A Mechanofluorochromic push-pull small molecule with aggregation-controlled linear and nonlinear optical properties

Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2015.

Supporting Information

for Adv. Mater., DOI: 10.1002/adma.201501697

A Mechanofluorochromic Push–Pull Small Molecule with Aggregation-Controlled Linear and Nonlinear Optical Properties

Yue Jiang, Denis Gindre, Magali Allain, Ping Liu, Clément

Cabanetos, and Jean Roncali*

A Mechanofluorochromic push-pull type small molecule with aggregation-controlled linear and nonlinear optical properties

Supporting Information

Yue Jiang, Denis Gindre, Magali Allain, Ping Liu, Clément Cabanetos and Jean Roncali*

General

All reagents and chemicals from commercial sources were used without further purification. Reactions were carried out under nitrogen atmosphere unless otherwise stated. Solvents were dried and purified using standard techniques.

H NMR and

C NMR spectra were recorded on a Bruker AVANCE III 300 (

H, 300 MHz and

C, 75 MHz). High resolution mass spectra (HRMS) and matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF) were performed on Bruker Biflex Ⅲ.

Thermogravimetric analyses (TGA) and differential Scanning Calorimetry (DSC) were carried out under dry nitrogen gas flow with a 10

C min

heating rate on TGA Q500 V20.10 Build and a DSC Q20 V24.4 Build 116 respectively .

The films discussed in the manuscript were prepared by spin-casting from 10mg/mL in DCM on glass

substrates. Single crystals for X-ray diffraction were prepared by slow evaporation of acetonitrile solutions.

Scheme S1. Synthesis of compounds 1 and 2. i) t-BuONa, Pd

(dba)

, P(t-Bu)

, toluene, 50-60

C; ii) Pd(PPh

)

, toluene, 120

C; iii) triethylamine; chloroform; iv) NaH, THF, 0

C, rt.

Synthesis

4-bromo-N-hexyl-N-phenylaniline (1a). N-hexylaniline (1g, 5.64 mmol), 1-Bromo-4-iodobenzene (1.92g, 6.77 mmol), sodium t-butoxide (1.63g, 16.92 mmol), Tris(dibenzylideneacetone)dipalladium(0) (211mg, 0.23 mmol) were dried under vacuum overnight and transferred into 250 mL flask protected by argon. 60 mL dry toluene was added and degassed 30 min, followed by addition of Tri-t-butylphosphine (1M in toluene) (1.35 mL, 1.35 mmol). After 10 min degassing, the mixture was stirred at 60

C overnight, quenched with distilled water and extracted by diethyl ether, the crude product was purified by gel chromatography on silica gel eluting with using petroleum: DCM=5:1 to give (620 mg, 33%) of a colorless oil.

H NMR (300 MHz, CDCl

) δ 0.91(3H, t, J= 7.00Hz) 1.32(6H, s) 1.67(2H, m, J=15.04 Hz) 3.68(2H, t, J=7.38 Hz) 6.81 6.84(2H, d, J=9.31Hz) 7.05(3H, t, J=7.76Hz) 7.39(4H, m, J=21.00Hz).

C NMR (76 MHz, CDCl3) δ 14.07 22.69 26.74 27.27 31.01 31.64 52.43 112.18 120.85 122.43 122.53 129.47 131.98 147.24 147.54.

HRMS-FAB+ (cald 331.0936, found 331.0942).

5-(4-((N-hexyl-N-phenyl)amino)phenyl)thiophene-2-carbaldehyde (1c). Compound 1a (620 mg, 1.87 mmol)

and the Stille reagent 1b (899 mg, 2.81mmol) were dissolved in 60mL of toluene. The solution was was degased with argon for 30 min and tetrakis(triphenylphosphine)palladium(0) (108 mg, 0.094 mmol) was added and mixture was refluxed at 120

C overnight. When no starting material was detected by TLC, the mixture was cooled to room temp and quenched by distilled water. After extraction with diethyl ether, solvent evaporation and washing with petroleum: dichloromethane 1:4, the crude compound was dissolved in 100 mL of acetone, 1M HCl was added until dissolution (ca 80mL) and the mixture was stirred overnight.

Extraction with diethyl ether, evaporation and washing with petroleum: DCM 1:1 gave 200 mg, (29%) of a yellow solid.

H NMR (300 MHz, CDCl

) δ 0.91(3H, t, J=6.96Hz) 1.34(6H, s) 1.71(2H, m, J=13.06Hz) 3.74(2H, t, J=7.89Hz) 6.83(2H, d, J=9.03Hz) 7.19(3H, m, J=6.79) 7.28(1H, d, J=4.00Hz) 7.39(2H, t, J=6.95Hz) 7.52(2H, d, J=9.03Hz) 7.73(1H, d, J=4.06Hz) 9.86(1H, s).

C NMR (76 MHz, CDCl

) δ 14.07 22.69 26.73 27.36 31.64 52.48 116.21 122.00 122.89 124.58 125.58 127.39 129.77 138.07 140.50 149.36 155.54 182.67. HRMS-FAB+(cal.363.1657, found 363.1660).

2-((5-(4-((N-hexyl-N-phenyl)amino)phenyl)thiophene-2-yl)methylene)malononitrile (1). 1c (200 mg, 0.55 mmol) and malononitrile (73 mg, 1.1 mmol) were dissolved in 50 ml of chloroform. Two drops of triethylamine were added and the mixture was stirred overnight. The product was purified by chromatography on silica gel (eluent DCM) to give 130 mg (58%) of a red solid.

H NMR (300 MHz, CDCl

) δ 0.92(3H, t, J=6.86Hz) 1.35(6H, s) 1.72(2H, m, J=15.22Hz) 3.77(2H, t, J=8.00Hz) 6.79(2H, d, J=8.75Hz) 7.24(3H, m, J=7.50Hz) 7.31(1H, d, J=4.32Hz) 7,44(2H, t, J=7.96Hz) 7.56(2H, d, J=9.10Hz) 7.68(1H, d, J=4.32Hz) 7.75(1H, s).

C NMR (76 MHz, CDCl

) δ 14.06 22.67 26.69 27.32 31.61 52.56 77.25 114.01 115.32 121.48 122.33 125.44 126.44 127.82 129.93 132.30 140.80 146.27 150.24 158.37.

HRMS-FAB+ (cal.411.1769, found 411.1762). Td 316

.

4-bromo-N-(2-(2-ethoxyethoxy)ethyl)-N-phenylbenzenamine (2a). 4-bromo-diphenylamine (1g, 4.03 mmol) was dried under vacuum overnight and introduced in 20mL of dry THF under argon. Sodium hydride (60%

in mineral oil) 193 mg, 4.84 mmol)) was added in one portion at -78

C. The mixture was stirred at low temp

for 30min and 1.5 h at room temp. 1-Bromo-2-(2-ethoxyethoxy)ethane (0.92 mL, 6.05mmol) was injected at 0

C. After stirring 30 min at 0

C and 30min at 50

C, the reaction was quenched with distilled water.

