alanine (0.84 g, 0.48 mmol) in

10 mL dry THF was added dry Et3N (0.08 mL, 0.55 mmol) under N2 atmosphere. The

resultant solution was cooled to 0°C. Subsequently, ethyl chloroformate (0.05 mL, 0.55

mmol) was introduced drop wise. The solution was stirred at 0 oC for 1 h, and amine 8

(0.1 g, 0.37 mmol) in 10 mL dry THF was added, under N2 atmosphere. The reaction

mixture was stirred at 0 °C for 1 h, at room temperature for 2 h, and refluxed for 18 h.

The reaction mixture was cooled to room temperature and filtered. The filtrate was

concentrated to get the crude product, which was dissolved in DCM (10 mL) and washed

with sat. NaHCO3 followed by brine. The organic layer was dried over anhydrous

Na2SO4 and evaporated under reduced pressure to get the crude product 9. The crude

product 9 was further dissolved in MeOH (2 mL) followed by addition of methanolic

methyl amine solution (2 mL) at 0 oC. The reaction was monitored by TLC and after

completion of reaction (48 h), solvent was stripped off and the crude product was purified

by column chromatography (eluent: pet ether/ethyl acetate: 20:80, Rf: 0.3) to yield 3

(0.04 g, 25%); mp: 161-164 oC; [α]26D: -9.52° (c 0.63, CHCl3); IR (CHCl3) ν (cm-1)

3430, 3352, 3019, 1690, 1662, 1580, 1330, 1217, 1160, 1128, 1021, 771; 1H NMR (500

MHz, CDCl3) δ: 9.29 (s, 1H), 7.92-7.90 (d, J = 8 Hz, 2H), 7.60-7.57 (t, J = 7.7 Hz, 1H),


S8

7.30-7.28 (t, J = 7.7 Hz, 1H), 6.54 (s, 2H), 5.06 (s, 1H), 4.14-4.12 (m, 1H), 2.68-2.67 (d,

J = 5 Hz, 3H), 1.58-1.56 (d, J = 7 Hz, 3H ), 1.52 (s, 9H), 1.36 (s, 3H), 1.27 (s, 3H); 13C

NMR (125 MHz, CDCl3) δ: 174.1, 171.4, 157.3, 134.2, 133.5, 133.1, 129.0, 125.9, 125.3,

82.0, 28.5, 26.5, 26.4, 24.9, 17.9; HRMS: C19H30N4O6NaS Calcd: 465.1778; Found:

465.1760.

N-isobutyl-2-nitrobenzenesulfonamide 10:

Compound 10 was synthesized by the above mentioned procedure for 7 using 2-

nitrosulfonyl chloride and isobutyl amine. Yield (87%); mp: 78-79 oC; IR (CHCl3) ν (cm-

1) 3621, 3393, 3019, 1596, 1542, 1362, 1216, 1170, 1124, 1046, 758; 1H NMR (500

MHz, CDCl3) δ: 8.14-8.12 (d, J = 9 Hz, 1H), 7.87-7.85 (d, J = 9 Hz, 1H), 7.17-7.13 (m,

2H), 5.33-5.30 (t, J = 6.6 Hz, 1H), 2.92-2.89 (t, J = 6.6 Hz, 2H), 1.83-1.75 (septet, J = 6.7

Hz, 1H), 0.92 (s, 3H), 0.90 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 148.1, 133.8, 133.5,

132.8, 131.1, 125.4, 51.2, 28.5, 19.8; HRMS: C10H15N2O4S Calcd: 259.0747; Found:

259.0741.

tert-butyl (2-((2-(N-isobutylsulfamoyl)phenyl)amino)-2-oxoethyl)carbamate 4:

Compound 4 was synthesized by the above mentioned procedure for 1 using amine 11.

Yield (90%); mp: 127-129 oC; IR (CHCl3) ν (cm-1) 3684, 3447, 3336, 3265, 3020, 2933,

2874, 2400, 1700, 1584, 1523, 1442, 1328, 1215, 1072, 930, 852, 752, 591, 487; 1H

NMR (400 MHz, CDCl3) δ: 9.63 (s, 1H), 8.11-8.09 (d, J = 8.3 Hz, 1H), 7.91-7.89 (d, J =

8 Hz, 1H), 7.58-7.55 (m, 1H), 7.25-7.23 (d, J = 7.8 Hz, 1H), 5.99 (bs, 1H), 3.90-3.89 (d,

J = 6 Hz, 2H), 2.61-2.58 (t, J = 6.4 Hz, 2H), 1.69-1.58 (m, 1H), 1.53 (s, 9H), 0.84-0.82


S9

(d, J = 6.8 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ: 168.0, 157.9, 134.1, 133.3, 129.4,

124.4, 82.0, 50.1, 45.8, 28.5, 19.7; HRMS: C17H28O5N3S, Calcd: 386.1744 Found:

386.1741.

(S)-tert-butyl-2-(2-(N-isobutylsulfamoyl)phenylcarbamoyl)pyrrolidine-1-

carboxylate 5:

Compound 5 was synthesized by the above mentioned procedure for 1 using amine 11.

Yield (85%); mp: 104-105 oC; [α]26D: -77.15° (c 0.7, CHCl3); IR (CHCl3) ν (cm-1) 3615,

3353, 3020, 1675, 1584, 1389, 1215, 1157, 1046, 757; 1H NMR (400 MHz, CDCl3) δ:

9.48 (s, 1H), 8.08-8.06 (d, J = 8 Hz, 1H), 7.89-7.87 (d, J = 8 Hz, 1H), 7.56-7.53 (t, J =

7.7 Hz, 1H), 7.23-7.20 (t, J = 7.8 Hz, 1H), 6.39 (s, 1H), 4.33-4.32 (dd, J = 8.7, 3.5 Hz,

1H), 3.55-3.51 (m, 1H), 3.47-3.41 (m, 1H), 2.69-2.63 (m, 1H), 2.47-2.45 (m, 1H), 2.32-

2.21 (m, 2H), 1.95-1.91 (m, 2H), 1.65-1.61 (m, 1H), 1.52 (s, 9H), 0.83-0.80 (t, J = 7 Hz,

6H); 13C NMR (125 MHz, CDCl3) δ: 171.1, 156.7, 134.3, 133.1, 129.8, 129.3, 124.5,

124.2, 81.6, 62.7, 50.2, 47.7, 30.6, 28.6, 28.2, 24.4, 19.7; HRMS: C20H31N3O5NaS Calcd:

448.1877; Found: 448.448.1858.

Crystal Data: Data for all the compounds were collected on SMART APEX-II CCD

Single Crystal X-ray diffractometer using Mo-Kα radiation (λ = 0.7107 Å) to a

maximum θ range of 25.00°. Crystal to detector distance 5.0 cm, 512 x 512 pixels /

frame, Oscillation / frame -0.5º, maximum detector swing angle = –30.0º, beam center =

(260.2, 252.5), in plane spot width = 1.24, SADABS correction applied. The structures

were solved by direct methods using SHELXTL. All the data were corrected for


S10

Lorentzian, polarisation and absorption effects. SHELX-97 (ShelxTL) was used for

structure solution and full matrix least squares refinement on F2. Hydrogen atoms were

included in the refinement as per the riding model.

Crystal data for 1:

Single crystals of 1 were grown by slow evaporation of the solution in diethyl ether.

Colorless rectangular like crystal of approximate size 0.39 x 0.21 x 0.09 mm3, was used

for data collection. Multi-run data acquisition. Total scans = 3, total frames = 626,

exposure / frame = 10.0 sec / frame, θ range = 2.18 to 25.00°, completeness to θ of 25.00

º is 99.9%. C18H27N3O7S, MW = 429.49, crystals belong to orthorhombic, space group

Pna21, a = 14.8435 (6), b = 9.8421 (4), c = 29.388 (1) Å, V = 4293.3 (3) Å3, Z = 8, Dc =

1.329 g/cc, (Mo–Kα) = 0.194 mm-1, 17432 reflections measured, 5881 unique, [I>2σ(I)]

R1 = 0.0350, wR2 = 0.0884, largest diff. peak and hole 0.535 and -0.506 e.Å-3. Flack

parameter [0.49(8)].

