Supporting information Contents

Supporting information Evidence of intramolecular СAr-H∙∙∙O=C hydrogen bonds in the structure of (diaryl)tetrahydrofuranones using spectroscopic tools and DFT calculations D. V. Semenok,a J. J. Medvedev,a S. I. Selivanov,a J. Sieler,b M.S. Avdontseva,a A.S. Mereshchenko,a V.A. Nikolaev a* a

Saint-Petersburg State University, University Prosp. 26, St.-Petersburg 198504, Russia

Universität Leipzig, Institut für Anorganische Chemie, Johannisallee 29, D-04103 Leipzig, Germany

b

Contents

I. Description of the compounds 1-2а,b (1Н, 13С NMR, IR, MS)……..…………………………........S2 II. 1H NMR spectra of the compounds 1a-d, 2a-d in different solvents……………………...….…….S3 III. 1H NMR spectra of the compounds 1-2 a,b with addition of CF3COOH …………………………...S5 IV. 1H NMR spectra of the compounds 1-2 a,b at different temperatures…………………….…………S6 V. Calculated frequencies of CO vibrations in IR spectra………………………………………………S7 VI. Hydrogen bond energy estimation based on the temperature gradient of chemical shifts in 1H NMR spectra of studied compounds in nonane solution. ……………………………………………...S8 VII. Cartesian coordinates for the DFT-optimized structures of 1a-d, 2a-d, minima and maxima of relaxed redundant scan of 1a,b along the dihedral angle between tetrahydrofuran and aryl rings……...S13 VIII. Quantum-chemical calculations for the compounds 1 and 2……………………………………...S33 IX. X-Ray diffraction data for the compounds 1a-d and 2a-d.………………………...…..…….…....S35