Extraction with diethyl ether, evaporation of the solvent and chromatography on silica gel with DCM as eluent were gave 870 mg, (60%) of a colorless oil.

H NMR (300 MHz, CDCl

) δ 1.26 (3H, t, J=7.00 Hz) 3.59 (6H, m) 3.86 (2H, t, J=6.17 Hz) 3.95(2H, t, J=6.32 Hz) 6.90(2H, d, J=9.16 Hz) 7.03(1H, t, J=7.40 Hz) 7.11(2H, d, J=8.47 Hz) 7.32(4H,sd, J=9.10 Hz).

13

C NMR (76 MHz, CDCl

) δ 15.20 30.27 51.67 66.75 66.77 68.01 69.82 69.87 70.62 70.81 71.25 112.64 121.17 122.44 122.56 129.47 131.98 147.10 149.19. HRMS-MALDI-TOF (cal.363.1, found 363.2).

5-(4-((N-(2-(2-ethoxyethoxy)ethyl)-N-phenyl)amino)phenyl)thiophene-2-carbaldehyde (2b). Compound 2a (870 mg, 2.40 mmol) and compound 1b (1.15g, 3.6 mmol) were dissolved in 70mL of toluene and degassed with argon for 30min. Tetrakis(triphenylphosphine)palladium(0) (139 mg, 0.12 mmol) was added and the mixture was again degassed 15 min. The mixture was refluxed overnight. When no starting material was detected by TLC, the mixture was cooled to room temp and quenched with water. After extraction with diethyl ether, the solvent was evaporated and the solid was washed with dichloromethane. This intermediate compound (800mg), mixture of dioxolane and aldehyde, was dissolved in 100mL of acetone, 1M HCl (90mL) was added and the mixture was stirred overnight. Extraction with diethyl ether, solvent evaporation and chromatography on silica gel eluting with DCM gave 300 mg, (32%) of a yellow oil.

H NMR (300 MHz, CDCl

) δ 1.24(3H, t, J=7.06Hz) 3.51-3.62(6H, m, J=33.7Hz) 3.75(2H, t, J=6.66Hz) 4.01(2H, t, J=6.24Hz) 6.92(2H, d, J=8.90Hz) 7.18(1H, t, J=7.50Hz) 7.26(3H, m, J=7.72Hz) 7.40(2H, t, J=7.56Hz) 7.53(2H, d, J=8.57Hz) 7.71(1H, d, J=4.26Hz) 9.85(1H, s).

C NMR (76 MHz, CDCl

) δ 15.23 51.68 66.75 68.01 69.89 70.85 116.79 122.18 123.41 124.55 125.35 127.34 129.75 138.06 140.63 146.52 149.35 155.30 182.59. HRMS-FAB+(cal.395.1555, found 395.1554).

2-((5-(4-((N-(2-(2-ethoxyethoxy)ethyl)-N-phenyl)amino)phenyl)thiophene-2-yl)methylene)malononitrile (2).

2b (300 mg, 0.76 mmol) and malononitrile (100 mg, 1.52 mmol) were dissolved in 50 ml of chloroform.

Two drops of triethylamine were added and the mixture was stirred overnight. The product was purified by chromatography on silica gel (eluent DCM: AcOEt 50:1) to give 190 mg (56%) of a red solid.

H NMR (300 MHz, CDCl3) δ 1.20 (3H, t, J= 7.02Hz) 3.50 (2H, q, J=7.14 Hz) 3.57 (4H, m, J=5.01 Hz) 3.71 (2H, t, J=6.26 Hz) 3.98 (2H, t, J=6.26 Hz) 6.84 (2H, d, J=8.90 Hz) 7.23 (4H, dd, J=16.60. 14.21 Hz) 7.39 (2H, t, J=7.80 Hz) 7.50 (2H, d, J=8.90 Hz) 7.64 (1H, d, J=4.47 Hz) 7.71(1H, s).

C NMR (76 MHz, CDCl3) δ 15.21 51.75 66.77 67.99 69.88 70.88 73.99 113.96 114.86 115.93 122.03 122.52 125.41 126.28 127.75 129.90 132.45 140.78 146.07 150.24 150.27 158.15. HRMS-MALDI-TOF-DCTB+ (cal.443.1667, found 443.1662). Td 311

.

(5-(1,3-dioxolan-2-yl)thiophen-2-yl)trimethylstannane (1b). Thiophene-2-carboxaldehyde (10g, 89.84 mmol), ethylene glycol (17.56 g, 282.96 mmol) and PTSA (611 mg) in 100mL of toluene were placed in a round-bottom flask equipped with Dean-Stark Trap and refluxed under argon at 140

C for 40 hours. The pure compound (light golden oil) 11g, (79%) was obtained by distillation at 140

C under 15mbar.

H NMR (300 MHz, CDCl

) δ 4.10(4H, m) 6.16(1H, s) 7.02(1H, t) 7.20(1H, d, J=3.48) 7.36(1H, d, J=4.79).

This compound (3g, 19mmol) was dissolved in 20mL of dry THF cooled to -78

C, and 1.6 M n-butyllithium (18 mL, 28.5 mmol) was added slowly. After 1 h stirring at -78°C, the mixture was stirred 2h at room temp and cooled again to -78°C. Trimethyltin chloride (5.68 g, 28.5 mmol) was added in one portion and the mixture was stirred at room temp overnight. The target compound, as dark orange crystals (5.67g, 93%), was stored under argon and used without further purification.

H NMR (300 MHz, CDCl

) δ 0.39(9H, s) 4.11(4H, m) 6.19(1H, s) 7.12(1H, d, J=3.86) 7.30(1H, d, J=5.01).

S CHO S

O O

S

O O Sn

X Y

Figure. S1. UV-Vis absorption spectra of compounds 1 (blue) and 2 (red). Dashed line in DCM, solid lines as thin films on glass

.

Wavelength(nm)

300 400 500 600 700 800

Absorption(a.u.)

0.0 0.2 0.4 0.6 0.8 1.0

Hexane Toluene Dichloromethane THF

Acetonitrile

Figure S2. UV-Vis absorption spectra of compound 2 in various solvents

Wavelength [nm]

300 400 500 600 700 800

Normalized Absorption

0.0 0.2 0.4 0.6 0.8 1.0

E_T

30 32 34 36 38 40 42 44 46 48

em/10-3 cm-1

14.0 15.0 16.0 17.0 18.0 19.0 20.0

Hexane

Toluene

THF

Dichloromethane

Acetonitrile

.