Crystal data for 2:

Single crystals of 2 were grown by slow evaporation of the solution in DCM/ ether.

Colorless needle like crystal of approximate size 0.36 x 0.18 x 0.07 mm3, was used for

data collection. Multi-run data acquisition. Total scans = 4, total frames = 1378, exposure

/ frame = 10.0 sec / frame, θ range = 2.42 to 25.00°, completeness to θ of 25.00 º is 99.8

%. C18H28N4O6S, MW = 428.50, crystals belong to monoclinic, space group P21/c, a =

17.3832(5), b = 8.5835(2), c = 15.0137(4) Å, V = 2165.69 (10) Å3, Z = 4, Dc = 1.314

g/cc, (Mo–Kα) = 0.190 mm-1, 16473 reflections measured, 3807 unique, [I>2σ(I)] R1 =

0.0315, wR2 = 0.0822, largest diff. peak and hole 0.419 and -0.422 e.Å-3.


S11

Crystal data for 3:

Single crystals of 3 were grown by slow evaporation of the solution in ethyl acetate and

pet ether. Colorless needle-like crystal of approximate size 0.43 x 0.25 x 0.12 mm3, was

used for data collection. Multi-run data acquisition. Total scans = 7, total frames = 2463,


º is 99.9 %. C19H30N4O6S, MW = 442.53, Crystals belong to Triclinic, space group P-1, a

= 8.4700(9), b = 10.2422(15), c = 14.857(2) Å, V = 1112.4(3) Å3, Z = 2, Dc = 1.321 g/cc,

(Mo–Kα) = 0.187 mm-1, 15904 reflections measured, 3913 unique, [I>2σ(I)] R1 =

0.0546, wR2 = 0.1144, largest diff. peak and hole 0.548 and -0.327 e.Å-3.

Crystal data for 4:

Single crystals of 4 were grown by slow evaporation of the solution in diethyl ether/pet

ether. Colorless rectangular like crystal of approximate size 0.42 x 0.10 x 0.05 mm3, was



º is 99.7 %.C17H27N3O5S, MW = 385.48, crystals belong to orthorhombic, space group

Fdd2, a = 29.2950 (3), b = 46.5380 (5), c = 5.7943 (1) Å, V = 7899.55 (18) Å3, Z = 16,

Dc = 1.296 g/cc, (Mo–Kα) = 0.196 mm-1, 24244 reflections measured, 3477 unique,

[I>2σ(I)] R1 = 0.0748, wR2 = 0.1906, Largest diff. peak and hole 0.692 and -0.432 e.Å-3.

Flack parameter [-0.12(7)]. DFIX restraint was applied to disordered methyl groups so

that the C-C distance is similar in the iso-butyl group. Restrain for C24 and

C24'disordered atoms was applied so that they are not connected to each other.


S12

Crystal data for 5:

Single crystals of 5 were grown by slow evaporation of the solution in diethyl ether.

Colorless rectangular like crystal of approximate size 0.45 x 0.32 x 0.30 mm3, was used

for data collection. Multi-run data acquisition. Total scans = 6, total frames = 2176,


º is 100.0 %. C20H31N3O5S, MW = 425.54, Crystals belong to Monoclinic, space group

P21, a = 10.1664(7), b = 10.5548(7), c = 10.8876(7) Å, V = 1165.25(13) Å3, Z = 2, Dc =

1.213 g/cc, (Mo–Kα) = 0.172 mm-1, 17083 reflections measured, 4098 unique, [I>2σ(I)]

R1 = 0.0366, wR2 = 0.1028, largest diff. peak and hole 0.443 and -0.176 e.Å-3. Flack

parameter [0.03(7)].

Crystal data for 6:

Single crystals of 6 were grown by slow evaporation of the solution in chloroform and

pet ether. Colorless needle like crystal of approximate size 0.44 x 0.28 x 0.055mm3, was



º is 99.9 %. C11H17N3O3S, MW = 271.34, crystals belong to monoclinic, space group

P21/c, a = 12.6119(3) Å, b = 7.6788(1) Å, c = 15.0308(3) Å, V = 1337.34(5) Å3, Z = 4,

Dc = 1.348 g/cc, (Mo–Kα) = 0.247 mm-1, 9599 reflections measured, 2351 unique,

[I>2σ(I)] R1 = 0.0372, wR2 = 0.0969, largest diff. peak and hole 0.296 and -0.404 e.Å-3.


S13


S14


S15


S16


S17

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5

CDCl3

8.1

18.0

97.8

9

7.7

57.7

47.7

47.7

37.7

27.7

0 7.2

7 6.1

8

3.6

4

1.5

7

1H NMR (400 MHz, CDCl3)

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5Chemical Shift (ppm)

CHLOROFORM-d

1.3

8

2.7

4

2.7

5

4.8

6

5.6

5

5.6

6

6.7

8

6.8

0

6.8

26.8

3

6.8

5

7.2

7

7.3

4

7.3

6

7.7

0

7.7

0

7.7

2

7.7

2



S18

10 9 8 7 6 5 4 3 2 1Chemical Shift (ppm)

CHLOROFORM-d

1.4

0

1.5

7

3.4

9

3.9

4

3.9

6

5.2

9

5.3

0

5.3

1

6.5

4

7.2

2

7.2

27.2

47

.27

7.5

47.5

6

7.8

6

7.8

6

7.8

8

8.0

8

8.1

0

9.5

5


9 8 7 6 5 4 3 2 1Chemical Shift (ppm)

CHLOROFORM-d

1.3

1

1.5

4

1.7

6

2.7

1

2.7

2

3.9

1

3.9

3

5.4

5

5.4

7

5.4

8

6.5

7

7.2

77.2

9

7.6

0

7.6

27.9

0

7.9

1

7.9

2

7.9

6

7.9

8

9.3

1



S19

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

CDCl3

8.1

48

.12

7.8

57

.76

7.7

57

.74

7.7

4

7.2

7

5.3

35

.31

5.3

0

2.9

22

.91

2.8

9

1.8

31

.82 1.8

11

.79

1.7

81

.77

1.7

5

0.9

20

.90


O2N

SO

O

NH

10

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5

CDCl3

9.2

9

7.9

27.9

07.6

07.5

9

7.2

97.2

7

6.5

4

5.0

6

4.1

64.1

54.1

44.1

34.1

24.1

0

2.6

82.6

7

1.5

8

1.5

21.3

61.2

7


Diastereotopic geminal methyl groups of Aib


S20

9 8 7 6 5 4 3 2 1

CDCl3

9.4

8

8.0

88.0

6 7.8

97.8

77.5

6 7.5

47.5

37.2

77.2

3 7.2

27.2

0

6.3

9

4.3

34.3

34.3

24.3

1

3.5

33.5

23.4

73.4

53.4

32.6

72.6

62.6

52.4

52.2

92.2

62.2

41.9

31.9

21.9

11.5

2

0.8

30.8

10.8

0


NH

O

S O

O

HN

N

H

O

O

5

10 9 8 7 6 5 4 3 2 1Chemical Shift (ppm)

CHLOROFORM-d

0.8

20.8

4

1.5

3

1.6

3

1.6

4

1.6

6

1.6

92.5

82.6

02.6

1

3.8

9

3.9

0

5.3

45.3

6

5.3

7

5.9

9

7.2

37.2

5

7.2

7

7.5

57.5

6

7.8

9

7.9

1

8.0

9

8.1

1

9.6

3



S21

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30

Chloroform-d

173.7

3

147.5

2

136.2

0133.2

8132.9

2 130.1

2

125.3

4 77.0

0

60.1

2

52.8

6

26.3

0

13C NMR (100 MHz, CDCl3)

136 128 120 112 104 96 88 80 72 64 56 48 40 32 24

13

3.3

61

33

.00

13

0.1

9

12

5.4

2

52

.93

26

.38

NO2

SO

O

HN

OMeO

7

DEPT-135 (100 MHz, CDCl3)