I. Description of the compounds 1a,b and 2a,b.

Spectral data for the 1c,d and 2c,d were published before in our works8b, 8f 5,5-dimethyl-2,2-diphenyldihydrofuran-3(2H)-one (1a), colorless cryst., m.p. 79-80 оС. 1 H NMR (400 MHz, 5 mg in 0.8 ml CDCl3, TMS = 0 ppm), δ, ppm: 1.390 s (6H, 2CH3), 2.590 s (2H, CH2), 7.230 d (2H, 3JHH = 7.3 Hz), 7.291 t (4H, 3JHH = 7.4 Hz), 7.536 d (4H, 3JHH = 7.6 Hz). 13 C NMR (100 MHz, 50 mg in 0.8 ml CDCl3), δ, ppm: 29.66 (2C, 2CH3), 49.32 (1C, СH2), 77.71 (1C, С2), 86.77 (1C, C5), 126.08 (4C), 127.43 (2C), 128.14 (4C), 142.31 (2C), 213.28 (1C, C=O). IR (in CCl4), cm-1: 599.8 w., 699.7 m., 740.5 s., 1030.0 w., 1048.8 w., 1164.0 m., 1448.5 w., 1491.0 w., 1755.8 m., 2931.7 w., 2977.1 w., 3064.9 w. MS, m/z: 267.1383 [MH]+, 289.1199 [MNa]+. 5,5-dimethyl-2,2-di(4-fluorophenyl)dihydrofuran-3(2H)-one (1b) colorless cryst., m.p. 80-81 оС. 1 H NMR (400 MHz, 5 mg in 0.8 ml CDCl3, TMS = 0 ppm), δ, ppm: 1.394 s (6H, 2CH3), 2.60 s (2H, CH2), 6.988 dd (4H, 3JHH = 8.8 Hz, 3JHF = 5.4 Hz), 7.492 dd (4H, 3J = 8.8, 5.3 Hz). 13 C NMR (100 MHz, 20 mg in 0.8 ml CDCl3), δ, ppm: 29.62 (2C, 2CH3), 49.17 (1C, СH2), 78.00 (1C, С2), 85.84 (1C, C5), 115.10 d (4C, 2JCF =21.5 Hz), 127.80 d (4C, 3JCF =8.1 Hz), 138.01 d (2С, 4JCF =2.9 Hz), 162.21 d (2C, 1JCF =246.8 Hz), 213.14 s (1C, C=O). 19F NMR (376 MHz, 5 mg in 0.8 ml CDCl3), δ, ppm: -114.96 s (2F, 2PhF). IR (in CCl4), cm-1: 581.3 w., 740.3 m., 835.9 w., 1051.6 w., 1158.4 m., 1233.7 m., 1505.9 s., 1604.8 w., 1757.1 m., 2342.5 w., 2360.4 w., 2977.5 w. MS, m/z: 303.1191 [MH]+. 2,2-dimethyl-5,5-diphenyldihydrofuran-3(2H)-one (2a), colorless cryst., m.p. 64-65 оС. 1 H NMR (400 MHz, 5 mg in 0.8 ml CDCl3,TMS = 0 ppm), δ, ppm: 1.210 s (6H, 2CH3), 3.330 s (2H, CH2), 7.240 d (2H,3JHH = 6.7 Hz), 7.307 t (4H, 3JHH = 7.6 Hz), 7.410 d (4H, 3JHH = 8.2 Hz). 13 C NMR (100 MHz, 30 mg in 0.8 ml CDCl3), δ, ppm: 25.31 (2C, 2СН3), 48.04 (1C, СН2), 81.35 (1C, С2), 82.64 (1C, С5), 126.0 (4C), 127.34 (2C), 128.28 (4C), 146.09 (2С), 217.0 (1C, С=О). IR (in CCl4), cm-1: 699.40 m., 740.25 w., 994.46 w., 1131.12 w., 1173.0 w., 1376.1 w., 1448.4 w., 1492.6 w., 1760.1 s., 2931.6 w., 2983.2 w., 3027.8 w., 3064.9 w. MS, m/z: 267.1381 [MH]+, 289.1198 [MNa]+. 2,2-dimethyl-5,5-di(4-fluorophenyl)dihydrofuran-3(2H)-one (2b) colorless cryst., m.p. 58-59 °С. 1 H NMR (400 MHz, 5 mg in 0.8 ml CDCl3,TMS = 0 ppm), δ, ppm: 1.205 s (6H, 2CH3), 3.270 s (2H, CH2), 7.001 dd (4H, 3JHH = 8.9 Hz, 3JHF = 5.4 Hz), 7.355 dd (4H, 3JHH =8.9, 5.3 Hz). 13 C NMR (100 MHz, 30 mg in 0.8 ml CDCl3), δ, ppm: 25.28 (2C, 2CH3), 48.18 (1C, СH2), 81.51 (1C, C2), 81.92 (1C, C5), 115.23 d (4C, 2JCF =21.5 Hz), 127.72 d (4C, 3JCF =8.1 Hz), 141.75 d (2С, 4JCF =3.2 Hz), 162.03 d (2C, 1JCF =247 Hz), 216.29 (1C, C=O). 19F NMR (376 MHz, 5 mg in 0.8 ml CDCl3), δ, ppm: -114.92 s (2F). IR (in CCl4), cm-1: 592.6 w., 736.2 w., 837.1 m., 995.1 w., 1095.3 w., 1159.2 m., 1236.1 m., 1508.5 s., 1605.9 w., 1762.0 s., 2932.8 w., 2982.2 w., 3052.1 w. MS, m/z: 303.1191 [MH]+, 325.1010 [MNa]+.