Figure S3. Variation of the fluorescence emission maximum (in cm

) of 2 (top) and Stokes shift (SS) (bottom) vs the E

parameter of solvent polarity

E_T

30 40 50

SS/cm-1

0 2000 4000 6000

Hexane Toluene

THF

Dichloromethane

Acetonitrile

500nm exciting

Wavelengh(nm)

550 600 650 700 750 800

Fluorescence

0 10000 20000 30000 40000

THF 100%

THF 80%

THF-20%

Figure S4. Aggregation quenching of photoluminescence of 2 upon addition of water to the THF solution. Full quenching is observed for 80% water (excitation 500 nm)

Second Harmonic Generation scanning microscopy experiments.

The 2

order NLO properties of the materials was investigated by means the SHG scanning microscopy setup (Figure S5) which can provide 2D (thin films) or 3D (bulk materials) mapping of the SHG signal. The laser beam (pulse duration 100 fs, repetition rate 80 MHz) is focused and moved on the sample by means of two galvanometric mirrors, while the SHG signal is detected with of a photon counter coupled with a fast photomultiplier. The laser beam scans a selected area on the sample, while for every position of the focused beam, the SHG signal is acquired and stored in order to finally produce 1 pixel of the image and finally provide the SHG image (200x200 pixels). The laser power has been adjusted to 120 mW, the laser wavelength was 800 nm and the pixeltime was 20 μsec.

Figure S5. Experimental set up for SHG scanning microscopy experiments.

The laser source is a Ti:Sapphire (Tsunami, Spectra Physics). The pump laser is a 10 W solid-state laser (Millenia Xs, Spectra Physics). The angular deviation of the beam was controlled with an X-Y scanner (Cambridge Technology). The laser power was adjusted by means of a electro-optic modulator (Pockels cell).

A Faraday rotator was used as an optical isolator. The beam was focused on the sample with an x20 objective

lens (Olympus, N.A. 0.25). The SHG signal is filtered with an IR blocking filter (NT48-071, Edmund Optics

and BG39, Schott) and detected by a photomultiplier (H744P-40, Hamamatsu) and a photon counter (C9744,

Hamamatsu). The glass slide were the sample was deposited is placed on XYZ motorized stages (Newport)

controlled by an 8 axes motion controller/ Driver (XPS, Newport). The light polarization, the voltage control

of the galvanometric mirrors and the micropositioning of the sample are precisely piloted by means of a

homemade National Instrument Labview™ program. This program is used to store the signal for each position

of the scanned laser beam on the sample, to provide finally the SHG images.

X-ray diffraction and crystallographic structure

X-ray single-crystal diffraction data were collected at 180K on an Agilent SuperNova diffractometer equipped with Atlas CCD detector and mirror monochromated micro-focus Cu-K

radiation (λ = 1.54184 Å). The structure was solved by direct methods and refined on F

by full matrix least-squares techniques using SHELX97 programs (G.M. Sheldrick, 1998). All non-H atoms were refined anisotropically and multiscan empirical absorption was corrected using CrysAlisPro program (CrysAlisPro, Agilent Technologies, V1.171.37.35g, 2014). The H atoms were included in the calculation without refinement. The structure refinement showed disordered electron density which could not be reliably modeled and the program PLATON/SQUEEZE were used to remove the scattering contribution corresponding to acetonitrile solvent from the intensity data. The assumed solvent composition (1 CH3CN per asymmetric unit) was used in the calculation of the empirical formula, formula weight, density, linear absorption coefficient and F(000).

Table 1. Crystal data and structure refinement for yue1166c. (06/03/2015)

CCDC 1058632

Identification code yue1166c

Empirical formula C54 H53 N7 O4 S2

Formula weight 928.15

Temperature 180(2) K

Wavelength 1.54184 A

Crystal system, space group Triclinic, P -1

Unit cell dimensions a = 6.89250(10) A alpha = 99.816(2) deg.

b = 13.7398(2) A beta = 96.041(2) deg.

c = 26.7150(6) A gamma = 95.0320(10) deg.

Volume 2464.62(8) A^3

Z, Calculated density 2, 1.251 Mg/m^3

Absorption coefficient 1.400 mm^-1

F(000) 980

Crystal size 0.3329 x 0.3023 x 0.042 mm

Theta range for data collection 3.28 to 76.62 deg.

Limiting indices -8<=h<=7, -17<=k<=17, -33<=l<=33

Reflections collected / unique 32459 / 10309 [R(int) = 0.0292]

Completeness to theta = 76.62 99.4 %

Absorption correction Semi-empirical from equivalents

Refinement method Full-matrix least-squares on F^2

Data / restraints / parameters 10309 / 0 / 579

Goodness-of-fit on F^2 1.042

Final R indices [I>2sigma(I)] R1 = 0.0383, wR2 = 0.1019 [9393 Fo]

R indices (all data) R1 = 0.0427, wR2 = 0.1056

Largest diff. peak and hole 0.261 and -0.304 e.A^-3

Table 2. Atomic coordinates and equivalent isotropic displacement parameters for

yue1166c.

U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

________________________________________________________________

x y z U(eq)

________________________________________________________________

C(1) 0.70874(19) 0.41244(10) 1.11760(5) 0.0343(3)

C(2) 0.50874(18) 0.40899(9) 1.12800(5) 0.0292(2)

C(3) 0.47886(19) 0.41648(10) 1.18065(5) 0.0349(3)

C(4) 0.35218(17) 0.39843(9) 1.09115(5) 0.0279(2)

C(5) 0.34679(17) 0.38458(8) 1.03717(5) 0.0266(2)

C(6) 0.17518(17) 0.37375(10) 1.00352(5) 0.0318(2)

C(7) 0.20575(18) 0.35527(10) 0.95214(5) 0.0317(2)

C(8) 0.40101(16) 0.35190(8) 0.94510(4) 0.0258(2)

C(9) 0.48671(16) 0.33581(8) 0.89715(4) 0.0255(2)

C(10) 0.37077(17) 0.29327(9) 0.85095(5) 0.0288(2)

C(11) 0.44720(17) 0.28072(9) 0.80482(5) 0.0291(2)

C(12) 0.64619(17) 0.31044(8) 0.80219(4) 0.0264(2)

C(13) 0.76380(17) 0.35167(9) 0.84876(5) 0.0296(2)

C(14) 0.68559(17) 0.36314(9) 0.89458(4) 0.0283(2)

C(15) 0.60377(17) 0.28305(9) 0.70798(4) 0.0292(2)

C(16) 0.46717(19) 0.34865(10) 0.69914(5) 0.0347(3)

