Contents · 2009-12-04 · Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2006 S3 Supplementary data 350 400 450 500 550

Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2006

S1

Supporting Information

Novel strategy to selectively detect Fe(III) in aqueous media driven by hydrolysis of rhodamine 6G Schiff base

5

Min Hee Lee,a Thang Van Giap,b Sang Hoon Kim,a Young Hoon Lee,a Chulhun Kang,b,* and Jong Seung Kima,*

aDepartment of Chemistry, Korea University, Seoul 136-701, Korea bThe School of East-West Medical Science, Kyung Hee University, Yongin 446-701, Korea 10

*Corresponding authors: [email protected] (C. Kang); [email protected] (J. S. Kim)

Contents 15

General instrumentations and reagents ---------------------------------- page S2

UV/Vis and Fluorescence Spectroscopic Methods --------------------- page S2

Cell culture --------------------------------------------------------------------- page S2

Supplementary data ---------------------------------------------------------- page S3 20

Figures S1~S8

Experimental Section -------------------------------------------------------- page S7

1H (400 MHz) / 13C (100 MHz) NMR and FAB-MS Analysis--------- page S8

Figures S9~S11

X-ray Crystal Structure of 1------------------------------------------------ page S10 25

Tables S1-S6


S2

General instrumentations and reagents All fluorescence and UV/Vis absorption spectra were recorded in RF-5301PC and S-3100

spectrophotometer, respectively. NMR was recorded at Varian instrument (400 MHz). All reagents

and cationic compounds such as chloride salts of Na+, K+, Li+, Cs+, Ag+, Cd2+, Mg2+, Ca2+, Ba2+, Zn2+, 30

Hg2+, Pb2+, Co2+, Cu2+, Fe2+ and Fe3+ were purchased from Aldrich and used as received. All solvents

were analytical reagents. CH3CN for spectra detection was HPLC reagent without fluorescent impurity

and H2O was deionized water.

UV/Vis and Fluorescence Spectroscopic Methods 35

Stock solutions (0.01 M) of metal chloride salts were prepared in deionized water. Stock solution of

FS1 was prepared in CH3CN. Excitation was carried out at 528 nm with all excitation and emission slit

widths are 3 nm. Titration experiments were performed with 1 µM solutions of FS1 in CH3CN and

various concentrations of FeCl3 in deionized water. The concentrations of each FeCl3 solution were

varied, but the total volume was fixed at 4.0 mL. 40

Cell Culture A human hepatoma cell line, Hep G2, was grown in Dulbecco's Modified Eagle Medium (DMEM)

medium supplemented with 10 % fetal calf serum, 1 % penicillin and 10,000 Unit /ml of streptomycin.

at 37 °C under humidified air containing 5% CO2. 1 x 105 of the cells were located and stabilized in a 45

well of a 24-well plate and the medium was replaced with a new one containing 500 μM of ferric

citrate. After 24 hrs of incubation, the medium was removed and the cells were briefly washed with 1

mL of phosphate buffered saline (PBS). And, 1mL of FS1 containing medium (the final concentration

was 1 μM) was placed and incubated at the incubator. Then, the images were obtained using a

confocal microscope from Carl Zeiss (LSM 510 META model). FS1 was excited at 543 nm using a 50

HeNe laser and emission image was acquired using a longpath filter (>560 nm). All images were taken

under the same experimental parameters to minimize possible variations in fluorescence intensity.

55


S3

Supplementary data

350 400 450 500 5500.0

0.5

1.0

Abs

orba

nce

Wavelength (nm)

1, other metal cations

Fe3+

Fe2+

O

N

NH

NH

ONH2

1

350 400 450 500 5500.0

0.5

1.0

Abs

orba

nce

Wavelength (nm)

1, other metal cations

Fe3+

Fe2+

O

N

NH

NH

ONH2

1

Figure S1. Absorption spectra of 1 (10 µM) to various Cl– salts of metal cations such as K+, Na+, Fe2+,

Ca2+, Mg2+, Mn2+ and Fe3+ ions. (50 equiv, respectively) 60

350 400 450 500 5500.0

0.6

1.2

1.8

Abs

orba

nce

Wavelength (nm)

Fe3+

350 400 450 500 5500.0

0.6

1.2

1.8

Abs

orba

nce

Wavelength (nm)

Fe3+

Figure S2. Absorption titration spectra of FS1 (10 µM) in aqueous solution (H2O:CH3CN = 95:5, v/v).

Spectra shown are for [Fe3+] (A: 0, 1, 10, 20, 40, 50, 100, 150, 250, 350, 450 µM). 65


S4

300 400 500 6000.0

0.5

1.0

Nor

mal

ized

Inte

nsity

Wavelength (nm)

FeCl3

FS1 + Fe3+

OH

NO2

O

300 400 500 6000.0

0.5

1.0

Nor

mal

ized

Inte

nsity

Wavelength (nm)

FeCl3

FS1 + Fe3+

OH

NO2

O

70

Figure S3. The normalized absorption spectra of FS1 + Fe3+, 2-hydroxy-5-nitrobenzaldehyde, and

FeCl3 in aqueous solution (H2O:CH3CN = 95:5, v/v).

75

1000

800

600

400

200

Fluo

resc

ence

Enh

ance

men

t

a b c d e f g h i j k l m n o p 0

Metal cations

1000

800

600

400

200

Fluo

resc

ence

Enh

ance

men

t

a b c d e f g h i j k l m n o p 0

Metal cations

Figure S4. Fluorescence responses at 551 nm of FS1 (1 µM) to various metal cation in aqueous

solution (H2O:CH3CN = 95:5, v/v). White bars represent the addition of metal cation to FS1 (50 µM,

respectively); a) Fe3+; b) Fe2+; c) K+; d) Na+; e) Ca2+; f) Mg+; g) Mn2+; h) Ag+; i) Hg2+; j) Ba2+; k)

Cd2+; l) Co2+; m) Cu2+; n) Ni2+; o) Pb2+; p) Zn2+; black bars represent the subsequent addition of Fe3+ 80

(50 µM) in the presence of other cations.