S2

II. 1H NMR spectra of the compounds 1a-d, 2a-d in different solvents Н NMR spectra were measured using “Bruker-400 Avance” NMR spectrometer with the internal (СН3)4Si standard unless otherwise stated. For 1H NMR measurements, sample weights were equal to 5-7 mg. 1

Table 1. Chemical shifts of ortho-protons of 1a-d, 2a-d in different solvents. Solvent

ε

D

1a

2a

Δ1

1b

2b

Δ2

1с

2с

Δ3

1d

2d

Δ4

n-Hexane*

1.9

0.1

7.60

7.40

0.20

7.55

7.34

0.21

7.67

7.45

0.22

7.60

7.39

0.21

Nonane*

2.0

0

7.71

7.52

0.19

7.62

7.44

0.18

7.66

7.42

0.24

-

-

-

CCl4

2.2

0

7.49

7.35

0.14

7.48

7.33

0.15

7.35

7.22

0.13

7.44

7.28

0.16

CDCl3

4.7

1.2

7.54

7.41

0.13

7.49

7.35

0.14

7.49

7.36

0.13

7.45

7.29

0.16

Acetone-d6

20.9

2.8

7.54

7.52

0.02

7.56

7.54

0.02

7.50

7.43

0.07

7.52

7.46

0.07

DMSO-d6

45

4.0

7.44

7.47

-0.03

7.45

7.48

-0.03

7.40

7.41

-0.01

7.40

7.37

0.03

Ortho-H

* Internal standard is CHCl3 (7.260 ppm) Table 2. Chemical shifts of meta-protons of 1a-d, 2a-d in different solvents. ε

D

n-Hexane* Nonane*

1.9 2.0

0.1 0

1a 7.20 7.32

2a 7.22 7.34

Δ1 -0.02 -0.02

1b 6.89 6.98

CCl4 CDCl3 Acetone-d6

2.2 4.7 20.9

0 1.1 2.8

7.22 7.32 7.32

7.24 7.31 7.33

-0.02 -0.01 -0.01

DMSO-d6

45

4.0

7.34

7.32

+0.02

Solvent

2b 6.91 7.03

Meta-H Δ2 1c -0.02 7.34 -0.05 7.34

2c 7.40 7.38

Δ3 -0.06 -0.04

1d 7.03 -

2d 7.09 -

Δ4 -0.06 -

6.93 6.99 7.10

6.95 7.00 7.10

-0.02 -0.01 0

7.16 7.30 7.35

7.20 7.34 7.40

-0.04 -0.04 -0.05

6.99 7.01 7.12

7.05 7.07 7.20

-0.06 -0.06 -0.06

7.18

7.16

+0.02

7.35

7.34

+0.01

7.19

7.23

-0.04

* Internal standard is CHCl3 (7.260 ppm) Table 3. Chemical shifts of para-protons of 1a-d, 2a-d in different solvents. Solvent

ε

D

n-Hexane** CCl4 CDCl3 Acetone-d6

1.9 2.2 4.7 20.9

0.1 0 1.1 2.8

1a* 7.09 7.15 7.23 7.26

2a* 7.12 7.17 7.24 7.24

Δ1 -0.03 -0.02 -0.01 0.02

1с* 7.27 7.21 7.24 7.29

2с* 7.35 7.29 7.26 7.37

Δ2 -0.08 -0.08 -0.02 -0.08

45

4.0

7.27

7.23

0.04

7.29

7.30

-0.01

DMSO-d6

Para-H

*Right part of the multiplet. **Internal standard is CHCl3 (7.260 ppm) Table 4. Chemical shifts of СH2-protons of 1-2 a,b in different solvents. ε

D

n-Hexane* Nonane*

1.9 2.0

0.08 0

1a 2.44 2.57

2a 3.17 3.30

Δ1 -0.73 -0.73

1b 2.45 2.56

2b 3.12 3.27

Δ Δ2 -0.67 -0.71

Cyclohexane*

2.0

0

-

-

-

2.45

3.12

-0.67

CCl4 CDCl3 Acetone-d6

2.2 4.7 20.9

0 1.1 2.8

2.51 2.59 2.69

3.21 3.33 3.45

-0.70 -0.74 -0.77

2.51 2.60 2.73

3.16 3.27 3.46

-0.65 -0.67 -0.73

45

4.0

2.75

3.53

-0.78

2.78

3.54

-0.76

Solvent

DMSO-d6

CH2 group in 1-2 a,b

*Internal standard is CHCl3 (7.260 ppm)