C(17) 0.3583(2) 0.33790(12) 0.65134(6) 0.0422(3)

C(18) 0.3887(2) 0.26322(13) 0.61190(5) 0.0462(3)

C(19) 0.5261(2) 0.19867(12) 0.62050(5) 0.0440(3)

C(20) 0.6318(2) 0.20709(10) 0.66866(5) 0.0357(3)

C(21) 0.93645(17) 0.31503(11) 0.75573(5) 0.0345(3)

C(22) 1.00432(19) 0.42344(12) 0.75792(5) 0.0409(3)

C(23) 0.9749(3) 0.54991(13) 0.70926(8) 0.0594(4)

C(24) 0.8738(3) 0.57064(17) 0.66084(10) 0.0725(6)

C(25) 0.8561(4) 0.4318(2) 0.59464(10) 0.0859(7)

C(26) 0.9463(6) 0.3934(4) 0.54806(11) 0.150(2)

C(27) 0.0650(2) 0.19473(10) 1.17803(5) 0.0361(3)

C(28) 0.09337(19) 0.17123(9) 1.12510(5) 0.0301(2)

C(29) 0.2870(2) 0.15411(10) 1.11411(5) 0.0351(3)

C(30) -0.06358(18) 0.16534(9) 1.08862(5) 0.0290(2)

C(31) -0.07615(17) 0.14522(9) 1.03459(5) 0.0284(2)

C(32) -0.25040(18) 0.14352(10) 1.00294(5) 0.0325(2)

C(33) -0.22993(18) 0.12526(10) 0.95096(5) 0.0329(3)

C(34) -0.03996(17) 0.11124(8) 0.94138(4) 0.0268(2)

C(35) 0.03361(17) 0.08984(8) 0.89202(4) 0.0255(2)

C(36) -0.08341(16) 0.09821(9) 0.84672(4) 0.0273(2)

C(37) -0.01920(17) 0.07632(9) 0.79934(4) 0.0278(2)

C(38) 0.16913(16) 0.04497(8) 0.79430(4) 0.0256(2)

C(39) 0.28643(17) 0.03650(9) 0.83978(4) 0.0281(2)

C(40) 0.21935(17) 0.05844(9) 0.88686(4) 0.0279(2)

C(41) 0.10452(17) 0.01592(9) 0.70083(4) 0.0278(2)

C(42) -0.03616(19) -0.06557(10) 0.68726(5) 0.0357(3)

C(43) -0.1603(2) -0.07753(12) 0.64152(5) 0.0423(3)

C(44) -0.1405(2) -0.00950(12) 0.60921(5) 0.0420(3)

C(45) 0.0009(2) 0.07149(11) 0.62271(5) 0.0392(3)

C(46) 0.12277(18) 0.08502(10) 0.66876(5) 0.0325(2)

C(47) 0.44117(17) 0.01165(10) 0.74299(5) 0.0306(2)

C(48) 0.4867(2) -0.09355(11) 0.74460(5) 0.0370(3)

C(49) 0.4384(3) -0.25548(12) 0.69885(7) 0.0504(4)

C(50) 0.3765(3) -0.31756(13) 0.64706(8) 0.0590(4)

C(51) 0.4756(4) -0.36284(18) 0.56558(8) 0.0748(6)

C(52) 0.6318(5) -0.3390(2) 0.53333(9) 0.0957(9)

N(1) 0.72433(14) 0.29514(8) 0.75615(4) 0.0302(2)

N(2) 0.4547(2) 0.42088(11) 1.22273(5) 0.0505(3)

N(3) 0.86933(18) 0.41613(13) 1.10988(5) 0.0522(3)

N(4) 0.23637(14) 0.02783(8) 0.74731(4) 0.0290(2)

N(5) 0.0378(2) 0.21388(11) 1.21997(5) 0.0512(3)

N(6) 0.44337(19) 0.14070(12) 1.10558(5) 0.0508(3)

O(1) 0.93365(16) 0.44795(8) 0.71073(4) 0.0446(2)

O(2) 0.9495(2) 0.52597(15) 0.61668(6) 0.0788(5)

O(3) 0.41623(14) -0.15416(7) 0.69692(4) 0.0381(2)

O(4) 0.51551(17) -0.29818(8) 0.61359(4) 0.0496(3)

S(1) 0.54703(4) 0.37175(2) 1.003212(10) 0.02685(8)

S(2) 0.11407(4) 0.12208(2) 0.997932(10) 0.02698(8)

H(4) 0.2306 0.4006 1.1032 0.034

H(6) 0.0517 0.3784 1.0142 0.038

H(7) 0.1047 0.3461 0.9253 0.038

H(10) 0.2388 0.2730 0.8514 0.035

H(11) 0.3659 0.2521 0.7750 0.035

H(13) 0.8962 0.3714 0.8485 0.036

H(14) 0.7673 0.3898 0.9247 0.034

H(16) 0.4486 0.3998 0.7253 0.042

H(17) 0.2647 0.3809 0.6458 0.051

H(18) 0.3169 0.2566 0.5798 0.055

H(19) 0.5481 0.1492 0.5939 0.053

H(20) 0.7209 0.1620 0.6745 0.043

H(21A) 0.9731 0.2766 0.7249 0.041

H(21B) 1.0039 0.2929 0.7848 0.041

H(22A) 0.9530 0.4643 0.7858 0.049

H(22B) 1.1465 0.4346 0.7635 0.049

H(23A) 1.1153 0.5668 0.7109 0.071

H(23B) 0.9292 0.5898 0.7384 0.071

H(24A) 0.7356 0.5472 0.6582 0.087

H(24B) 0.8845 0.6419 0.6622 0.087

H(25A) 0.7173 0.4357 0.5856 0.103

H(25B) 0.8696 0.3871 0.6189 0.103

H(26A) 0.9225 0.4347 0.5230 0.224

H(26B) 0.8894 0.3266 0.5343 0.224

H(26C) 1.0851 0.3939 0.5568 0.224

H(30) -0.1817 0.1764 1.1014 0.035

H(32) -0.3696 0.1536 1.0153 0.039

H(33) -0.3334 0.1227 0.9253 0.039

H(36) -0.2075 0.1191 0.8489 0.033

H(37) -0.1008 0.0822 0.7702 0.033

H(39) 0.4108 0.0158 0.8379 0.034

H(40) 0.3000 0.0522 0.9161 0.034

H(42) -0.0476 -0.1121 0.7086 0.043

H(43) -0.2567 -0.1313 0.6327 0.051

H(44) -0.2222 -0.0182 0.5784 0.050

H(45) 0.0143 0.1170 0.6009 0.047

H(46) 0.2161 0.1401 0.6781 0.039

H(47A) 0.5236 0.0562 0.7707 0.037

H(47B) 0.4751 0.0290 0.7111 0.037

H(48A) 0.6273 -0.0949 0.7517 0.044

H(48B) 0.4245 -0.1182 0.7716 0.044

H(49A) 0.3586 -0.2779 0.7234 0.061

H(49B) 0.5743 -0.2624 0.7099 0.061

H(50A) 0.3664 -0.3874 0.6496 0.071

H(50B) 0.2486 -0.3024 0.6336 0.071

H(51A) 0.3480 -0.3542 0.5489 0.090

H(51B) 0.4744 -0.4313 0.5703 0.090

H(52A) 0.6276 -0.2722 0.5274 0.144

H(52B) 0.6101 -0.3843 0.5012 0.144

H(52C) 0.7580 -0.3453 0.5507 0.144

________________________________________________________________

Table 3. Bond lengths [A] for yue1166c.