S5

[FS1+H]+

[1+H]+

M. W.: 456.6

H2O

M. W.: 605.7

Fe3+

O

N

NH

NH

ONH O

NO2

FS1

O

N

NH

NH

ONH2

1

OHO

NO2+

[FS1+H]+

[1+H]+

M. W.: 456.6

H2O

M. W.: 605.7

Fe3+

O

N

NH

NH

ONH O

NO2

FS1

O

N

NH

NH

ONH2

1

OHO

NO2+

Figure S5. FAB-MS data of FS1 in the absence (left) and the presence (right) of FeCl3 in aqueous

condition. 85

Figure S6. 1H NMR spectra of 2-hydroxy-5-nitrobenzaldehyde in CDCl3; a) commercial (Aldrich); b) 90

isolated from the mixture of FS1 and FeCl3 in aqueous condition.

11.6 11.2 10.8 10.4 10.0 9.6 9.2 8.8 8.4 8.0 7.6 7.2 6.8

0.79

42

1.00

00

1.06

99

1.11

01

1.09

57

a)

b)

11.6 11.2 10.8 10.4 10.0 9.6 9.2 8.8 8.4 8.0 7.6 7.2 6.8

0.79

42

1.00

00

1.06

99

1.11

01

1.09

57

a)

b)


S6

X-ray Crystal Structure of 1·(OTs)2·(H2O).

95

Figure S7. X-ray crystal structure of 1·(OTs)2·(H2O) form the mixture of FS1 and Fe(OTs)36H2O.

Displacement ellipsoids are scaled to a 7% probability level. Most of the hydrogen atoms have been

removed for clarity.

0 20 40 60 80 100Time (min)

Equation: y = A1*exp(-x/t1) + y0R^2 = 0.99118y0 197.87061 ± 0.10241A1 -193.6564 ± 0.40787t1 7.53842 ± 0.0275

Fluo

resc

ence

Inte

nsity

(a.u

.) at

551

nm

FS1 + FeCl3 (100 eq)

0 20 40 60 80 100


Time (min)

Fluo

resc

ence

Inte

nsity

(a.u

.) at

551

nm

FS1 at pH 3.5

0 20 40 60 80 100Time (min)


Fluo

resc

ence

Inte

nsity

(a.u

.) at

551

nm

FS1 + FeCl3 (100 eq)

0 20 40 60 80 100


Time (min)

Fluo

resc

ence

Inte

nsity

(a.u

.) at

551

nm

FS1 at pH 3.5

100

Figure S8. Time course of the fluorescence response of FS1 (1.0 µM) in the presence (left) and

absence (right) of Fe3+ (100 equiv) under the same conditions (at pH = 3.5). The excitation and

emission wavelengths were 528 and 551 nm, respectively. Excitation and emission slits = 1.5/3. The

boxes indicate kinetic analysis results based on first order decay model. 105


S7

Experimental Section

Compound 1 was prepared according to the literature procedure.1 Compound 2 110

ONH

NH

N

O

N

FS1

HO

NO2

1 (0.3 g, 0.6 mmol) was stirred with 2-hydroxy-5-nitrobenzaldehyde (0.1 g, 0.6 mmol) in methanol

for 10 h at room temperature. The precipitates were collected and recrystallized from hexane, finally 115

0.3 g of FS1 (81 % yield) was obtained as a white. Mp 230 – 240 ℃. IR (deposit from MeOH solution

on a NaCl plate, cm-1): 3390, 1681, 1635, 1618, 1513. FAB-MS m/z (M+) calcd 605.7, found 606.2. 1H

NMR (CDCl3, 400 MHz): δ 8.13 (dd, 1 H, J = 2.83 Hz); 8.02 (d, 1 H, J = 2.83 Hz); 7.93 (m, 1 H); 7.79

(s, 1 H); 7.47 ~ 7.44 (m, 2 H); 7.05 ~ 6.90 (m, 1 H); 6.88 (d, 1 H, J = 9.27 Hz); 6.34 (s, 2 H); 6.17 (s, 2

H); 3.51 (m, 4 H); 3.20 (t, 2 H, J = 6.63 Hz); 3.19 (m, 4 H); 1.83 (s, 6 H); 1.32 (t, 6 H, J = 7.13 Hz). 120

13C NMR (CDCl3, 100 MHz): 169.4, 168.5, 164.6, 153.3, 151.7, 147.0, 138.3, 132.7, 130.7, 128.2,

127.9, 123.8, 122.9, 119.1, 117.9, 116.5, 105.8, 96.4, 64.8, 55.5, 40.3, 38.3, 16.6, 14.6 ppm.

125

130

135

140

(1) J.-S. Wu, I.-C. Hwang, K. S. Kim and J. S. Kim, Org. Latt. 2007, 9, 907.


S8

1H (400 MHz) and 13C (100 MHz) NMR spectra

PPM 8.4 8.0 7.6 7.2 6.8 6.4 6.0 5.6 5.2 4.8 4.4 4.0 3.6 3.2 2.8 2.4 2.0 1.6 1.2 0.8 0.4

1.

019

0.97

3

1.

009

2.

080

1.

027

1.

053

2.

040

5.

998

6.

004

4.

116

3.

997

2.

042

2.

011

1.

043

8.

1495

8.

1484

8.

1425

8.

1413

8.

1263

8.

1252

8.

1193

8.

1181

8.

0404

8.

0334

7.

9556

7.

9456

7.

9336

7.

8004

7.

4789

7.

4775

7.

4690

7.

4606

7.

4574

7.

2692

7.

2677

7.

0607

7.

0391

6.

9130

6.

8898

6.

3514

6.

1778

3.

5421

3.

5259

3.

5103

3.

4168

3.

4008

3.

2128

3.

1963

1.

8410

1.

3537

1.

3360

1.