S22


CHLOROFORM-d

25

.69

26

.59

60

.14

77

.00

11

7.9

8

11

8.4

11

24

.29

12

9.2

4

13

4.3

0

14

4.6

5

17

4.5

7


144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16Chemical Shift (ppm)

25

.69

26

.58

11

7.9

8

11

8.4

2

12

9.2

4

13

4.3

1



S23


CHLOROFORM-d

25

.67

28

.54

45

.70

52

.64

58

.49

77

.00

82

.15

12

4.5

7

12

8.7

5

13

1.6

913

3.3

1

13

4.4

6

15

7.9

2

16

7.9

8

17

3.8

2



25

.68

28

.54

45

.70

52

.64

12

4.5

8

12

8.7

6

13

3.3

1



S24


CHLOROFORM-d

25

.55

28

.46

45

.76

60

.33

77

.00

81

.88

12

9.0

21

32

.84

13

3.6

3

15

8.1

8

16

8.0

8

17

4.2

6


144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24Chemical Shift (ppm)

25

.55

26

.57

28

.46

45

.76

12

5.3

3

12

5.6

712

9.0

2

13

3.6

4



S25

128 120 112 104 96 88 80 72 64 56 48 40 32 24 16

133.5

7

129.0

6

125.9

9125.3

5

52.5

1

28.5

026.5

324.8

9

17.9

8


170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20

Chloroform-d1

74

.09

17

1.3

5

15

7.3

2

13

4.1

91

33

.53

12

9.0

21

25

.94

12

5.3

1

81

.97

77

.00

60

.37

52

.47

28

.47

26

.42

24

.88

17

.95



S26

144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24

Chloroform-d

14

8.0

4

13

3.7

21

33

.49

13

2.7

51

31

.02

12

5.3

1

77

.00

51

.12

28

.45

19

.77


136 128 120 112 104 96 88 80 72 64 56 48 40 32 24

13

3.5

51

32

.81

13

1.0

7

12

5.3

7

51

.17

28

.50

19

.83


O2N

SO

O

NH

10


S27

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20Chemical Shift (ppm)

CHLOROFORM-d

19

.70

28

.52

45

.8150

.18

77

.00

82

.0312

4.4

4

12

9.4

1

13

3.3

81

34

.16

15

7.9

216

8.0

4



19

.70

28

.52

45

.80

50

.18

12

4.4

4

12

9.4

1

13

3.3

8



S28

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20

Chloroform-d

171.0

7

156.7

3

134.3

2133.1

3129.7

5129.2

7

124.5

0124.2

2

81.5

6

77.0

0

62.2

1 50.2

147.6

6

30.5

528.6

028.2

424.3

8

19.7

3


NH

O

S O

O

HN

N

H

O

O

5

128 120 112 104 96 88 80 72 64 56 48 40 32 24

13

3.2

1 12

9.3

4

12

4.3

0

62

.28

50

.27

47

.74

30

.63

28

.67

28

.32

24

.45

19

.81



S29

Table S1. Titration study of 2 in CDCl3 (20 mmol) with DMSO- d6

(volume of DMSO-d6 added at each addition = 5 µµµµL).

No V DMSO-

d6

(in µµµµL)

Chemical Shift δ δ δ δ (ppm)

NH1 NH2 NH3 NH4

1 0 5.35 9.32 6.54 6.53 2 5 5.79 9.31 6.65 6.54 3 10 6.08 9.29 6.71 6.55 4 15 6.31 9.28 6.75 6.55 5 20 6.38 9.27 6.78 6.54 6 25 6.45 9.26 6.80 6.54 7 30 6.54 9.25 6.81 6.58 8 35 6.53 9.24 6.83 6.65 9 40 6.52 9.23 6.83 6.68 10 45 6.53 9.22 6.84 6.72 11 50 6.52 9.21 6.85 6.76

0 10 20 30 40 50

5.5

6.0

6.5

7.0

7.5

8.0

8.5

9.0

9.5

Ch

em

ica

l S

hif

t in

pp

m

Volume of DMSO added in µµµµL

NH2

NH3

NH4

NH1

HN

O

SO

O

NH

HN O

O

HN

O

2

NH2

NH1

NH3

NH4


S30


(volume of DMSO- d6 added at each addition = 5 µµµµL).

NH

O

S O

O

N

NHO

O

O

HN

H

H

5

NH1

NH2

NH3

NH4

3

0 10 20 30 40 50

5.0

5.5

6.0

6.5

7.0

7.5

8.0

8.5

9.0

9.5

Ch

em

cia

l sh

ift

δδ δδ (

pp

m)

Volume of DMSO added (µµµµL)

NH1

NH2

NH3

NH4

No V DMSO-

d6

(in µµµµL)

Chemical Shift δδδδ (ppm)

NH1 NH2 NH3 NH4

1 0 4.98 9.29 6.54 6.54 2 5 5.54 9.29 6.54 6.67 3 10 5.89 9.29 6.53 6.75 4 15 6.12 9.27 6.53 6.79 5 20 6.28 9.26 6.53 6.82 6 25 6.37 9.25 6.51 6.84 7 30 6.46 9.23 6.51 6.86 8 35 6.51 9.22 6.51 6.86 9 40 6.57 9.20 6.50 6.88 10 45 6.60 9.19 6.50 6.88 11 50 6.62 9.17 6.49 6.88


S31


(volume of DMSO- d6 added at each addition = 5 µL).

0 10 20 30 40 50

5

6

7

8

9

10

Ch

em

ical S

hif

t δδ δδ (

pp

m)

Volume of DMSO-d6 added (µµµµL)

NH1

NH2

NH3

No V DMSO-

d6

(in µµµµL)

Chemical Shift δδδδ

(ppm)

NH1 NH2 NH3

1 0 5.24 9.64 5.97 2 5 5.84 9.61 6.11 3 10 6.15 9.58 6.18 4 15 6.34 9.55 6.22 5 20 6.43 9.54 6.24 6 25 6.50 9.52 6.26 7 30 6.55 9.51 6.27 8 35 6.59 9.49 6.28 9 40 6.63 9.48 6.29

10 45 6.67 9.46 6.29 11 50 6.69 9.45 6.30

HN

O

SO

O

NH

HN O

O

4

NH1

NH2

NH3


S32


(volume of DMSO- d6 added at each addition = 5 µL).

NH

O

S O

O

N

NO

O

H

H

NH1

NH2

5

0 10 20 30 40 50

6.0

6.5

7.0

7.5

8.0

8.5

9.0

9.5

10.0

Ch

em

ical S

hif

t δδ δδ (

pp

m)

Volume of DMSO added (µµµµL)

NH

NH2

No V DMSO-

d6

(in µµµµL)

Chemical Shift

δδδδ (ppm)

NH1 NH2

1 0 9.51 6.41 2 5 9.49 6.40 3 10 9.48 6.39 4 15 9.46 6.38 5 20 9.44 6.37 6 25 9.43 6.37 7 30 9.41 6.37 8 35 9.40 6.36 9 40 9.38 6.36

10 45 9.37 6.35 11 50 9.36 6.35


S33

Table S5. Variable temperature study of 2 (20 mmol, 400 MHz, CDCl3).