_____________________________________________________________

C(1)-N(3) 1.1454(19)

C(1)-C(2) 1.4330(18)

C(2)-C(4) 1.3618(17)

C(2)-C(3) 1.4305(17)

C(3)-N(2) 1.1460(19)

C(4)-C(5) 1.4182(17)

C(4)-H(4) 0.9300

C(5)-C(6) 1.3889(17)

C(5)-S(1) 1.7352(12)

C(6)-C(7) 1.3946(18)

C(6)-H(6) 0.9300

C(7)-C(8) 1.3820(17)

C(7)-H(7) 0.9300

C(8)-C(9) 1.4574(16)

C(8)-S(1) 1.7252(11)

C(9)-C(14) 1.4011(16)

C(9)-C(10) 1.4030(16)

C(10)-C(11) 1.3805(17)

C(10)-H(10) 0.9300

C(11)-C(12) 1.4087(16)

C(11)-H(11) 0.9300

C(12)-N(1) 1.3851(15)

C(12)-C(13) 1.4116(16)

C(13)-C(14) 1.3790(17)

C(13)-H(13) 0.9300

C(14)-H(14) 0.9300

C(15)-C(16) 1.3890(18)

C(15)-C(20) 1.3908(18)

C(15)-N(1) 1.4323(15)

C(16)-C(17) 1.3893(19)

C(16)-H(16) 0.9300

C(17)-C(18) 1.387(2)

C(17)-H(17) 0.9300

C(18)-C(19) 1.381(2)

C(18)-H(18) 0.9300

C(19)-C(20) 1.392(2)

C(19)-H(19) 0.9300

C(20)-H(20) 0.9300

C(21)-N(1) 1.4652(15)

C(21)-C(22) 1.511(2)

C(21)-H(21A) 0.9700

C(21)-H(21B) 0.9700

C(22)-O(1) 1.4087(18)

C(22)-H(22A) 0.9700

C(22)-H(22B) 0.9700

C(23)-O(1) 1.413(2)

C(23)-C(24) 1.487(3)

C(23)-H(23A) 0.9700

C(23)-H(23B) 0.9700

C(24)-O(2) 1.407(3)

C(24)-H(24A) 0.9700

C(24)-H(24B) 0.9700

C(25)-O(2) 1.396(3)

C(25)-C(26) 1.487(4)

C(25)-H(25A) 0.9700

C(25)-H(25B) 0.9700

C(26)-H(26A) 0.9600

C(26)-H(26B) 0.9600

C(26)-H(26C) 0.9600

C(27)-N(5) 1.1454(19)

C(27)-C(28) 1.4338(18)

C(28)-C(30) 1.3647(18)

C(28)-C(29) 1.4270(19)

C(29)-N(6) 1.149(2)

C(30)-C(31) 1.4145(17)

C(30)-H(30) 0.9300

C(31)-C(32) 1.3901(17)

C(31)-S(2) 1.7368(12)

C(32)-C(33) 1.3930(17)

C(32)-H(32) 0.9300

C(33)-C(34) 1.3838(17)

C(33)-H(33) 0.9300

C(34)-C(35) 1.4549(16)

C(34)-S(2) 1.7291(12)

C(35)-C(40) 1.3992(16)

C(35)-C(36) 1.4096(16)

C(36)-C(37) 1.3783(17)

C(36)-H(36) 0.9300

C(37)-C(38) 1.4155(16)

C(37)-H(37) 0.9300

C(38)-N(4) 1.3737(15)

C(38)-C(39) 1.4146(16)

C(39)-C(40) 1.3801(17)

C(39)-H(39) 0.9300

C(40)-H(40) 0.9300

C(41)-C(42) 1.3865(18)

C(41)-C(46) 1.3894(17)

C(41)-N(4) 1.4359(15)

C(42)-C(43) 1.3926(19)

C(42)-H(42) 0.9300

C(43)-C(44) 1.384(2)

C(43)-H(43) 0.9300

C(44)-C(45) 1.385(2)

C(44)-H(44) 0.9300

C(45)-C(46) 1.3895(18)

C(45)-H(45) 0.9300

C(46)-H(46) 0.9300

C(47)-N(4) 1.4615(15)

C(47)-C(48) 1.5125(19)

C(47)-H(47A) 0.9700

C(47)-H(47B) 0.9700

C(48)-O(3) 1.4104(17)

C(48)-H(48A) 0.9700

C(48)-H(48B) 0.9700

C(49)-O(3) 1.4227(18)

C(49)-C(50) 1.494(3)

C(49)-H(49A) 0.9700

C(49)-H(49B) 0.9700

C(50)-O(4) 1.416(2)

C(50)-H(50A) 0.9700

C(50)-H(50B) 0.9700

C(51)-O(4) 1.416(2)

C(51)-C(52) 1.496(4)

C(51)-H(51A) 0.9700

C(51)-H(51B) 0.9700

C(52)-H(52A) 0.9600

C(52)-H(52B) 0.9600

C(52)-H(52C) 0.9600

_____________________________________________________________

Table 4. Bond angles [deg] for yue1166c.