3180

Figure S9. 1H-NMR spectrum of FS1 in CDCl3. 145

PPM 180.0 160.0 140.0 120.0 100.0 80.0 60.0 40.0 20.0

169

.407

4 1

69.3

887

168

.569

2

164

.649

6

153

.354

1 1

51.7

429

147

.486

7

138

.375

4 1

38.3

681

132

.725

4 1

30.7

901

128

.462

7 1

28.2

008

128

.192

3 1

27.9

274

123

.842

3 1

22.9

378

119

.111

3 1

19.0

893

117

.997

8 1

17.9

907

117

.980

4 1

16.5

766

116

.558

0 1

16.5

528

105

.868

1 1

05.8

501

96.

4457

77.

3072

77.

1912

77.

0385

76.

9894

76.

9518

76.

6714

64.

8743

55.

5675

40.

3434

38.

3012

16.

6311

16.

6045

14.

6360

Figure S10. 13C-NMR spectrum of FS1 in CDCl3.

O

N

NH

NH

N

O HO

NO2

O

N

NH

NH

N

O HO

NO2


S9

FAB-MS Analysis 150

Figure S11. FAB-MS spectrum of FS1.

155

160

165

170

175

O

N

NH

NH

N

O

NO2

HO

C35H35N5O5Mol. Wt.: 605.7


S10

X-ray Crystal Structure of 1·(OTs)2·(H2O). 180

X-ray crystal structure of 1·(OTs)2·(H2O) form the mixture of FS1 and Fe(OTs)36H2O. Displacement

ellipsoids are scaled to a 7% probability level. Most of the hydrogen atoms have been removed for

clarity. 185

Table S1. Crystal data and structure refinement for 1·(OTs)2·(H2O).

Empirical formula C42 H45 N4 O9 S2 190

Formula weight 813.94

Temperature 170(2) K

Wavelength 0.71073 Å

Crystal system Triclinic

Space group P-1 195

Unit cell dimensions a = 12.036(5) Å �= 103.902(7)°

b = 13.718(5) Å �= 99.066(7)°

c = 14.809(6) Å � = 114.803(6)°

Volume 2059.8(14) Å3

Z 2 200

Density (calculated) 1.312 Mg/m3

Absorption coefficient 0.189 mm-1

F(000) 858

Crystal size 0.15 x 0.10 x 0.08 mm3


S11

Theta range for data collection 1.74 to 26.00 . 205

Index ranges -13 ≤ h ≤ 14, -16 ≤ k ≤ 16, -18 ≤ l ≤ 17

Reflections collected 10915

Independent reflections 7629 [R(int) = 0.0446]

Completeness to theta = 26.00 94.2 %

Refinement method Full-matrix least-squares on F2 210

Data / restraints / parameters 7629 / 0 / 520

Goodness-of-fit on F2 0.892

Final R indices [I>2sigma(I)] R1 = 0.0759, wR2 = 0.1942

R indices (all data) R1 = 0.1618, wR2 = 0.2483

Largest diff. peak and hole 0.687 and -0.700 e.Å-3 215


S12

Table S2. Atomic coordinates (Å x 104) and equivalent isotropic displacement parameters (Å2x 103) for 1·(OTs)2·(H2O). U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________

x y z U(eq)

________________________________________________________________________________ 220

N(1) 6604(5) 7230(4) 4691(3) 42(1)

N(2) 4811(5) 12976(4) 7802(3) 46(1)

N(3) 850(4) 6808(4) 2721(3) 38(1)

N(4) -1099(4) 6065(3) 825(3) 37(1)

O(1) 5508(3) 10002(3) 6153(2) 34(1) 225

O(2) 1409(4) 8581(3) 3720(2) 48(1)

C(1) 5093(5) 8893(4) 5600(3) 31(1)

C(2) 6041(5) 8643(4) 5428(3) 34(1)

C(3) 5686(5) 7510(4) 4862(3) 35(1)

C(4) 4358(5) 6656(4) 4477(3) 35(1) 230

C(5) 3470(5) 6970(4) 4690(3) 32(1)

C(6) 3781(5) 8088(4) 5262(3) 29(1)

C(7) 2877(5) 8422(4) 5525(3) 32(1)

C(8) 3318(5) 9571(4) 6079(3) 29(1)

C(9) 2508(5) 10032(4) 6350(3) 36(1) 235

C(10) 2978(5) 11140(4) 6890(3) 37(1)

C(11) 4331(5) 11877(4) 7229(3) 35(1)

C(13) 4632(5) 10332(4) 6396(3) 30(1)

C(12) 5153(5) 11457(4) 6966(3) 36(1)

C(14) 7971(6) 7984(5) 5128(4) 48(2) 240

C(15) 8428(6) 8131(5) 6194(4) 56(2)

C(16) 6155(6) 13698(5) 8321(4) 49(2)

C(17) 6570(6) 13408(6) 9191(4) 62(2)

C(18) 3988(5) 5460(4) 3888(4) 44(1)

C(19) 2096(6) 11614(5) 7168(4) 45(1) 245

C(20) 1540(5) 7566(4) 5291(3) 28(1)

C(21) 688(5) 7061(4) 4353(3) 31(1)

C(22) -527(5) 6183(4) 4152(3) 37(1)

C(23) -918(5) 5779(4) 4885(4) 37(1)

C(24) -116(6) 6271(5) 5810(4) 43(1) 250

C(25) 1087(6) 7128(5) 6005(3) 39(1)

C(26) 1037(5) 7559(4) 3579(3) 36(1)


S13

C(27) 1098(5) 7198(4) 1905(3) 39(1)

C(28) -42(5) 7219(5) 1340(3) 43(1)

S(3) 6266(1) 4787(1) 2106(1) 37(1) 255

O(31) 5550(4) 5044(3) 1402(3) 52(1)

O(32) 6569(4) 5519(3) 3092(2) 49(1)

O(33) 7396(3) 4781(3) 1878(2) 40(1)

C(31) 5222(5) 3372(4) 2023(3) 36(1)

C(32) 3921(6) 2979(5) 1782(4) 57(2) 260

C(33) 3133(7) 1859(6) 1708(5) 72(2)