No Temperature

(in K)


NH1 NH2/NH3 NH4

1 268 9.30 6.64 5.41 2 273 9.30 6.62 5.40 3 278 9.31 6.61 5.39 4 283 9.31 6.59 5.38 5 288 9.31 6.57 5.37 6 291 9.31 6.56 5.36 7 293 9.31 6.55 5.36 8 298 9.32 6.53 5.35 9 303 9.32 6.52 5.34 10 308 9.32 6.50 5.33 11 313 9.32 6.48 5.32 12 318 9.33 6.46 5.31 13 323 9.33 6.44 5.30

260 270 280 290 300 310 320 330

5

6

7

8

9

10

Ch

em

ica

l S

hif

t in

pp

m

Temperature in 0000K

NH2

NH3

NH4

NH1

HN

O

SO

O

NH

HN O

O

HN

O

2

NH2

NH1

NH3

NH4


S34


NH

O

S O

O

N

NHO

O

O

HN

H

H

NH1

NH2

NH3

NH4

3

260 270 280 290 300 310 320 330

4.5

5.0

5.5

6.0

6.5

7.0

7.5

8.0

8.5

9.0

9.5

10.0

Ch

em

ical sh

ift

δ

δ

δ δ (

pp

m)

Temperature (K)

NH1

NH2

NH3/NH4

No Temperature

(in K)


NH1 NH2 NH3/NH4

1 268 4.99 9.26 6.61 2 273 4.98 9.27 6.60 3 278 4.98 9.27 6.58 4 283 4.98 9.27 6.57 5 288 4.97 9.28 6.55 6 293 4.97 9.28 6.54 7 298 4.96 9.29 6.52 8 303 4.95 9.29 6.50 9 308 4.95 9.29 6.48 10 313 4.94 9.30 6.47 11 318 4.94 9.30 6.45 12 323 4.94 9.30 6.43


S35


No Temperature

(in K)

Chemical Shift δδδδ

(ppm)

NH1 NH2 NH3

1 268 5.29 9.65 6.06 2 273 5.29 9.65 6.05 3 278 5.28 9.65 6.04 4 283 5.27 9.65 6.02 5 288 5.26 9.65 6.00 6 291 5.25 9.64 5.99 7 293 5.25 9.64 5.99 8 298 5.24 9.64 5.97 9 303 5.23 9.64 5.94 10 308 5.22 9.64 5.92 11 313 5.21 9.64 5.90 12 318 5.21 9.63 5.88 13 323 5.19 9.63 5.85

260 270 280 290 300 310 320 330

5

6

7

8

9

10

Ch

em

ical S

hif

t in

pp

m

Temperature in 0000K

NH2

NH3

NH1

HN

O

SO

O

NH

HN O

O

4

NH1

NH2

NH3


S36


NH

O

S O

O

N

NO

O

H

H

NH1

NH2

5

260 270 280 290 300 310 320 330

6.0

6.5

7.0

7.5

8.0

8.5

9.0

9.5

10.0

Ch

em

cia

l sh

ift

δδ δδ (

pp

m)

Temperature (K)

NH1

NH2

No Temperature

(in K)

Chemical Shift

δδδδ (ppm)

NH1 NH2

1 268 9.50 6.44 2 273 9.50 6.44 3 278 9.50 6.43 4 283 9.50 6.42 5 288 9.49 6.41 6 293 9.49 6.40 7 298 9.49 6.39 8 303 9.49 6.37 9 308 9.49 6.36

10 313 9.49 6.34 11 318 9.49 6.31 12 323 9.49 6.29


S37

(a)

(b)

Figure S1. Partial COSY spectra of 2 (400MHz, CDCl3): aromatic (a) and aliphatic regions (b).

ppm

6.57.07.58.08.59.09.5 ppm

6.5

7.0

7.5

8.0

8.5

9.0

9.5

NH2NH3,NH4

C5HC8H C6H

C7H

ppm

1.52.02.53.03.54.04.55.05.5 ppm

2

3

4

5

6

NH1

C2H C12H

C13H, C14HtBoc

HN

O

SO

O

NH

HN O

O

HN

O

2

1

3

4

5

6

78

9

10

1113

12

14 15

1617

14

NH1

NH2

NH3

NH4


S38

(a)

(b)

Figure S2. Partial HSQC spectra of 2 (400MHz, CDCl3): aromatic (a) and aliphatic regions (b).

ppm

6789 ppm

80

90

100

110

120

130

NH2

NH3,NH4

C5H C8H C6H

C7H

NH1

ppm

234 ppm

25

30

35

40

45

C2HC12H

C13H, C14HtBoc

HN

O

SO

O

NH

HN O

O

HN

O

2

1

3

4

5

6

78

9

10

1113

12

14 15

1617

14

NH1

NH2

NH3

NH4


S39

(a)

(b)

Figure S3. Partial HMBC spectra of 2 (400MHz, CDCl3): aromatic (a) and aliphatic regions (b).

ppm

1.52.02.53.03.54.0 ppm

30

40

50

60

70

80

C2HC12H

C13H,

C14HtBoc

HN

O

SO

O

NH

HN O

O

HN

O

2

1

3

4

5

6

78

9

10

1113

12

14 15

1617

14

NH1

NH2

NH3

NH4

ppm

1.52.02.53.03.54.0 ppm

30

40

50

60

70

80

C2HC12H

C13H,

C14HtBoc


S40

ppm

23456789 ppm

2

3

4

5

6

7

8

9

Figure S4. Full 2D NOESY spectrum of 2 (400MHz, CDCl3).


S41

Figure S5. 2D NOESY excerpts of 2 (400 MHz, CDCl3).

HN

O

SO

O

NH

HN O

O

HN

O

2

1

3

4

5

6

78

9

10

1113

12

14 15

1617

14

NH1

NH2

NH3

NH4

32

ppm

3.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.6

tBoc

NH2NH3,NH4

NH1

C2H

C12H

ppm

4.04.55.05.56.06.57.07.58.0 ppm

9.3

9.4

NH2

C5HNH3,NH4

NH1C2H

ppm

1.301.35 ppm

7.90

7.95

C13H, C14H

C8H


S42

(a)

(b)


ppm

7.27.37.47.57.67.77.87.98.08.1 ppm

7.2

7.3

7.4

7.5

7.6

7.7

7.8

7.9

8.0

8.1

C10H &C7H

C9H

C8H

ppm

1.52.02.53.03.54.04.55.05.56.06.5 ppm

2

3

4

5

6

NH3 &NH4

NH1

C2H

C15H

C3H

C17H

C12H &C13H

NH

O

S O

O

N

NHO

O

O

HN

HH

HH

H

H

H

H

1

23

5

7

9

12

13

15

11

16

17

NH1

NH2

NH3

NH4

4


S43

(a)

(b)

Figure S7. Partial HSQC spectra 3 (400MHz, CDCl3): aromatic (a) and aliphatic regions (b).

ppm

7.37.47.57.67.77.87.98.08.1 ppm

124

126

128

130

132

134

C10H &

C7HC9H C8H

ppm

1.52.02.53.03.54.04.5 ppm

20

25

30

35

40

45

50

55

C2H

C15H

C3H

C17H C12H &C13H NH

O

S O

O

N

NHO

O

O

HN

HH

HH

H

H

H

H

1

23

5

7

9

12

13

15

11

16

17

NH1

NH2

NH3

NH4

4


S44

(a)

(b)

Figure S8. Partial HMBC (1H-13C) spectra aromatic (a) and aliphatic (b) regions of 3

(400 MHz, CDCl3).

ppm

23456789 ppm

130

140

150

160

170

ppm

1.52.02.53.03.54.04.55.05.56.06.57.0 ppm

20

30

40

50

60

70

80

NH

O

S O

O

N

NHO

O

O

HN

HH

HH

H

H

H

H

1

23

5

7

9

12

13

15

11

16

17

NH1

NH2

NH3

NH4

4


S45

Figure S9. 2D NOESY spectrum of 3 (400 MHz, CDCl3).

ppm

23456789 ppm

2

3

4

5

6

7

8

9


S46

NH

O

S O

O

N

NHO

O

O

HN

HH

H

H

H

H

H

H

1

23

5

7

9

12

13

15

11

16

17

NH1

NH2

NH3

NH4

3


ppm

1.21.31.41.51.61.7 ppm

6.5

6.6

NH3 &

NH4

C3H

C17H

C12H &

C13H

ppm

4.14.2 ppm

6.5

6.6

NH3 &NH4

C2H

ppm

4.14.2 ppm

6.5

6.6

NH3 &NH4

C2H

ppm

1.21.41.61.82.0 ppm

4.1

4.2

C2H

C3H

C17H

C12H &C13H

ppm

5.055.105.15 ppm

6.5

6.6

NH3 &NH4

NH1


S47

(a)

(b)

Figure S11. Partial COSY spectra of 4 (400 MHz, CDCl3) aromatic (a) and aliphatic (b)

regions.