_____________________________________________________________

N(3)-C(1)-C(2) 179.07(16)

C(4)-C(2)-C(3) 120.19(11)

C(4)-C(2)-C(1) 123.83(11)

C(3)-C(2)-C(1) 115.98(11)

N(2)-C(3)-C(2) 178.92(15)

C(2)-C(4)-C(5) 129.69(11)

C(2)-C(4)-H(4) 115.2

C(5)-C(4)-H(4) 115.2

C(6)-C(5)-C(4) 123.94(11)

C(6)-C(5)-S(1) 109.98(9)

C(4)-C(5)-S(1) 126.00(9)

C(5)-C(6)-C(7) 113.57(11)

C(5)-C(6)-H(6) 123.2

C(7)-C(6)-H(6) 123.2

C(8)-C(7)-C(6) 113.35(11)

C(8)-C(7)-H(7) 123.3

C(6)-C(7)-H(7) 123.3

C(7)-C(8)-C(9) 128.37(11)

C(7)-C(8)-S(1) 110.70(9)

C(9)-C(8)-S(1) 120.92(8)

C(14)-C(9)-C(10) 116.89(11)

C(14)-C(9)-C(8) 122.27(10)

C(10)-C(9)-C(8) 120.83(10)

C(11)-C(10)-C(9) 121.83(11)

C(11)-C(10)-H(10) 119.1

C(9)-C(10)-H(10) 119.1

C(10)-C(11)-C(12) 121.15(11)

C(10)-C(11)-H(11) 119.4

C(12)-C(11)-H(11) 119.4

N(1)-C(12)-C(11) 121.17(10)

N(1)-C(12)-C(13) 121.68(10)

C(11)-C(12)-C(13) 117.08(10)

C(14)-C(13)-C(12) 121.09(11)

C(14)-C(13)-H(13) 119.5

C(12)-C(13)-H(13) 119.5

C(13)-C(14)-C(9) 121.94(11)

C(13)-C(14)-H(14) 119.0

C(9)-C(14)-H(14) 119.0

C(16)-C(15)-C(20) 119.64(12)

C(16)-C(15)-N(1) 121.23(11)

C(20)-C(15)-N(1) 119.04(11)

C(15)-C(16)-C(17) 120.09(13)

C(15)-C(16)-H(16) 120.0

C(17)-C(16)-H(16) 120.0

C(18)-C(17)-C(16) 120.23(14)

C(18)-C(17)-H(17) 119.9

C(16)-C(17)-H(17) 119.9

C(19)-C(18)-C(17) 119.71(13)

C(19)-C(18)-H(18) 120.1

C(17)-C(18)-H(18) 120.1

C(18)-C(19)-C(20) 120.45(14)

C(18)-C(19)-H(19) 119.8

C(20)-C(19)-H(19) 119.8

C(15)-C(20)-C(19) 119.84(13)

C(15)-C(20)-H(20) 120.1

C(19)-C(20)-H(20) 120.1

N(1)-C(21)-C(22) 113.42(11)

N(1)-C(21)-H(21A) 108.9

C(22)-C(21)-H(21A) 108.9

N(1)-C(21)-H(21B) 108.9

C(22)-C(21)-H(21B) 108.9

H(21A)-C(21)-H(21B) 107.7

O(1)-C(22)-C(21) 107.26(11)

O(1)-C(22)-H(22A) 110.3

C(21)-C(22)-H(22A) 110.3

O(1)-C(22)-H(22B) 110.3

C(21)-C(22)-H(22B) 110.3

H(22A)-C(22)-H(22B) 108.5

O(1)-C(23)-C(24) 108.80(16)

O(1)-C(23)-H(23A) 109.9

C(24)-C(23)-H(23A) 109.9

O(1)-C(23)-H(23B) 109.9

C(24)-C(23)-H(23B) 109.9

H(23A)-C(23)-H(23B) 108.3

O(2)-C(24)-C(23) 113.79(18)

O(2)-C(24)-H(24A) 108.8

C(23)-C(24)-H(24A) 108.8

O(2)-C(24)-H(24B) 108.8

C(23)-C(24)-H(24B) 108.8

H(24A)-C(24)-H(24B) 107.7

O(2)-C(25)-C(26) 109.2(3)

O(2)-C(25)-H(25A) 109.8

C(26)-C(25)-H(25A) 109.8

O(2)-C(25)-H(25B) 109.8

C(26)-C(25)-H(25B) 109.8

H(25A)-C(25)-H(25B) 108.3

C(25)-C(26)-H(26A) 109.5

C(25)-C(26)-H(26B) 109.5

H(26A)-C(26)-H(26B) 109.5

C(25)-C(26)-H(26C) 109.5

H(26A)-C(26)-H(26C) 109.5

H(26B)-C(26)-H(26C) 109.5

N(5)-C(27)-C(28) 178.35(16)

C(30)-C(28)-C(29) 124.08(11)

C(30)-C(28)-C(27) 119.02(12)

C(29)-C(28)-C(27) 116.89(11)

N(6)-C(29)-C(28) 179.55(18)

C(28)-C(30)-C(31) 130.62(11)

C(28)-C(30)-H(30) 114.7

C(31)-C(30)-H(30) 114.7

C(32)-C(31)-C(30) 122.82(11)

C(32)-C(31)-S(2) 110.03(9)

C(30)-C(31)-S(2) 127.14(9)

C(31)-C(32)-C(33) 113.75(11)

C(31)-C(32)-H(32) 123.1

C(33)-C(32)-H(32) 123.1

C(34)-C(33)-C(32) 113.16(11)

C(34)-C(33)-H(33) 123.4

C(32)-C(33)-H(33) 123.4

C(33)-C(34)-C(35) 128.00(11)

C(33)-C(34)-S(2) 110.86(9)

C(35)-C(34)-S(2) 121.14(9)

C(40)-C(35)-C(36) 116.94(10)

C(40)-C(35)-C(34) 122.41(10)

C(36)-C(35)-C(34) 120.63(10)

C(37)-C(36)-C(35) 121.89(10)

C(37)-C(36)-H(36) 119.1

C(35)-C(36)-H(36) 119.1

C(36)-C(37)-C(38) 120.99(10)

C(36)-C(37)-H(37) 119.5

C(38)-C(37)-H(37) 119.5

N(4)-C(38)-C(39) 122.01(10)

N(4)-C(38)-C(37) 120.83(10)

C(39)-C(38)-C(37) 117.10(10)

C(40)-C(39)-C(38) 121.08(11)

C(40)-C(39)-H(39) 119.5

C(38)-C(39)-H(39) 119.5

C(39)-C(40)-C(35) 122.00(11)

C(39)-C(40)-H(40) 119.0

C(35)-C(40)-H(40) 119.0

C(42)-C(41)-C(46) 120.20(11)

C(42)-C(41)-N(4) 120.25(11)

C(46)-C(41)-N(4) 119.53(11)

C(41)-C(42)-C(43) 119.74(12)

C(41)-C(42)-H(42) 120.1

C(43)-C(42)-H(42) 120.1

C(44)-C(43)-C(42) 120.12(13)

C(44)-C(43)-H(43) 119.9

C(42)-C(43)-H(43) 119.9

C(43)-C(44)-C(45) 120.00(12)

C(43)-C(44)-H(44) 120.0

C(45)-C(44)-H(44) 120.0

C(44)-C(45)-C(46) 120.23(13)