C(34) 3607(7) 1154(5) 1879(4) 59(2)

C(35) 4889(8) 1574(6) 2152(4) 65(2)

C(36) 5713(7) 2698(5) 2229(4) 58(2)

C(37) 2720(8) -73(6) 1755(5) 89(2) 265

S(4) 10489(1) 3943(1) 1390(1) 40(1)

O(41) 9952(4) 4346(3) 702(2) 49(1)

O(42) 10793(4) 4641(3) 2389(2) 49(1)

O(43) 11525(4) 3765(3) 1167(3) 54(1)

C(41) 9256(6) 2567(5) 1225(3) 41(1) 270

C(42) 8039(7) 2332(6) 994(5) 74(2)

C(43) 7086(8) 1227(7) 852(6) 84(2)

C(44) 7324(7) 349(6) 920(4) 59(2)

C(45) 8574(11) 666(8) 1206(7) 117(3)

C(46) 9554(8) 1735(7) 1350(6) 94(3) 275

C(47) 6315(7) -819(6) 756(5) 85(2)

O(1W) 6695(4) 6323(4) 332(3) 62(1)

________________________________________________________________________________


S14

Table S3. Bond lengths [Å] and angles [°] for 1·(OTs)2·(H2O). _____________________________________________________ 280

N(1)-C(3) 1.353(6)

N(1)-C(14) 1.453(7)

N(1)-H(1) 0.8800

N(2)-C(11) 1.352(6)

N(2)-C(16) 1.445(7) 285

N(3)-C(26) 1.347(6)

N(3)-C(27) 1.459(5)

N(4)-C(28) 1.459(6)

N(4)-H(4A) 0.8800

N(4)-H(4B) 0.8800 290

O(1)-C(1) 1.368(5)

O(1)-C(13) 1.373(5)

O(2)-C(26) 1.229(5)

C(1)-C(2) 1.364(6)

C(1)-C(6) 1.410(7) 295

C(2)-C(3) 1.416(6)

C(2)-H(2) 0.9500

C(3)-C(4) 1.440(7)

C(4)-C(5) 1.361(6)

C(4)-C(18) 1.492(6) 300

C(5)-C(6) 1.416(6)

C(5)-H(5) 0.9500

C(6)-C(7) 1.419(6)

C(7)-C(8) 1.406(6)

C(7)-C(20) 1.460(7) 305

C(8)-C(13) 1.399(7)

C(8)-C(9) 1.425(6)

C(9)-C(10) 1.349(6)

C(9)-H(9) 0.9500

C(10)-C(11) 1.430(7) 310

C(10)-C(19) 1.518(6)

C(11)-C(12) 1.398(6)

C(13)-C(12) 1.371(6)

C(12)-H(12) 0.9500

C(14)-C(15) 1.522(7) 315


S15

C(14)-H(14A) 0.9900

C(14)-H(14B) 0.9900

C(15)-H(15A) 0.9800

C(15)-H(15B) 0.9800

C(15)-H(15C) 0.9800 320

C(16)-C(17) 1.509(8)

C(16)-H(16A) 0.9900

C(16)-H(16B) 0.9900

C(17)-H(17A) 0.9800

C(17)-H(17B) 0.9800 325

C(17)-H(17C) 0.9800

C(18)-H(18A) 0.9800

C(18)-H(18B) 0.9800

C(18)-H(18C) 0.9800

C(19)-H(19A) 0.9800 330

C(19)-H(19B) 0.9800

C(19)-H(19C) 0.9800

C(20)-C(21) 1.398(7)

C(20)-C(25) 1.410(6)

C(21)-C(22) 1.374(7) 335

C(21)-C(26) 1.498(6)

C(22)-C(23) 1.393(6)

C(22)-H(22) 0.9500

C(23)-C(24) 1.362(7)

C(23)-H(23) 0.9500 340

C(24)-C(25) 1.356(8)

C(24)-H(24) 0.9500

C(25)-H(25) 0.9500

C(27)-C(28) 1.505(7)

C(27)-H(27A) 0.9900 345

C(27)-H(27B) 0.9900

C(28)-H(28A) 0.9900

C(28)-H(28B) 0.9900

S(3)-O(32) 1.447(3)

S(3)-O(31) 1.451(4) 350

S(3)-O(33) 1.455(3)

S(3)-C(31) 1.775(5)


S16

C(31)-C(36) 1.353(7)

C(31)-C(32) 1.376(8)

C(32)-C(33) 1.391(9) 355

C(32)-H(32) 0.9500

C(33)-C(34) 1.364(9)

C(33)-H(33) 0.9500

C(34)-C(35) 1.349(9)

C(34)-C(37) 1.513(9) 360

C(35)-C(36) 1.405(9)

C(35)-H(35) 0.9500

C(36)-H(36) 0.9500

C(37)-H(37A) 0.9800

C(37)-H(37B) 0.9800 365

C(37)-H(37C) 0.9800

S(4)-O(43) 1.439(4)

S(4)-O(42) 1.447(3)

S(4)-O(41) 1.458(3)

S(4)-C(41) 1.772(6) 370

C(41)-C(42) 1.326(8)

C(41)-C(46) 1.373(8)

C(42)-C(43) 1.404(10)

C(42)-H(42) 0.9500

C(43)-C(44) 1.371(9) 375

C(43)-H(43) 0.9500

C(44)-C(45) 1.339(10)

C(44)-C(47) 1.479(9)

C(45)-C(46) 1.381(11)

C(45)-H(45) 0.9500 380

C(46)-H(46) 0.9500

C(47)-H(47A) 0.9800

C(47)-H(47B) 0.9800

C(47)-H(47C) 0.9800

385

C(3)-N(1)-C(14) 124.6(4)

C(3)-N(1)-H(1) 117.7

C(14)-N(1)-H(1) 117.7

C(11)-N(2)-C(16) 122.5(4)


S17

C(26)-N(3)-C(27) 119.8(4) 390

C(28)-N(4)-H(4A) 120.0

C(28)-N(4)-H(4B) 120.0

H(4A)-N(4)-H(4B) 120.0

C(1)-O(1)-C(13) 119.4(4)