ppm

56789 ppm

5.5

6.0

6.5

7.0

7.5

8.0

8.5

9.0

9.5

10.0

NH2 C5H

C8H

C6H C7HNH3 NH1

ppm

1234 ppm

1

2

3

4

C2H C10H

tBocC12H,

C13H

C11H

HN

O

SO

O

NH

HN O

O

1

2

3

4 5

6

78

9

10

1112 13

14 15

1617

NH3

NH2

NH1


S48

(a)

(b)

Figure S12. Partial HSQC spectra of 4 (400 MHz, CDCl3) aromatic (a) and aliphatic (b)

regions.

ppm

8 ppm

124

126

128

130

132

134

C5H C8H C6H C7H

ppm

1234 ppm

20

25

30

35

40

45

50

C2H C10HtBoc

C12H,

C13H

C11H

HN

O

SO

O

NH

HN O

O

1

2

3

4 5

6

78

9

10

1112 13

14 15

1617

NH3

NH2

NH1


S49

(a)

(b)

Figure S13. Partial HMBC spectra of 4 (400 MHz, CDCl3) aromatic (a) and aliphatic (b)

regions.

ppm

78 ppm

125

130

135

C5HC8H C6H C7H

ppm

12345 ppm

20

30

40

50

60

70

80

C2H C10H

tBoc

C12H,

C13H

NH1C11H

HN

O

SO

O

NH

HN O

O

1

2

3

4 5

6

78

9

10

1112 13

14 15

1617

NH3

NH2

NH1


S50

Figure S14. Full 2D spectrum of 4 (400 MHz, CDCl3)

ppm

123456789 ppm

1

2

3

4

5

6

7

8

9

10


S51


HN

O

SO

O

NH

HN O

O

1

2

3

4 5

6

78

9

10

1112 13

14 15

1617

NH3

NH2

NH1

ppm

1.01.52.02.53.03.54.04.55.05.56.0 ppm

1.6

tBoc

NH3 NH1

C2H

C12H,

C13HtBocC10H

ppm

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

4.0

NH2C5H NH3

NH1

C2H

tBoc

C12H,

C13H

C2H


S52

(a)

(b)


ppm

7.27.37.47.57.67.77.87.98.08.18.2 ppm

7.2

7.4

7.6

7.8

8.0

8.2

C12H

C9H

C11H

C10H

ppm

1.01.52.02.53.03.54.04.5 ppm

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5C2H

C5H

C3H

C4H

C13’H

C13H

C14H

C15H &C16H

C18H

NH

O

S O

O

N

NO

O

H

1

4

5

6

9

12

13

1516

1718

H

14

NH1

NH2

23

7

810

11


S53

(a)

(b)

Figure S17. Partial HSQC spectra of 5 (500MHz, CDCl3): aromatic (a) and aliphatic regions (b).

ppm

7.27.47.67.88.08.2 ppm

122

124

126

128

130

132

134

136

C12HC9H C11H C10H

ppm

1.01.52.02.53.03.54.04.5 ppm

20

30

40

50

60

C2H C5H C3H

C4

H

C1

3’H

C13H

C14

H C15H &C16H

C18H

NH

O

S O

O

N

NO

O

H

1

4

5

6

9

12

13

1516

1718

H

14

NH1

NH2

23

7

810

11


S54

(a)

(b)

Figure S18. Partial HMBC (1H-13C) spectra (a) aromatic and (b) aliphatic regions of 5

(500 MHz, CDCl3).

ppm

23456789 ppm

120

125

130

135

140

145

150

155

160

165

170

175

ppm

1.01.52.02.53.03.54.04.5 ppm

20

30

40

50

60

70

80

NH

O

S O

O

N

NO

O

H

1

4

5

6

9

12

13

1516

1718

H

14

NH1

NH2

23

7

810

11


S55

Figure S19. 2D NOESY spectrum of 5 (500 MHz, CDCl3).

ppm

12345678910 ppm

1

2

3

4

5

6

7

8

9

10


S56

Figure S20. 2D NOESY excerpts of 5(500 MHz, CDCl3).

ppm

1.41.51.61.71.81.9 ppm

6.4

6.6

C18H

C14H

NH2

ppm

1.41.51.61.71.81.9 ppm

0.80

0.85

0.90

C18H

C14H

C15H &C16H

ppm

4.24.34.44.5 ppm

6.3

6.4

6.5

6.6

NH2

C2H

NH

O

S O

O

N

NO

O

H

1

4

5

6

9

12

13

15

16

1718

H

HH

H

H

HH

14H

NH1

NH2

11

10

2

3

6


S57

Compound-1

Figure S21. ORTEP diagram of 1. Ellipsoids were drawn with 50% probability.

Table S9: Torsion angles [°] for 1.

O(5)-S-N(3)-C(10) 21.9(3)

O(4)-S-N(3)-C(10) 153.3(3)

C(5)-S-N(3)-C(10) -93.5(3)

C(15)-O(1)-C(1)-O(2) -2.6(5)

C(15)-O(1)-C(1)-N(1) 177.1(2)

C(2)-N(1)-C(1)-O(2) -23.9(4)

C(2)-N(1)-C(1)-O(1) 156.4(2)

C(1)-N(1)-C(2)-C(3) 79.9(3)

C(4)-N(2)-C(3)-O(3) -0.6(4)

C(4)-N(2)-C(3)-C(2) 177.8(3)

N(1)-C(2)-C(3)-O(3) -170.4(3)

N(1)-C(2)-C(3)-N(2) 11.1(4)

C(3)-N(2)-C(4)-C(5) 149.2(3)

C(3)-N(2)-C(4)-C(9) -31.9(4)

C(9)-C(4)-C(5)-C(6) -2.1(4)

N(2)-C(4)-C(5)-C(6) 176.8(3)

C(9)-C(4)-C(5)-S 176.0(2)

N(2)-C(4)-C(5)-S -5.0(3)

O(5)-S-C(5)-C(4) 175.5(2)

O(4)-S-C(5)-C(4) 44.6(3)

N(3)-S-C(5)-C(4) -68.8(2)

O(5)-S-C(5)-C(6) -6.3(3)

O(4)-S-C(5)-C(6) -137.2(2)

N(3)-S-C(5)-C(6) 109.4(2)

C(4)-C(5)-C(6)-C(7) 2.7(4)

S-C(5)-C(6)-C(7) -175.5(2)


S58

C(5)-C(6)-C(7)-C(8) -1.7(5)

C(6)-C(7)-C(8)-C(9) 0.1(5)

C(7)-C(8)-C(9)-C(4) 0.5(5)

C(5)-C(4)-C(9)-C(8) 0.5(4)

N(2)-C(4)-C(9)-C(8) -178.4(3)

S-N(3)-C(10)-C(11) 173.2(2)

S-N(3)-C(10)-C(13) -70.3(3)

S-N(3)-C(10)-C(12) 52.7(4)

C(14)-O(7)-C(13)-O(6) 2.9(5)

C(14)-O(7)-C(13)-C(10) -173.0(3)

N(3)-C(10)-C(13)-O(6) 143.7(3)

C(11)-C(10)-C(13)-O(6) -100.7(3)

C(12)-C(10)-C(13)-O(6) 19.1(4)

N(3)-C(10)-C(13)-O(7) -40.5(4)

C(11)-C(10)-C(13)-O(7) 75.2(3)

C(12)-C(10)-C(13)-O(7) -165.0(2)

C(1)-O(1)-C(15)-C(17) -62.6(3)

C(1)-O(1)-C(15)-C(16) 62.3(3)

C(1)-O(1)-C(15)-C(18) -180.0(3)

O(5')-S'-N(3')-C(10') -19.8(3)

O(4')-S'-N(3')-C(10') -151.5(3)

C(5')-S'-N(3')-C(10') 94.9(3)

C(15')-O(1')-C(1')-O(2') -6.1(4)

C(15')-O(1')-C(1')-N(1') 174.4(2)

C(2')-N(1')-C(1')-O(2') 25.5(4)

C(2')-N(1')-C(1')-O(1') -155.0(2)