C(44)-C(45)-H(45) 119.9

C(46)-C(45)-H(45) 119.9

C(41)-C(46)-C(45) 119.69(12)

C(41)-C(46)-H(46) 120.2

C(45)-C(46)-H(46) 120.2

N(4)-C(47)-C(48) 114.45(10)

N(4)-C(47)-H(47A) 108.6

C(48)-C(47)-H(47A) 108.6

N(4)-C(47)-H(47B) 108.6

C(48)-C(47)-H(47B) 108.6

H(47A)-C(47)-H(47B) 107.6

O(3)-C(48)-C(47) 108.99(10)

O(3)-C(48)-H(48A) 109.9

C(47)-C(48)-H(48A) 109.9

O(3)-C(48)-H(48B) 109.9

C(47)-C(48)-H(48B) 109.9

H(48A)-C(48)-H(48B) 108.3

O(3)-C(49)-C(50) 109.63(15)

O(3)-C(49)-H(49A) 109.7

C(50)-C(49)-H(49A) 109.7

O(3)-C(49)-H(49B) 109.7

C(50)-C(49)-H(49B) 109.7

H(49A)-C(49)-H(49B) 108.2

O(4)-C(50)-C(49) 109.75(14)

O(4)-C(50)-H(50A) 109.7

C(49)-C(50)-H(50A) 109.7

O(4)-C(50)-H(50B) 109.7

C(49)-C(50)-H(50B) 109.7

H(50A)-C(50)-H(50B) 108.2

O(4)-C(51)-C(52) 108.5(2)

O(4)-C(51)-H(51A) 110.0

C(52)-C(51)-H(51A) 110.0

O(4)-C(51)-H(51B) 110.0

C(52)-C(51)-H(51B) 110.0

H(51A)-C(51)-H(51B) 108.4

C(51)-C(52)-H(52A) 109.5

C(51)-C(52)-H(52B) 109.5

H(52A)-C(52)-H(52B) 109.5

C(51)-C(52)-H(52C) 109.5

H(52A)-C(52)-H(52C) 109.5

H(52B)-C(52)-H(52C) 109.5

C(12)-N(1)-C(15) 121.86(10)

C(12)-N(1)-C(21) 119.67(10)

C(15)-N(1)-C(21) 116.86(10)

C(38)-N(4)-C(41) 121.13(10)

C(38)-N(4)-C(47) 120.86(10)

C(41)-N(4)-C(47) 117.75(9)

C(22)-O(1)-C(23) 112.86(13)

C(25)-O(2)-C(24) 114.28(18)

C(48)-O(3)-C(49) 110.40(11)

C(51)-O(4)-C(50) 112.08(15)

C(8)-S(1)-C(5) 92.40(6)

C(34)-S(2)-C(31) 92.19(6)

_____________________________________________________________

Table 5. Anisotropic displacement parameters for yue1166c.

The anisotropic displacement factor exponent takes the form:

-2 pi^2 [ h^2 a*^2 U11 + ... + 2 h k a* b* U12 ]

___________________________________________________________________________

U11 U22 U33 U23 U13 U12

___________________________________________________________________________

C(1) 0.0305(6) 0.0428(7) 0.0283(6) 0.0038(5) 0.0009(5) 0.0049(5)

C(2) 0.0292(6) 0.0298(5) 0.0292(6) 0.0067(4) 0.0047(4) 0.0027(4)

C(3) 0.0337(6) 0.0368(6) 0.0342(7) 0.0082(5) 0.0035(5) 0.0016(5)

C(4) 0.0246(5) 0.0278(5) 0.0328(6) 0.0078(4) 0.0068(4) 0.0026(4)

C(5) 0.0238(5) 0.0256(5) 0.0312(6) 0.0066(4) 0.0040(4) 0.0024(4)

C(6) 0.0225(5) 0.0379(6) 0.0354(6) 0.0093(5) 0.0035(4) 0.0011(4)

C(7) 0.0235(5) 0.0401(6) 0.0314(6) 0.0094(5) -0.0003(4) 0.0016(5)

C(8) 0.0230(5) 0.0251(5) 0.0294(5) 0.0074(4) 0.0001(4) 0.0015(4)

C(9) 0.0244(5) 0.0252(5) 0.0277(5) 0.0077(4) 0.0006(4) 0.0037(4)

C(10) 0.0231(5) 0.0317(6) 0.0307(6) 0.0071(4) 0.0009(4) -0.0021(4)

C(11) 0.0259(5) 0.0317(6) 0.0274(5) 0.0049(4) -0.0013(4) -0.0018(4)

C(12) 0.0252(5) 0.0284(5) 0.0266(5) 0.0070(4) 0.0022(4) 0.0044(4)

C(13) 0.0200(5) 0.0375(6) 0.0309(6) 0.0069(5) 0.0002(4) 0.0027(4)

C(14) 0.0238(5) 0.0331(6) 0.0271(5) 0.0060(4) -0.0017(4) 0.0029(4)

C(15) 0.0249(5) 0.0359(6) 0.0267(5) 0.0080(4) 0.0026(4) -0.0011(4)

C(16) 0.0306(6) 0.0382(6) 0.0352(6) 0.0083(5) 0.0020(5) 0.0029(5)

C(17) 0.0351(7) 0.0515(8) 0.0415(7) 0.0188(6) -0.0030(5) 0.0028(6)

C(18) 0.0446(8) 0.0640(9) 0.0280(6) 0.0148(6) -0.0031(5) -0.0090(7)

C(19) 0.0474(8) 0.0520(8) 0.0290(6) 0.0014(6) 0.0065(6) -0.0050(6)

C(20) 0.0346(6) 0.0396(7) 0.0324(6) 0.0049(5) 0.0065(5) 0.0011(5)

C(21) 0.0226(5) 0.0502(7) 0.0311(6) 0.0068(5) 0.0037(4) 0.0080(5)

C(22) 0.0276(6) 0.0543(8) 0.0375(7) 0.0036(6) 0.0039(5) -0.0048(5)

C(23) 0.0614(10) 0.0460(9) 0.0710(11) 0.0135(8) 0.0166(9) -0.0084(7)

C(24) 0.0670(12) 0.0632(11) 0.0962(16) 0.0383(11) 0.0152(11) 0.0029(9)

C(25) 0.0794(15) 0.1054(19) 0.0734(14) 0.0215(13)-0.0016(12) 0.0162(14)

C(26) 0.145(3) 0.254(6) 0.0540(15) 0.019(2) -0.0120(17) 0.089(4)

C(27) 0.0413(7) 0.0354(6) 0.0318(7) 0.0087(5) 0.0029(5) 0.0019(5)

C(28) 0.0341(6) 0.0290(5) 0.0286(6) 0.0076(4) 0.0059(5) 0.0031(4)