C(2)-C(1)-O(1) 114.9(5) 395

C(2)-C(1)-C(6) 124.0(4)

O(1)-C(1)-C(6) 121.1(4)

C(1)-C(2)-C(3) 118.1(5)

C(1)-C(2)-H(2) 120.9

C(3)-C(2)-H(2) 120.9 400

N(1)-C(3)-C(2) 119.6(5)

N(1)-C(3)-C(4) 120.0(4)

C(2)-C(3)-C(4) 120.4(4)

C(5)-C(4)-C(3) 117.9(4)

C(5)-C(4)-C(18) 121.8(5) 405

C(3)-C(4)-C(18) 120.3(4)

C(4)-C(5)-C(6) 123.7(5)

C(4)-C(5)-H(5) 118.2

C(6)-C(5)-H(5) 118.2

C(1)-C(6)-C(5) 115.8(4) 410

C(1)-C(6)-C(7) 119.5(4)

C(5)-C(6)-C(7) 124.6(5)

C(8)-C(7)-C(6) 118.5(5)

C(8)-C(7)-C(20) 121.2(4)

C(6)-C(7)-C(20) 120.1(4) 415

C(13)-C(8)-C(7) 119.3(4)

C(13)-C(8)-C(9) 116.4(4)

C(7)-C(8)-C(9) 124.3(5)

C(10)-C(9)-C(8) 122.1(5)

C(10)-C(9)-H(9) 118.9 420

C(8)-C(9)-H(9) 118.9

C(9)-C(10)-C(11) 119.6(4)

C(9)-C(10)-C(19) 121.2(5)

C(11)-C(10)-C(19) 119.2(4)

N(2)-C(11)-C(12) 120.3(5) 425

N(2)-C(11)-C(10) 119.9(4)


S18

C(12)-C(11)-C(10) 119.8(4)

C(12)-C(13)-O(1) 114.6(5)

C(12)-C(13)-C(8) 123.4(4)

O(1)-C(13)-C(8) 122.0(4) 430

C(13)-C(12)-C(11) 118.6(5)

C(13)-C(12)-H(12) 120.7

C(11)-C(12)-H(12) 120.7

N(1)-C(14)-C(15) 113.1(4)

N(1)-C(14)-H(14A) 109.0 435

C(15)-C(14)-H(14A) 109.0

N(1)-C(14)-H(14B) 109.0

C(15)-C(14)-H(14B) 109.0

H(14A)-C(14)-H(14B) 107.8

C(14)-C(15)-H(15A) 109.5 440

C(14)-C(15)-H(15B) 109.5

H(15A)-C(15)-H(15B) 109.5

C(14)-C(15)-H(15C) 109.5

H(15A)-C(15)-H(15C) 109.5

H(15B)-C(15)-H(15C) 109.5 445

N(2)-C(16)-C(17) 112.9(5)

N(2)-C(16)-H(16A) 109.0

C(17)-C(16)-H(16A) 109.0

N(2)-C(16)-H(16B) 109.0

C(17)-C(16)-H(16B) 109.0 450

H(16A)-C(16)-H(16B) 107.8

C(16)-C(17)-H(17A) 109.5

C(16)-C(17)-H(17B) 109.5

H(17A)-C(17)-H(17B) 109.5

C(16)-C(17)-H(17C) 109.5 455

H(17A)-C(17)-H(17C) 109.5

H(17B)-C(17)-H(17C) 109.5

C(4)-C(18)-H(18A) 109.5

C(4)-C(18)-H(18B) 109.5

H(18A)-C(18)-H(18B) 109.5 460

C(4)-C(18)-H(18C) 109.5

H(18A)-C(18)-H(18C) 109.5

H(18B)-C(18)-H(18C) 109.5


S19

C(10)-C(19)-H(19A) 109.5

C(10)-C(19)-H(19B) 109.5 465

H(19A)-C(19)-H(19B) 109.5

C(10)-C(19)-H(19C) 109.5

H(19A)-C(19)-H(19C) 109.5

H(19B)-C(19)-H(19C) 109.5

C(21)-C(20)-C(25) 116.6(5) 470

C(21)-C(20)-C(7) 123.1(4)

C(25)-C(20)-C(7) 119.9(5)

C(22)-C(21)-C(20) 120.9(4)

C(22)-C(21)-C(26) 118.8(4)

C(20)-C(21)-C(26) 120.0(5) 475

C(21)-C(22)-C(23) 120.0(5)

C(21)-C(22)-H(22) 120.0

C(23)-C(22)-H(22) 120.0

C(24)-C(23)-C(22) 120.4(5)

C(24)-C(23)-H(23) 119.8 480

C(22)-C(23)-H(23) 119.8

C(25)-C(24)-C(23) 119.5(4)

C(25)-C(24)-H(24) 120.2

C(23)-C(24)-H(24) 120.2

C(24)-C(25)-C(20) 122.6(5) 485

C(24)-C(25)-H(25) 118.7

C(20)-C(25)-H(25) 118.7

O(2)-C(26)-N(3) 123.3(4)

O(2)-C(26)-C(21) 121.0(4)

N(3)-C(26)-C(21) 115.6(4) 490

N(3)-C(27)-C(28) 111.7(4)

N(3)-C(27)-H(27A) 109.3

C(28)-C(27)-H(27A) 109.3

N(3)-C(27)-H(27B) 109.3

C(28)-C(27)-H(27B) 109.3 495

H(27A)-C(27)-H(27B) 107.9

N(4)-C(28)-C(27) 111.3(4)

N(4)-C(28)-H(28A) 109.4

C(27)-C(28)-H(28A) 109.4

N(4)-C(28)-H(28B) 109.4 500


S20

C(27)-C(28)-H(28B) 109.4

H(28A)-C(28)-H(28B) 108.0

O(32)-S(3)-O(31) 112.0(2)

O(32)-S(3)-O(33) 111.9(2)