C(1')-N(1')-C(2')-C(3') -84.4(3)

C(4')-N(2')-C(3')-O(3') 1.6(4)

C(4')-N(2')-C(3')-C(2') -179.1(3)

N(1')-C(2')-C(3')-O(3') 171.0(3)

N(1')-C(2')-C(3')-N(2') -8.4(4)

C(3')-N(2')-C(4')-C(9') 32.5(4)

C(3')-N(2')-C(4')-C(5') -149.0(3)

C(9')-C(4')-C(5')-C(6') 0.4(4)

N(2')-C(4')-C(5')-C(6') -178.0(3)

C(9')-C(4')-C(5')-S' -176.6(2)

N(2')-C(4')-C(5')-S' 4.9(3)

O(5')-S'-C(5')-C(6') 6.2(3)

O(4')-S'-C(5')-C(6') 136.6(2)

N(3')-S'-C(5')-C(6') -110.1(2)

O(5')-S'-C(5')-C(4') -176.8(2)

O(4')-S'-C(5')-C(4') -46.3(3)

N(3')-S'-C(5')-C(4') 67.0(2)

C(4')-C(5')-C(6')-C(7') -1.0(4)


S59

S'-C(5')-C(6')-C(7') 176.0(2)

C(5')-C(6')-C(7')-C(8') 0.3(5)

C(6')-C(7')-C(8')-C(9') 1.1(5)

C(5')-C(4')-C(9')-C(8') 0.9(4)

N(2')-C(4')-C(9')-C(8') 179.4(2)

C(7')-C(8')-C(9')-C(4') -1.7(4)

S'-N(3')-C(10')-C(12') -52.6(4)

S'-N(3')-C(10')-C(11') -173.5(2)

S'-N(3')-C(10')-C(13') 70.4(3)

C(14')-O(7')-C(13')-O(6') -2.6(5)

C(14')-O(7')-C(13')-C(10') 173.6(3)

N(3')-C(10')-C(13')-O(6') -146.2(3)

C(12')-C(10')-C(13')-O(6') -21.1(4)

C(11')-C(10')-C(13')-O(6') 98.5(3)

N(3')-C(10')-C(13')-O(7') 37.6(3)

C(12')-C(10')-C(13')-O(7') 162.6(3)

C(11')-C(10')-C(13')-O(7') -77.7(3)

C(1')-O(1')-C(15')-C(16') -175.7(3)

C(1')-O(1')-C(15')-C(17') 66.1(4)

C(1')-O(1')-C(15')-C(18') -58.1(3)

Compound-2



S60


O(5)-S(1)-N(3)-C(10) 25.0(1)

O(4)-S(1)-N(3)-C(10) 156.1(1)

C(5)-S(1)-N(3)-C(10) -90.7(1)

C(15)-O(1)-C(1)-O(2) 3.0(2)

C(15)-O(1)-C(1)-N(1) -177.9(1)

C(2)-N(1)-C(1)-O(2) -10.7(2)

C(2)-N(1)-C(1)-O(1) 170.2(1)

C(1)-N(1)-C(2)-C(3) 86.7(2)

C(4)-N(2)-C(3)-O(3) 3.6(2)

C(4)-N(2)-C(3)-C(2) -176.4(1)

N(1)-C(2)-C(3)-O(3) -171.0(1)

N(1)-C(2)-C(3)-N(2) 9.0(2)

C(3)-N(2)-C(4)-C(9) -45.3(2)

C(3)-N(2)-C(4)-C(5) 134.9(1)

C(9)-C(4)-C(5)-C(6) -1.9(2)

N(2)-C(4)-C(5)-C(6) 177.9(1)

C(9)-C(4)-C(5)-S(1) 174.2(1)

N(2)-C(4)-C(5)-S(1) -5.9(2)

O(5)-S(1)-C(5)-C(6) -5.0(1)

O(4)-S(1)-C(5)-C(6) -134.5(1)

N(3)-S(1)-C(5)-C(6) 113.5(1)

O(5)-S(1)-C(5)-C(4) 178.8(1)

O(4)-S(1)-C(5)-C(4) 49.2(1)

N(3)-S(1)-C(5)-C(4) -62.7(1)

C(4)-C(5)-C(6)-C(7) 2.6(2)

S(1)-C(5)-C(6)-C(7) -173.6(1)

C(5)-C(6)-C(7)-C(8) -1.1(2)

C(6)-C(7)-C(8)-C(9) -1.2(2)

C(7)-C(8)-C(9)-C(4) 1.9(2)

C(5)-C(4)-C(9)-C(8) -0.3(2)

N(2)-C(4)-C(9)-C(8) 179.9(1)

S(1)-N(3)-C(10)-C(11) 42.6(2)

S(1)-N(3)-C(10)-C(12) 162.6(1)

S(1)-N(3)-C(10)-C(13) -81.9(1)

C(14)-N(4)-C(13)-O(6) -0.8(2)

C(14)-N(4)-C(13)-C(10) 176.2(1)

N(3)-C(10)-C(13)-O(6) -13.4(2)

C(11)-C(10)-C(13)-O(6) -137.4(1)

C(12)-C(10)-C(13)-O(6) 100.7(1)

N(3)-C(10)-C(13)-N(4) 169.5(1)

C(11)-C(10)-C(13)-N(4) 45.5(2)

C(12)-C(10)-C(13)-N(4) -76.4(1)


S61

C(1)-O(1)-C(15)-C(16) 62.6(2)

C(1)-O(1)-C(15)-C(17) -179.3(1)

C(1)-O(1)-C(15)-C(18) -62.3(2)

Compound-3



O(4)-S-N(3)-C(11) -154.4(3)

O(3)-S-N(3)-C(11) -22.7(3)

C(6)-S-N(3)-C(11) 91.4(3)

C(2)-N(1)-C(1)-O(1) 4.2(5)

C(2)-N(1)-C(1)-O(6) -177.0(3)

C(16)-O(6)-C(1)-O(1) -6.6(5)

C(16)-O(6)-C(1)-N(1) 174.6(3)

C(1)-N(1)-C(2)-C(3) 161.1(3)

C(1)-N(1)-C(2)-C(4) -75.7(4)

C(5)-N(2)-C(4)-O(2) 3.9(5)

C(5)-N(2)-C(4)-C(2) -173.8(3)

N(1)-C(2)-C(4)-O(2) 157.7(3)

C(3)-C(2)-C(4)-O(2) -78.4(4)

N(1)-C(2)-C(4)-N(2) -24.6(4)

C(3)-C(2)-C(4)-N(2) 99.4(3)

C(4)-N(2)-C(5)-C(10) 75.3(4)

C(4)-N(2)-C(5)-C(6) -102.5(4)

C(10)-C(5)-C(6)-C(7) 1.5(5)


S62

N(2)-C(5)-C(6)-C(7) 179.3(3)

C(10)-C(5)-C(6)-S -178.0(2)

N(2)-C(5)-C(6)-S -0.2(4)

O(4)-S-C(6)-C(7) 124.4(3)

O(3)-S-C(6)-C(7) -5.0(3)

N(3)-S-C(6)-C(7) -121.5(3)

O(4)-S-C(6)-C(5) -56.1(3)

O(3)-S-C(6)-C(5) 174.5(3)

N(3)-S-C(6)-C(5) 58.0(3)

C(5)-C(6)-C(7)-C(8) -1.0(5)

S-C(6)-C(7)-C(8) 178.5(2)

C(6)-C(7)-C(8)-C(9) 0.5(5)

C(7)-C(8)-C(9)-C(10) -0.5(5)

C(8)-C(9)-C(10)-C(5) 1.0(5)

C(6)-C(5)-C(10)-C(9) -1.4(5)

N(2)-C(5)-C(10)-C(9) -179.3(3)

S-N(3)-C(11)-C(14) -56.1(3)

S-N(3)-C(11)-C(13) 67.8(4)

S-N(3)-C(11)-C(12) -173.3(2)

C(15)-N(4)-C(14)-O(5) -1.8(5)

C(15)-N(4)-C(14)-C(11) -179.5(3)