S3

Figure 1. Dependence of relative chemical shifts (Δδ) on dipole moment of solvent (D) for the protons of compounds 1a,b; 2a,b (left diagram) and 1c,d; 2c,d (right diagram). Table 5. Calculated values of chemical shifts of different protons compared with experimental values (in brackets). Bold font indicates the discrepancy more than 0.1 ppm between experiment and calculations. «MestReNova 10.0.2-15465 (2015-06-17), Modgraph NMR Predict Desktop, shift algorithm “Best”», 400 MHz, CDCl3* (GMMX: 5, points: 32K, increment/conformer method) # (CH3)2 CH2 Ortho-H Meta-H 1.39 (1.39) 2.50 (2.59) 7.36 (7.29) 1a 7.80 (7.54) 1.39 (1.21) 7.37 (7.31) 2a 3.20 (3.33) 7.59 (7.41) 1.40 (1.39) 2.50 (2.60) 1b 7.77 (7.49) 7.12 (6.99) 3.20 (3.27) 2b 1.39 (1.20) 7.56 (7.35) 7.13 (7.00) 7.37 (7.30) 1c 1.21 (1.61) 7.71 (7.49) 7.38 (7.34) 2c 1.46 (1.35) 7.59 (7.36) 1d 1.22 (1.61) 7.69 (7.45) 7.13 (7.01) 7.14 (7.07) 2d 1.46 (1.34) 7.57 (7.29) *Using of DMSO-d6 does not lead to changes of chemical shifts of ortho-protons in 1a-d. Table 6. Calculated values of chemical shifts of different protons of 1a compared with experimental values. Bold font indicates the discrepancy more than 0.1 ppm between experiment and calculations.

# 1a (calc) 1a (exp) 1a (MestReNova) Δ (calc - exp)

B3LYP/6-311+G(2d,p) GIAO, relatively TMS (CH3)2 CH2 Ortho-H 1.12 2.25 7.67 1.39 2.59 7.54 1.39 2.50 7.80 -0.27 -0.34 +0.14

Meta-H 7.16 7.29 7.36 -0.13

S4

III. 1H NMR spectra of the compounds 1-2 a,b with addition of CF3COOH H NMR spectra were measured in tetrachloromethane solution at 22 оС using internal (СН3)4Si (0 ppm) standard. Sample volume was 0.7 ml where 5 mg of 1-2 a,b was dissolved. 1

Table 7. Chemical shifts of ortho-protons of 1 a,b for different concentrations of CF3COOH (CCl4 solution). Mol. ratio CF3COOH / compound

Ortho-H 1a

2a

Δ1

1b

2b

Δ2

0 4

7.49 7.47

7.35 7.35

+0.14 +0.12

7.48 7.45

7.33 7.33

+0.15 +0.12

20

7.42 7.37

7.35 7.34

+0.07 +0.03

7.42 7.38

7.33 7.33

+0.09 +0.05

100

Table 8. Chemical shifts of meta-protons of 1 a,b for different concentrations of CF3COOH (CCl4 solution). Mol. ratio CF3COOH / compound

Meta-H 1a

2a

Δ1

1b

2b

Δ2

0 4

7.22 7.24

7.24 7.25

-0.02 -0.01

6.93 6.95

6.96 6.98

-0.03 -0.03

20

7.27 7.31

7.29 -

-0.02 -

6.98 7.00

6.99 7.00

-0.01 0

100

Table 9. Chemical shifts of para-protons of 1 a,b for different concentrations of CF3COOH (CCl4 solution). Mol. ratio CF3COOH / compound