O(31)-S(3)-O(33) 113.0(2) 505

O(32)-S(3)-C(31) 107.1(2)

O(31)-S(3)-C(31) 105.5(2)

O(33)-S(3)-C(31) 106.8(2)

C(36)-C(31)-C(32) 120.3(6)

C(36)-C(31)-S(3) 119.8(5) 510

C(32)-C(31)-S(3) 119.8(4)

C(31)-C(32)-C(33) 118.1(6)

C(31)-C(32)-H(32) 120.9

C(33)-C(32)-H(32) 120.9

C(34)-C(33)-C(32) 122.3(7) 515

C(34)-C(33)-H(33) 118.8

C(32)-C(33)-H(33) 118.8

C(35)-C(34)-C(33) 118.4(6)

C(35)-C(34)-C(37) 120.7(7)

C(33)-C(34)-C(37) 120.9(7) 520

C(34)-C(35)-C(36) 120.8(6)

C(34)-C(35)-H(35) 119.6

C(36)-C(35)-H(35) 119.6

C(31)-C(36)-C(35) 119.9(7)

C(31)-C(36)-H(36) 120.0 525

C(35)-C(36)-H(36) 120.0

C(34)-C(37)-H(37A) 109.5

C(34)-C(37)-H(37B) 109.5

H(37A)-C(37)-H(37B) 109.5

C(34)-C(37)-H(37C) 109.5 530

H(37A)-C(37)-H(37C) 109.5

H(37B)-C(37)-H(37C) 109.5

O(43)-S(4)-O(42) 113.8(2)

O(43)-S(4)-O(41) 112.7(2)

O(42)-S(4)-O(41) 112.0(2) 535

O(43)-S(4)-C(41) 105.2(2)

O(42)-S(4)-C(41) 106.7(2)


S21

O(41)-S(4)-C(41) 105.6(2)

C(42)-C(41)-C(46) 119.3(6)

C(42)-C(41)-S(4) 120.5(5) 540

C(46)-C(41)-S(4) 120.2(5)

C(41)-C(42)-C(43) 119.0(6)

C(41)-C(42)-H(42) 120.5

C(43)-C(42)-H(42) 120.5

C(44)-C(43)-C(42) 124.2(7) 545

C(44)-C(43)-H(43) 117.9

C(42)-C(43)-H(43) 117.9

C(45)-C(44)-C(43) 113.3(7)

C(45)-C(44)-C(47) 122.6(7)

C(43)-C(44)-C(47) 124.0(8) 550

C(44)-C(45)-C(46) 125.0(7)

C(44)-C(45)-H(45) 117.5

C(46)-C(45)-H(45) 117.5

C(41)-C(46)-C(45) 119.0(7)

C(41)-C(46)-H(46) 120.5 555

C(45)-C(46)-H(46) 120.5

C(44)-C(47)-H(47A) 109.5

C(44)-C(47)-H(47B) 109.5

H(47A)-C(47)-H(47B) 109.5

C(44)-C(47)-H(47C) 109.5 560

H(47A)-C(47)-H(47C) 109.5

H(47B)-C(47)-H(47C) 109.5

_____________________________________________________________

Symmetry transformations used to generate equivalent atoms:

565


S22

Table S4. Anisotropic displacement parameters (Å2x 103) for 1·(OTs)2·(H2O). The anisotropic displacement factor exponent takes the form: -2�2[ h2 a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________

U11 U22 U33 U23 U13 U12

______________________________________________________________________________ 570

N(1) 48(3) 43(3) 41(2) 5(2) 20(2) 30(3)

N(2) 43(3) 44(3) 46(3) 5(2) 11(2) 22(3)

N(3) 48(3) 51(3) 23(2) 19(2) 20(2) 24(2)

N(4) 39(3) 37(3) 30(2) 9(2) 9(2) 15(2)

O(1) 36(2) 36(2) 32(2) 7(2) 14(2) 20(2) 575

O(2) 64(3) 41(2) 35(2) 20(2) 17(2) 17(2)

C(1) 43(4) 29(3) 25(2) 9(2) 17(2) 18(3)

C(2) 36(3) 40(3) 29(3) 11(2) 15(2) 21(3)

C(3) 49(4) 34(3) 26(2) 9(2) 18(3) 22(3)

C(4) 50(4) 33(3) 29(3) 10(2) 16(3) 26(3) 580

C(5) 39(3) 36(3) 28(2) 14(2) 15(2) 21(3)

C(6) 40(4) 33(3) 25(2) 14(2) 14(2) 23(3)

C(7) 41(4) 49(3) 22(2) 20(2) 16(2) 29(3)

C(8) 35(3) 37(3) 23(2) 12(2) 10(2) 22(3)

C(9) 41(4) 46(3) 32(3) 18(2) 18(3) 26(3) 585

C(10) 46(4) 39(3) 33(3) 13(2) 19(3) 24(3)

C(11) 47(4) 30(3) 28(3) 7(2) 12(2) 19(3)

C(13) 33(3) 39(3) 26(2) 12(2) 13(2) 23(3)

C(12) 38(4) 43(3) 33(3) 12(2) 12(2) 25(3)

C(14) 49(4) 61(4) 52(3) 18(3) 29(3) 38(4) 590

C(15) 45(4) 68(4) 53(4) 13(3) 9(3) 33(4)

C(16) 53(5) 35(3) 59(4) 9(3) 23(3) 23(3)

C(17) 64(5) 74(5) 42(3) 9(3) 24(3) 30(4)

C(18) 46(4) 42(3) 44(3) 7(2) 17(3) 24(3)

C(19) 52(4) 57(4) 48(3) 17(3) 26(3) 40(3) 595

C(20) 41(3) 25(3) 32(3) 14(2) 21(2) 22(3)

C(21) 39(3) 39(3) 25(3) 16(2) 17(2) 21(3)

C(22) 43(4) 39(3) 36(3) 18(2) 15(3) 23(3)

C(23) 32(3) 45(3) 46(3) 25(3) 23(3) 20(3)