N(3)-C(11)-C(14)-O(5) 132.6(3)

C(13)-C(11)-C(14)-O(5) 8.5(4)

C(12)-C(11)-C(14)-O(5) -111.5(3)

N(3)-C(11)-C(14)-N(4) -49.6(4)

C(13)-C(11)-C(14)-N(4) -173.8(3)

C(12)-C(11)-C(14)-N(4) 66.2(4)

C(1)-O(6)-C(16)-C(18) 53.5(4)

C(1)-O(6)-C(16)-C(19) -71.7(4)

C(1)-O(6)-C(16)-C(17) 170.8(3)


S63

Compound-4



O(4)-S(1)-N(3)-C(10) 45.4(4)

O(5)-S(1)-N(3)-C(10) 174.6(4)

C(5)-S(1)-N(3)-C(10) -71.2(4)

C(14)-O(1)-C(1)-O(2) 1.3(1)

C(14)-O(1)-C(1)-N(1) 177.7(6)

C(2)-N(1)-C(1)-O(2) -9.8(1)

C(2)-N(1)-C(1)-O(1) 173.7(6)

C(1)-N(1)-C(2)-C(3) -55.9(7)

C(4)-N(2)-C(3)-O(3) 3.8(8)

C(4)-N(2)-C(3)-C(2) -176.8(4)

N(1)-C(2)-C(3)-O(3) -40.7(7)

N(1)-C(2)-C(3)-N(2) 139.8(4)

C(3)-N(2)-C(4)-C(9) -53.3(7)

C(3)-N(2)-C(4)-C(5) 128.6(5)

C(9)-C(4)-C(5)-C(6) 1.4(7)

N(2)-C(4)-C(5)-C(6) 179.5(4)

C(9)-C(4)-C(5)-S(1) 177.1(4)

N(2)-C(4)-C(5)-S(1) -4.8(6)

O(4)-S(1)-C(5)-C(4) 174.4(4)

O(5)-S(1)-C(5)-C(4) 45.2(5)

N(3)-S(1)-C(5)-C(4) -67.7(5)

O(4)-S(1)-C(5)-C(6) -9.9(5)

O(5)-S(1)-C(5)-C(6) -139.1(4)

N(3)-S(1)-C(5)-C(6) 108.0(4)


S64

C(4)-C(5)-C(6)-C(7) -1.3(8)

S(1)-C(5)-C(6)-C(7) -177.1(4)

C(5)-C(6)-C(7)-C(8) 2.0(9)

C(6)-C(7)-C(8)-C(9) -2.8(9)

C(5)-C(4)-C(9)-C(8) -2.3(8)

N(2)-C(4)-C(9)-C(8) 179.6(5)

C(7)-C(8)-C(9)-C(4) 2.9(9)

S(1)-N(3)-C(10)-C(11) -121.1(5)

N(3)-C(10)-C(11)-C(23') 54.4(9)

N(3)-C(10)-C(11)-C(23) -56.3(9)

N(3)-C(10)-C(11)-C(24) -166.6(9)

N(3)-C(10)-C(11)-C(24') 167.1(9)

C(1)-O(1)-C(14)-C(15) 59.6(8)

C(1)-O(1)-C(14)-C(17) 178.1(7)

C(1)-O(1)-C(14)-C(16) -65.7(9)

Compound-5



O(4)-S-N(3)-C(13) -51.9(2)

O(3)-S-N(3)-C(13) 179.0(2)

C(8)-S-N(3)-C(13) 63.9(2)

C(17)-O(5)-C(1)-O(1) -3.2(3)


S65

C(17)-O(5)-C(1)-N(1) 178.7(2)

C(2)-N(1)-C(1)-O(1) 23.7(3)

C(5)-N(1)-C(1)-O(1) 175.8(2)

C(2)-N(1)-C(1)-O(5) -158.1(2)

C(5)-N(1)-C(1)-O(5) -6.1(3)

C(1)-N(1)-C(2)-C(6) -85.6(2)

C(5)-N(1)-C(2)-C(6) 119.5(2)

C(1)-N(1)-C(2)-C(3) 151.8(2)

C(5)-N(1)-C(2)-C(3) -3.1(2)

N(1)-C(2)-C(3)-C(4) 22.3(2)

C(6)-C(2)-C(3)-C(4) -102.7(2)

C(2)-C(3)-C(4)-C(5) -33.6(3)

C(1)-N(1)-C(5)-C(4) -171.0(2)

C(2)-N(1)-C(5)-C(4) -17.2(2)

C(3)-C(4)-C(5)-N(1) 30.9(2)

C(7)-N(2)-C(6)-O(2) -1.6(4)

C(7)-N(2)-C(6)-C(2) 177.8(2)

N(1)-C(2)-C(6)-O(2) 172.6(2)

C(3)-C(2)-C(6)-O(2) -69.1(3)

N(1)-C(2)-C(6)-N(2) -6.8(3)

C(3)-C(2)-C(6)-N(2) 111.5(2)

C(6)-N(2)-C(7)-C(12) 28.8(3)

C(6)-N(2)-C(7)-C(8) -151.9(2)

C(12)-C(7)-C(8)-C(9) 2.2(3)

N(2)-C(7)-C(8)-C(9) -177.2(2)

C(12)-C(7)-C(8)-S -175.2(2)

N(2)-C(7)-C(8)-S 5.4(3)

O(4)-S-C(8)-C(9) 9.6(2)

O(3)-S-C(8)-C(9) 139.4(2)

N(3)-S-C(8)-C(9) -107.6(2)

O(4)-S-C(8)-C(7) -172.9(2)

O(3)-S-C(8)-C(7) -43.2(2)

N(3)-S-C(8)-C(7) 69.9(2)

C(7)-C(8)-C(9)-C(10) -2.3(4)

S-C(8)-C(9)-C(10) 175.1(2)

C(8)-C(9)-C(10)-C(11) 0.9(5)

C(9)-C(10)-C(11)-C(12) 0.7(5)

C(10)-C(11)-C(12)-C(7) -0.7(5)

N(2)-C(7)-C(12)-C(11) 178.7(2)

C(8)-C(7)-C(12)-C(11) -0.7(4)

S-N(3)-C(13)-C(14) 139.3(2)

N(3)-C(13)-C(14)-C(16) 61.9(4)

N(3)-C(13)-C(14)-C(15) -177.0(3)

C(1)-O(5)-C(17)-C(19) -55.6(3)


S66

C(1)-O(5)-C(17)-C(18) 70.1(3) C(1)-O(5)-C(17)-C(20) -174.6(2)

Compound-6



O(2)-S-N(2)-C(2) -39.5(2)

O(3)-S-N(2)-C(2) -168.6(1)

C(3)-S-N(2)-C(2) 77.2(2)

C(9)-N(1)-C(1)-O(1) 1.1(3)

C(9)-N(1)-C(1)-C(2) 177.4(2)

S-N(2)-C(2)-C(11) 104.5(2)

S-N(2)-C(2)-C(10) -19.3(2)

S-N(2)-C(2)-C(1) -136.1(1)

O(1)-C(1)-C(2)-N(2) -160.5(2)

N(1)-C(1)-C(2)-N(2) 23.1(2)

O(1)-C(1)-C(2)-C(11) -41.5(2)

N(1)-C(1)-C(2)-C(11) 142.2(2)

O(1)-C(1)-C(2)-C(10) 78.2(2)

N(1)-C(1)-C(2)-C(10) -98.2(2)

O(2)-S-C(3)-C(4) 4.3(2)

O(3)-S-C(3)-C(4) 133.6(2)

N(2)-S-C(3)-C(4) -115.3(2)

O(2)-S-C(3)-C(8) -178.9(2)

O(3)-S-C(3)-C(8) -49.6(2)

N(2)-S-C(3)-C(8) 61.5(2)


S67

C(8)-C(3)-C(4)-C(5) -1.8(3)

S-C(3)-C(4)-C(5) 175.0\4(2)

C(3)-C(4)-C(5)-C(6) 1.1(4)

C(4)-C(5)-C(6)-C(7) -0.2(4)