Para-H 1a

2a

Δ1

0 4

7.16 7.18

7.17 7.19

-0.01 -0.01

20

7.23 7.28*

7.23 7.30*

0 -0.02

100

*Edge of the multiplet was used Table 10. Chemical shifts of ortho-protons of 1,2 a for different concentrations of CF3COOH (n-hexane solution). Mol. ratio CF3COOH / compound

0 4

Ortho-H

Meta-H

1a*

2a*

Δ1

1a*

2a*

Δ2

7.60 7.54

7.40 7.40

+0.20 +0.14

7.20 7.22

7.22 7.25

-0.02 -0.03

*Internal standard is CHCl3 (7.260 ppm)

S5

IV. 1H NMR spectra of the compounds 1-2 a,b at different temperatures H NMR spectra were measured in nonane solution in the wide range of temperatures (from -45 to +140 оС) using internal CHCl3 (7.26 ppm) standard. 1

Table 11. Temperature dependence of the chemical shifts of ortho-protons of the compounds 1-2 a,b. This dependence was fitted to the following function: ∆δa [δHortho (1) - δHortho (2)] = - 5·10-4T + 0.344 (R2 = 0.96), ∆δb [δHortho (1) δHortho (2)] = - 3·10-4T + 0.182 (R2 = 0.94). Temperature Ko

Ortho-H 1a

2a

Δ1

1b

2b

Δ2

228 268

7.75 7.73

7.50 7.51

0.25 0.22

7.55 7.55

7.42 7.44

0.13 0.11

298

7.72 7.70 7.69 7.68

7.52 7.52 7.52 7.52

0.20 0.18 0.17 0.16

7.54 7.53 7.52 7.52

7.44 7.45 7.44 7.45

0.1 0.08 0.08 0.07

338 373 413

Table 12. Temperature dependence of the chemical shifts of meta-protons of the compounds 1-2 a,b. This dependence was fitted to the following function: ∆δa [δHmeta (1) – δHmeta (2)] = - 9·10-5T + 0.013 (R2 = 0.89), ∆δb [δHmeta (1) – δHmeta (2)] = + 2·10-5T - 0.139 (R2 = 0.26). Temperature Ko

Meta-H 1a

2a

Δ1

1b

2b

Δ2

228 268

7.34 7.32

7.33 7.33

0.01 -0.01

6.89 6.89

7.02 7.02

-0.13 -0.13

298

7.32 7.32 7.31 7.31

7.34 7.34 7.33 7.33

-0.02 -0.02 -0.02 -0.02

6.89 6.89 6.89 6.89

7.03 7.02 7.02 7.02

-0.14 -0.13 -0.13 -0.13

338 373 413

Table 13. Temperature dependence of the chemical shifts of СH2- protons of the compounds 1-2 a,b. This dependence was fitted to the following function: ∆δa [δHCH2 (1) – δHCH2 (2)] = - 2·10-4T - 0.655 (R2 = 0.69), ∆δb [δHCH2 (1) – δHCH2 (2)] = + 1.7·10-4T - 0.851 (R2 = 0.89). Temperature Ko

CH2-group 1a

2a

Δ1

1b

2b

Δ2

228 268

2.58 2.57

3.28 3.29

-0.70 -0.72

2.46 2.46

3.27 3.26

-0.81 -0.80

298

2.58 2.58 2.58 2.58

3.30 3.30 3.30 3.31

-0.72 -0.72 -0.72 -0.73

2.47 2.47 2.48 2.49

3.27 3.26 3.27 3.27

-0.80 -0.79 -0.79 -0.78

338 373 413

S6

V. Calculated frequencies of CO vibrations in IR spectra. Table 14. Calculated values of the frequency of carbonyl group oscillations (1st column), including corrected (2nd column) and experimental (3rd column) frequencies of carbonyl vibrations (in cm-1) Basis 6-31 G*, PBE1PBE, PCM (CCl4). Vibrational scaling factor: 0.986 ± 0.026 (http://cccbdb.nist.gov/vibscale.asp)

#

ν(СO)calc.