C(24) 64(4) 49(3) 41(3) 31(3) 36(3) 33(3) 600

C(25) 56(4) 55(4) 28(3) 24(2) 24(3) 37(3)

C(26) 45(4) 39(3) 32(3) 21(2) 18(3) 21(3)


S23

C(27) 49(4) 45(3) 32(3) 21(2) 21(3) 23(3)

C(28) 52(4) 52(4) 27(3) 21(2) 18(3) 21(3)

S(3) 44(1) 45(1) 33(1) 12(1) 17(1) 28(1) 605

O(31) 59(3) 48(2) 58(2) 25(2) 17(2) 32(2)

O(32) 48(3) 54(2) 36(2) -4(2) 14(2) 27(2)

O(33) 47(3) 57(2) 37(2) 24(2) 25(2) 35(2)

C(31) 42(4) 31(3) 31(3) 5(2) 13(3) 15(3)

C(32) 49(5) 66(4) 62(4) 25(3) 26(3) 27(4) 610

C(33) 65(5) 75(5) 80(5) 40(4) 41(4) 24(4)

C(34) 73(6) 52(4) 45(3) 24(3) 23(4) 17(4)

C(35) 74(6) 66(5) 64(4) 38(4) 22(4) 33(4)

C(36) 68(5) 63(4) 49(3) 26(3) 16(3) 32(4)

C(37) 105(7) 69(5) 78(5) 38(4) 33(5) 18(5) 615

S(4) 52(1) 52(1) 31(1) 25(1) 24(1) 29(1)

O(41) 64(3) 63(3) 38(2) 34(2) 29(2) 32(2)

O(42) 75(3) 57(2) 28(2) 25(2) 24(2) 35(2)

O(43) 59(3) 70(3) 57(2) 31(2) 32(2) 40(2)

C(41) 45(4) 61(4) 33(3) 24(3) 20(3) 32(3) 620

C(42) 62(6) 77(5) 100(5) 46(4) 28(4) 40(5)

C(43) 59(6) 84(6) 112(6) 36(5) 32(5) 34(5)

C(44) 66(5) 62(4) 49(4) 30(3) 17(4) 26(4)

C(45) 106(9) 115(8) 179(10) 106(7) 46(7) 65(7)

C(46) 50(5) 81(6) 162(8) 74(6) 14(5) 30(5) 625

C(47) 85(6) 70(5) 58(4) 24(4) 10(4) 2(4)

O(1W) 73(3) 77(3) 51(2) 25(2) 26(2) 46(3)

______________________________________________________________________________


S24

Table S5. Hydrogen coordinates (Å x 104) and isotropic displacement parameters (Å2x 103) for 1·(OTs)2·(H2O) 630

________________________________________________________________________________

x y z U(eq)

________________________________________________________________________________

H(1) 6355 6542 4286 50 635

H(4A) -1013 5472 872 45

H(4B) -1822 5964 468 45

H(2) 6914 9213 5680 40

H(5) 2594 6407 4441 38

H(9) 1609 9544 6145 43 640

H(12) 6053 11940 7177 43

H(14A) 8182 8743 5072 58

H(14B) 8438 7673 4760 58

H(15A) 7984 8456 6566 83

H(15B) 9353 8646 6449 83 645

H(15C) 8240 7386 6254 83

H(16A) 6336 14504 8542 59

H(16B) 6665 13620 7872 59

H(17A) 6119 13542 9664 93

H(17B) 7495 13892 9494 93 650

H(17C) 6366 12603 8982 93

H(18A) 4253 5097 4309 65

H(18B) 4409 5470 3373 65

H(18C) 3057 5029 3595 65

H(19A) 1203 11023 6850 68 655

H(19B) 2259 12274 6957 68

H(19C) 2258 11852 7875 68

H(22) -1100 5852 3513 44

H(23) -1749 5158 4740 44

H(24) -397 6015 6315 51 660

H(25) 1647 7445 6648 46

H(27A) 1319 6685 1466 47

H(27B) 1841 7976 2152 47

H(28A) -325 7660 1792 51

H(28B) 206 7607 866 51 665


S25

H(32) 3571 3459 1670 69

H(33) 2232 1575 1533 86

H(35) 5238 1104 2295 78

H(36) 6614 2986 2424 70

H(37A) 3160 -529 1629 134 670

H(37B) 1954 -382 1207 134

H(37C) 2470 -104 2351 134

H(42) 7816 2904 925 88

H(43) 6221 1078 700 101

H(45) 8804 113 1318 140 675

H(46) 10421 1893 1532 112

H(47A) 5818 -1187 67 127

H(47B) 5747 -778 1154 127

H(47C) 6712 -1265 939 127

________________________________________________________________________________ 680


S26

Table S6. Torsion angles [°] for 1·(OTs)2·(H2O). ________________________________________________________________

C(13)-O(1)-C(1)-C(2) -177.8(4)

C(13)-O(1)-C(1)-C(6) 1.1(6)

O(1)-C(1)-C(2)-C(3) 179.8(4) 685

C(6)-C(1)-C(2)-C(3) 0.9(7)

C(14)-N(1)-C(3)-C(2) 6.5(7)

C(14)-N(1)-C(3)-C(4) -173.0(4)

C(1)-C(2)-C(3)-N(1) -178.9(4)

C(1)-C(2)-C(3)-C(4) 0.6(6) 690

N(1)-C(3)-C(4)-C(5) 178.3(4)

C(2)-C(3)-C(4)-C(5) -1.2(6)

N(1)-C(3)-C(4)-C(18) 0.0(7)

C(2)-C(3)-C(4)-C(18) -179.5(4)

C(3)-C(4)-C(5)-C(6) 0.5(7) 695

C(18)-C(4)-C(5)-C(6) 178.7(4)

C(2)-C(1)-C(6)-C(5) -1.7(6)

O(1)-C(1)-C(6)-C(5) 179.5(4)

C(2)-C(1)-C(6)-C(7) 176.7(4)

O(1)-C(1)-C(6)-C(7) -2.1(6) 700

C(4)-C(5)-C(6)-C(1) 0.9(6)