C(5)-C(6)-C(7)-C(8) -0.2(4)

C(6)-C(7)-C(8)-N(3) -176.6(2)

C(6)-C(7)-C(8)-C(3) -0.4(3)

C(4)-C(3)-C(8)-N(3) 177.4(2)

S-C(3)-C(8)-N(3) 0.7(3)

C(4)-C(3)-C(8)-C(7) 1.3(3)

S-C(3)-C(8)-C(7) -175.4(2)


S68

Table S15: Analysis of Potential Hydrogen Bonds of compound 1 =======================================================================

Donor --- H....Acceptor [ARU] D - H H...A D...A D - H...A

-----------------------------------------------------------------------

Intramolecular

1 N2 --H2 ..O4 0.86 2.12 2.793(3) 134

2 N2 --H2 ..N1 0.86 2.37 2.795(3) 111

3 N2' --H2' ..O4' 0.86 2.13 2.804(3) 135

4 N2' --H2' ..N1' 0.86 2.36 2.789(3) 111

5 N3 --H3 ..O2 0.86 2.20 3.044(3) 169

6 N3' --H3' ..O2' 0.86 2.17 3.016(3) 167

7 C6 --H6 ..O5 0.93 2.50 2.896(5) 106

8 C6' --H6' ..O5' 0.93 2.50 2.894(5) 106

9 C9 --H9 ..O3 0.93 2.40 2.892(3) 113

10 C9' --H9' ..O3' 0.93 2.42 2.897(3) 112

11 C12 --H12A ..O5 0.96 2.58 3.168(4) 120

12 C12' --H12F ..O5' 0.96 2.54 3.143(4) 121

13 C16 --H16A ..O2 0.96 2.46 3.016(4) 116

14 C17 --H17C ..O2 0.96 2.50 3.044(4) 116

15 C17' --H17D ..O2' 0.96 2.52 3.068(4) 116

16 C18' --H18F ..O2' 0.96 2.45 3.003(4) 116

Intermolecular

-----------------------------------------------------------------------

17 N1 --H1 ..O3'i 0.86 2.32 2.825(3) 118

18 N1' --H1' ..O3ii 0.86 2.37 2.832(3) 114

19 C12' --H12D ..O3iii 0.96 2.59 3.286(4) 129

20 C17 --H17B ..O6'iv 0.96 2.59 3.451(4) 150

Equivalent Position Code

===============================

[4455.]i = -1/2+x,1/2-y,z

[4565.]ii = 1/2+x,3/2-y,z

[4555.]iii = 1/2+x,1/2-y,z

[3654.]iv = 3/2-x,1/2+y,-1/2+z

Table S16: Analysis of Potential Hydrogen Bonds of compound 2

======================================================================


----------------------------------------------------------------------

Intramolecular

1 N(2) --H(2) ..O(4) 0.86 2.27 2.843(2) 124

2 N(2) --H(2) ..N(1) 0.86 2.34 2.759(2) 111

3 N(3) --H(3) ..O(2) 0.86 2.17 2.992(2) 160

4 C(6) --H(6) ..O(5) 0.93 2.51 2.895(2) 105

5 C(9) --H(9) ..O(3) 0.93 2.57 2.941(2) 105

6 C(11) --H(11A) ..O(5) 0.96 2.52 3.112(2) 120

7 C(16) --H(16A) ..O(2) 0.96 2.49 3.049(2) 117

8 C(18) --H(18C) ..O(2) 0.96 2.47 3.030(2) 117

9 C(18) --H(18C) ..O(6) 0.96 2.55 3.257(2) 131

Intermolecular

-----------------------------------------------------------------------


S69

10 N(1) --H(1) ..O(6)i 0.86 1.93 2.753(2) 159

11 N(4) --H(4) ..O(3)ii 0.86 2.03 2.857(2) 161

12 C(11) --H(11B) ..O(3)ii 0.96 2.50 3.407(2) 157


=============================

[4554.]i = x,1/2-y,-1/2+z

[4565.]ii = x,3/2-y,1/2+z


=======================================================================


-----------------------------------------------------------------------

Intramolecular

1 N(2) --H(2) ..N(1) 0.86 2.37 2.755(4) 107

2 N(3) --H(3) ..O(1) 0.86 2.08 2.914(4) 162

3 N(4) --H(4) ..O(2) 0.86 2.09 2.937(4) 169

4 C(7) --H(7) ..O(3) 0.93 2.44 2.841(4) 106

5 C(13) --H(13A) ..O(3) 0.96 2.44 3.065(5) 123

6 C(18) --H(18A) ..O(1) 0.96 2.37 2.889(5) 114

Intermolecular

-------------------------------------------------------------------

7 N(1) --H(1) ..O(5)i 0.86 2.10 2.854(4) 146

8 C(8) --H(8) ..O(5)ii 0.93 2.52 3.224(5) 133


==========================

[1565.]i = x,1+y,z

[2656.]ii = 1-x,-y,1-z


=======================================================================


-----------------------------------------------------------------------

Intramolecular

1 N(2) --H(2) ..O(5) 0.86 2.33 2.831(6) 118

2 N(3) --H(3) ..O(2) 0.86 2.20 2.887(6) 137

3 C(6) --H(6) ..O(4) 0.93 2.47 2.858(7) 105

4 C(10) --H(10B) ..O(4) 0.97 2.58 2.964(7) 104

5 C(15) --H(15A) ..O(2) 0.96 2.40 2.990(1) 119

6 C(16) --H(16C) ..O(2) 0.96 2.46 3.056(8) 120

Intermolecular

-------------------------------------------------------------------

7 N(1) --H(1) ..O(3)i 0.86 2.01 2.858(6) 168

8 C(10) --H(10B) ..O(5)ii 0.97 2.50 3.381(7) 151

Translation of ARU-code to Equivalent Position Code

===================================================


S70

[10664.]i = 3/2-x,1-y,-1/2+z

[1556.]ii = x,y,1+z


====================================================================


--------------------------------------------------------------------

Intramolecular

1 N(2) --H(2) ..O(3) 0.86 2.10 2.789(2) 137

2 N(2) --H(2) ..N(1) 0.86 2.29 2.741(2) 113

3 N(3) --H(3) ..O(1) 0.86 2.25 3.017(3) 148

4 C(9) --H(9) ..O(4) 0.93 2.49 2.875(3) 105

5 C(12) --H(12) ..O(2) 0.93 2.36 2.881(3) 115

6 C(19) --H(19C) ..O(1) 0.96 2.38 2.975(4) 120

Intermolecular

-------------------------------------------------------------------

7 C(2) --H(2A) ..O(3)i 0.98 2.55 3.151(3) 119

8 C(20) --H(20A) ..O(2)ii 0.96 2.60 3.541(5) 167


===================================================

[2655.]i = 1-x,1/2+y,-z

[2645.]ii = 1-x,-1/2+y,-z

Table S20:Analysis of Potential Hydrogen Bonds of compound 6

=======================================================================


-----------------------------------------------------------------------

Intramolecular

1 N(1) --H(1N) ..N(2) 0.86 2.29 2.675(2) 107

2 N(1) --H(1N) ..N(3) 0.86 2.42 3.267(3) 169

3 N(3) --H(3B) ..O(3) 0.86 2.35 2.947(2) 127

4 C(4) --H(4A) ..O(2) 0.93 2.46 2.863(3) 106

5 C(10) --H(10C) ..O(2) 0.96 2.49 3.095(3) 121

Intermolecular

-------------------------------------------------------------------

6 N(2) --H(2N) ..O(1)i 0.86 2.07 2.873(2) 155

7 N(3) --H(3A) ..O(2)ii 0.86 2.55 3.361(2) 156

8 C(9) --H(9B) ..O(3)ii 0.96 2.54 3.357(3) 143

9 C(10) --H(10B) ..O(3)iii 0.96 2.52 3.427(3) 157


===================================================

[2645.]i = 1-x,-1/2+y,1/2-z

[4565.]ii = x,3/2-y,1/2+z

[1565.]iii = x,1+y,z


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