ν(CO)corr.

ν(CO)exp.

1a

1834.5

1808.8 ± 48

1755.8

2a

1841.4

1815.6 ± 48

1760.1

1b

1834.5

1808.8 ± 48

1757.1

2b

1843.1

1817.3 ± 48

1762.0

1c

1811.6

1786.2 ± 47

1691.7

2c

1820.3

1794.8 ± 47

1695.3

Comment 1: the error of ν(СO) calculations (± 2.5 %) in 10 times greater than Δ ν(СO) which characterizes our weak H-bond. This situation makes difficult a correct QC evaluation of the H-bond influence. Comment 2: the assumption about completely harmonic nature of C=O vibrations and isolation of this group allows us to make a very simple estimate of the weak H-bond energy.

EC

O

m Abreak 2

2

2 2

;

EC

O

EC

2 1

0 O

2 0

2

EC O ;

EC

O

5.7 10

3

EC

O

0

Where Abreak – is a formal the amplitude of oscillation with the total break of C=O bond, m – is the reduced mass in the CO system, ω – is a cyclic frequency of vibrations, ν – is a vibration frequency in IR spectra. In our case Δν ≤ 5 cm-1, and EC=O ≈ 530 kJ mol-1 that leads to the value EH-bond = ΔEC=O = 3 kJ mol-1 that corresponds to the energy estimation (4-7 kJ mol-1) based on the temperature gradient of chemical shifts in 1 H NMR spectra with good accuracy.

S7

VI. Hydrogen bond energy estimation based on the temperature gradient of chemical shifts in 1H NMR spectra of studied compounds in nonane solution. To simplify estimation of the hydrogen bond energy we made the following assumptions: 1. Molecule can exist in only two possible states: hydrogen-bound state (H-bond is formed) or hydrogennonbound state (H-bond is not formed); there is a fast exchange between these two states. 2. The probability of the population of hydrogen-bound state in volume is the linear function from the average chemical shift of the ortho-protons of all molecules and can take values between P1 (probability to find the molecule with hydrogen bond at 413 oK) and P0 (probability to find the molecule with hydrogen bond at 228 o K). 3. The temperature dependence of other factors effected on the values of chemical shift of the ortho-protons is assumed to be compensated by the analysis of the temperature dependence of the difference of the chemical shifts between regioisomers 1a-2a and 1b-2b, i.e. Δ = δ(1) - δ(2). 4. It was assumed that P0 , P1 0 and ΔH < 0. Basically, to find the values of the four unknowns (A, Ebond, P0 , P1), one should solve the system of four logarithmic equations (eq. 4):

S8

ln P0 X 0

P1 (1 X 0 )

ln 1 P0 X 0

P1 (1 X 0 )

A EY0

ln P0 X 1 P1 (1 X 1 )

ln 1 P0 X 1 P1 (1 X 1 )

A EY1

ln P0 X 2

P1 (1 X 2 )

ln 1 P0 X 2

P1 (1 X 2 )

A EY2

ln P0 X 3

P1 (1 X 3 )

ln 1 P0 X 3

P1 (1 X 3 )

A EY3

(4)

where indices i,j are related to i,j experimental values:

j

Xj

min

max

1 RTi

, Yi

min

However, during the analysis of the system of equations, the significant instability of the system is observed, which is related with logarithmic function features and redundancy of experimental points; the choice of different quarters of experimental points among fifteen sets resulted in different solutions. In order to overcome this problem, assumption #4 (P0 , P1 2sigma(I)) and wR2 was 0.1642 (all data).

Table 25. Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for 1a. Ueq is defined as 1/3 of of the trace of the orthogonalised UIJ tensor.