C(29) 0.0356(7) 0.0386(6) 0.0315(6) 0.0098(5) 0.0017(5) 0.0026(5)

C(30) 0.0305(6) 0.0282(5) 0.0304(6) 0.0075(4) 0.0081(4) 0.0055(4)

C(31) 0.0284(5) 0.0282(5) 0.0302(6) 0.0071(4) 0.0062(4) 0.0054(4)

C(32) 0.0272(6) 0.0391(6) 0.0337(6) 0.0088(5) 0.0067(5) 0.0095(5)

C(33) 0.0278(6) 0.0416(7) 0.0304(6) 0.0085(5) 0.0030(4) 0.0069(5)

C(34) 0.0270(5) 0.0259(5) 0.0278(5) 0.0063(4) 0.0024(4) 0.0031(4)

C(35) 0.0257(5) 0.0252(5) 0.0258(5) 0.0059(4) 0.0029(4) 0.0013(4)

C(36) 0.0220(5) 0.0307(5) 0.0296(5) 0.0066(4) 0.0021(4) 0.0035(4)

C(37) 0.0245(5) 0.0315(5) 0.0267(5) 0.0064(4) -0.0007(4) 0.0021(4)

C(38) 0.0245(5) 0.0263(5) 0.0252(5) 0.0045(4) 0.0025(4) 0.0000(4)

C(39) 0.0231(5) 0.0339(6) 0.0274(5) 0.0062(4) 0.0016(4) 0.0041(4)

C(40) 0.0258(5) 0.0317(6) 0.0261(5) 0.0069(4) 0.0001(4) 0.0026(4)

C(41) 0.0239(5) 0.0355(6) 0.0238(5) 0.0041(4) 0.0038(4) 0.0032(4)

C(42) 0.0347(6) 0.0413(7) 0.0300(6) 0.0078(5) 0.0035(5) -0.0040(5)

C(43) 0.0340(7) 0.0518(8) 0.0355(7) 0.0010(6) 0.0001(5) -0.0075(6)

C(44) 0.0327(6) 0.0625(9) 0.0282(6) 0.0049(6) -0.0023(5) 0.0053(6)

C(45) 0.0376(7) 0.0514(8) 0.0319(6) 0.0156(6) 0.0036(5) 0.0078(6)

C(46) 0.0294(6) 0.0366(6) 0.0320(6) 0.0085(5) 0.0042(5) 0.0016(5)

C(47) 0.0230(5) 0.0407(6) 0.0284(5) 0.0069(5) 0.0049(4) 0.0011(5)

C(48) 0.0356(6) 0.0474(7) 0.0302(6) 0.0093(5) 0.0052(5) 0.0109(5)

C(49) 0.0616(10) 0.0398(7) 0.0545(9) 0.0126(6) 0.0232(8) 0.0039(7)

C(50) 0.0540(9) 0.0450(8) 0.0736(12)-0.0030(8) 0.0225(8) -0.0099(7)

C(51) 0.0852(15) 0.0690(12) 0.0577(11)-0.0186(10) 0.0005(10) 0.0087(11)

C(52) 0.127(2) 0.113(2) 0.0483(11)-0.0020(12) 0.0268(13) 0.0309(18)

N(1) 0.0226(5) 0.0401(5) 0.0276(5) 0.0058(4) 0.0026(4) 0.0033(4)

N(2) 0.0596(8) 0.0582(8) 0.0345(6) 0.0100(5) 0.0109(6) 0.0018(6)

N(3) 0.0283(6) 0.0833(10) 0.0421(7) 0.0033(6) 0.0027(5) 0.0074(6)

N(4) 0.0238(5) 0.0388(5) 0.0242(5) 0.0059(4) 0.0024(4) 0.0026(4)

N(5) 0.0689(9) 0.0529(7) 0.0323(6) 0.0082(5) 0.0091(6) 0.0048(6)

N(6) 0.0349(6) 0.0729(9) 0.0478(7) 0.0161(6) 0.0060(5) 0.0114(6)

O(1) 0.0430(5) 0.0445(5) 0.0451(5) 0.0098(4) 0.0059(4) -0.0049(4)

O(2) 0.0584(8) 0.1132(13) 0.0691(9) 0.0399(9) 0.0068(7) -0.0124(8)

O(3) 0.0407(5) 0.0385(5) 0.0358(5) 0.0061(4) 0.0074(4) 0.0056(4)

O(4) 0.0495(6) 0.0469(6) 0.0474(6) -0.0050(5) 0.0107(5) -0.0018(5)

S(1) 0.02115(13)0.03368(15)0.02576(14)0.00534(10)0.00158(10)0.00486(10)

S(2) 0.02470(14)0.03200(14)0.02500(13)0.00624(10)0.00390(10)0.00421(10)

_________________________________________________________________________

N6

N5

H50A

C29

C27 H49B

H49A H51B

C49 C28 C50 H52C

O4 C51

N2

H48B C30

H48A

H50B H52B

H30 C52

H40 S2

C3

H51A

C48

N3

C31 O3

H39

C1

C40

C2

H52A C39

C32 C34

H32 C35

C4

H47A

C33 C47

H4

H42

C38

S1 C5

H33 H47B

N4

C42 C36

C37

H14

C6

H36

C8

H6

C41 H21B

C14

H43

C9

C7

H37 H13

C43

C13

C10 H10 H20

H7 H21A

C12 C21

C11 N1

H11

C46 C20

H46

C44

H22B

C15 C22

C45 H19

H44

H22A

C19

H45

O1

C16 H16 C18

H25B

C17 H23A

H18

C23

H26B

H26C H23B

C26 C25

H17 H25A

O2 C24 H26A H24A

H24B

N6

N5

H50A

C29

C27 H49B

H49A H51B

C49 C28 C50 H52C

O4 C51

N2

H48B

C30 H48A

H50B H52B

H30 C52

H40 S2

C3

H51A

C48

N3

C31 O3

H39

C1

C40

C2

H52A C39

C32 C34

H32 C35

C4

H47A

C33 C47

H4

H42

C38

S1

C5

H33 H47B

N4

C42 C36

C37

H14

C6

H36

C8

H6

C41 H21B

C14

H43

C9

C7

H37 H13

C43

C13

C10 H10 H20

H7 H21A

C12 C21

C11 N1

H11

C46 C20

H46

C44

H22B

C15 C22

C45 H19

H44

H22A

C19

H45

O1

C16 H16 C18

H25B

C17 H23A

H18

C23

H26B

H26C H23B

C26 C25

H17 H25A

O2 C24 H26A H24A

H24B

b

c

C H N O S

a

c

C H N O S

a

b

C H N O S