C(4)-C(5)-C(6)-C(7) -177.3(4)

C(1)-C(6)-C(7)-C(8) 3.3(6)

C(5)-C(6)-C(7)-C(8) -178.5(4)

C(1)-C(6)-C(7)-C(20) -171.8(4) 705

C(5)-C(6)-C(7)-C(20) 6.4(6)

C(6)-C(7)-C(8)-C(13) -3.4(6)

C(20)-C(7)-C(8)-C(13) 171.6(4)

C(6)-C(7)-C(8)-C(9) 176.7(4)

C(20)-C(7)-C(8)-C(9) -8.3(6) 710

C(13)-C(8)-C(9)-C(10) -0.4(6)

C(7)-C(8)-C(9)-C(10) 179.4(4)

C(8)-C(9)-C(10)-C(11) -1.8(7)

C(8)-C(9)-C(10)-C(19) 179.8(4)

C(16)-N(2)-C(11)-C(12) -12.4(7) 715

C(16)-N(2)-C(11)-C(10) 167.5(4)

C(9)-C(10)-C(11)-N(2) -177.3(4)


S27

C(19)-C(10)-C(11)-N(2) 1.0(7)

C(9)-C(10)-C(11)-C(12) 2.6(7)

C(19)-C(10)-C(11)-C(12) -179.0(4) 720

C(1)-O(1)-C(13)-C(12) 178.9(4)

C(1)-O(1)-C(13)-C(8) -1.3(6)

C(7)-C(8)-C(13)-C(12) -177.8(4)

C(9)-C(8)-C(13)-C(12) 2.1(6)

C(7)-C(8)-C(13)-O(1) 2.5(6) 725

C(9)-C(8)-C(13)-O(1) -177.6(4)

O(1)-C(13)-C(12)-C(11) 178.3(4)

C(8)-C(13)-C(12)-C(11) -1.4(7)

N(2)-C(11)-C(12)-C(13) 178.9(4)

C(10)-C(11)-C(12)-C(13) -1.0(7) 730

C(3)-N(1)-C(14)-C(15) 74.0(6)

C(11)-N(2)-C(16)-C(17) -74.2(6)

C(8)-C(7)-C(20)-C(21) 109.7(5)

C(6)-C(7)-C(20)-C(21) -75.4(6)

C(8)-C(7)-C(20)-C(25) -76.7(5) 735

C(6)-C(7)-C(20)-C(25) 98.2(5)

C(25)-C(20)-C(21)-C(22) 0.1(6)

C(7)-C(20)-C(21)-C(22) 173.9(4)

C(25)-C(20)-C(21)-C(26) 173.1(4)

C(7)-C(20)-C(21)-C(26) -13.1(6) 740

C(20)-C(21)-C(22)-C(23) -0.6(7)

C(26)-C(21)-C(22)-C(23) -173.7(4)

C(21)-C(22)-C(23)-C(24) 1.9(7)

C(22)-C(23)-C(24)-C(25) -2.6(7)

C(23)-C(24)-C(25)-C(20) 2.2(7) 745

C(21)-C(20)-C(25)-C(24) -0.9(7)

C(7)-C(20)-C(25)-C(24) -174.9(4)

C(27)-N(3)-C(26)-O(2) 0.3(8)

C(27)-N(3)-C(26)-C(21) 176.9(5)

C(22)-C(21)-C(26)-O(2) 121.8(6) 750

C(20)-C(21)-C(26)-O(2) -51.3(7)

C(22)-C(21)-C(26)-N(3) -54.8(6)

C(20)-C(21)-C(26)-N(3) 132.0(5)

C(26)-N(3)-C(27)-C(28) -85.6(6)


S28

N(3)-C(27)-C(28)-N(4) -68.5(5) 755

O(32)-S(3)-C(31)-C(36) -89.8(4)

O(31)-S(3)-C(31)-C(36) 150.8(4)

O(33)-S(3)-C(31)-C(36) 30.3(5)

O(32)-S(3)-C(31)-C(32) 88.0(4)

O(31)-S(3)-C(31)-C(32) -31.5(4) 760

O(33)-S(3)-C(31)-C(32) -151.9(4)

C(36)-C(31)-C(32)-C(33) -3.3(8)

S(3)-C(31)-C(32)-C(33) 178.9(4)

C(31)-C(32)-C(33)-C(34) 1.0(9)

C(32)-C(33)-C(34)-C(35) 1.7(9) 765

C(32)-C(33)-C(34)-C(37) -177.7(5)

C(33)-C(34)-C(35)-C(36) -2.0(9)

C(37)-C(34)-C(35)-C(36) 177.3(5)

C(32)-C(31)-C(36)-C(35) 3.0(8)

S(3)-C(31)-C(36)-C(35) -179.3(4) 770

C(34)-C(35)-C(36)-C(31) -0.2(9)

O(43)-S(4)-C(41)-C(42) -153.3(5)

O(42)-S(4)-C(41)-C(42) 85.5(5)

O(41)-S(4)-C(41)-C(42) -33.9(5)

O(43)-S(4)-C(41)-C(46) 27.6(6) 775

O(42)-S(4)-C(41)-C(46) -93.5(5)

O(41)-S(4)-C(41)-C(46) 147.0(5)

C(46)-C(41)-C(42)-C(43) -2.0(10)

S(4)-C(41)-C(42)-C(43) 178.9(5)

C(41)-C(42)-C(43)-C(44) -1.2(11) 780

C(42)-C(43)-C(44)-C(45) 4.5(11)

C(42)-C(43)-C(44)-C(47) -179.1(6)

C(43)-C(44)-C(45)-C(46) -5.0(13)

C(47)-C(44)-C(45)-C(46) 178.6(8)

C(42)-C(41)-C(46)-C(45) 1.7(11) 785

S(4)-C(41)-C(46)-C(45) -179.3(6)

C(44)-C(45)-C(46)-C(41) 2.1(14)

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Contents · 2009-12-04 · Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2006 S3 Supplementary data 350 400 450 500 550