Atom O1 O2 C14 C5 C13 C9 C8 C11 C19 C10 C3 C12 C2 C4 C15 C7 C6 C18 C17 C16 O9

x

y

z

U(eq)

3041.1(8) 3278.2(9) 2359.2(10) 3517.8(10) 2611.4(11) 2657.4(11) 2704.1(9) 2427.3(10) 2095.2(12) 2523.3(11) 3295.3(10) 2468.5(11) 2844.5(10) 3752(1) 2160.0(13) 3391.9(11) 3834.7(11) 1634.9(12) 1438.1(11) 1703.0(13) 4307.1(9)

2327(2) 2509(3) 3055(3) 3191(3) -397(3) -216(3) 452(3) -2533(3) 3643(3) -1696(3) 2503(3) -1872(3) 2102(3) 2834(3) 3260(3) 4835(3) 2657(3) 4420(3) 4610(3) 4061(4) 5848(2)

5715.3(16) 8561.7(17) 7010(2) 5732(2) 5994(2) 7969(2) 6936(2) 7122(2) 6110(3) 8066(2) 7567(2) 6097(2) 6791(2) 6857(2) 8057(3) 5630(3) 4760(2) 6262(3) 7318(3) 8206(3) 3680.4(17)

18.0(4) 26.4(5) 16.8(5) 18.0(5) 18.6(5) 19.7(6) 16.6(5) 18.6(6) 22.4(6) 19.6(6) 17.7(5) 19.7(6) 16.8(5) 20.3(6) 24.7(6) 23.3(6) 21.5(6) 26.4(7) 25.5(7) 28.8(7) 24.6(4)

S38

O10 C33 C35 C42 C46 C51 C54 C64 C69 C97 C101 C104 C117 C122 C125 C128 C129 C135 C156 O3 O4 C32 C40 C41 C43 C44 C58 C83 C84 C86 C90 C107 C112 C113 C124 C134 C136 C141 C152 O13 O14 C21 C39 C48 C71 C77 C81 C89

4594.4(8) 4916.9(9) 5173.8(11) 5182.9(10) 5377.7(12) 4927.7(11) 4106.0(11) 5253.5(11) 4307(1) 5589.8(12) 5063.7(11) 6048.5(12) 5830.3(13) 6169.4(12) 3859.3(11) 4775.5(10) 5043.0(11) 3817.7(11) 4219.5(12) 9594.1(8) 9306.1(9) 9916(1) 10173.6(11) 9105.8(11) 10182.8(10) 9926.4(11) 10379.0(12) 10253(1) 9305.9(10) 11046.6(12) 10041.4(11) 10064.1(11) 11168.7(11) 10590.7(12) 9775.6(10) 8817.6(11) 10829.3(13) 8859.4(11) 9218.7(12) 814.1(9) 525.6(8) 203.2(9) -65(1) 192.4(11) -258.2(12) -711.7(13) -53.2(11) 77.1(11)

5777(2) 7721(3) 9864(3) 10709(3) 4600(3) 8582(3) 4957(3) 5120(3) 5761(3) 4832(3) 10067(3) 4051(3) 3805(4) 3551(3) 5399(3) 6072(3) 8353(3) 5486(3) 3306(3) 5773(2) 5849(2) 7717(3) 9859(3) 4957(3) 10710(3) 8586(3) 4600(4) 5118(3) 5762(3) 4055(4) 8354(3) 10070(3) 3548(3) 4835(3) 6070(3) 5483(4) 3805(4) 5395(3) 3303(3) 848(2) 779(2) 2718(3) 5713(3) 3583(3) -403(3) -1201(4) 4856(3) 3354(3)

846.5(16) 2029(2) 3103(3) 2166(2) 3246(3) 1096(2) 862(2) 2205(2) 2683(2) 1338(3) 1147(2) 1524(3) 3425(3) 2560(3) 1944(3) 1938(2) 3049(2) -163(2) 812(3) 3567.1(16) 738.0(17) 2377(2) 1301(2) 3562(2) 2260(2) 3326(3) 1165(3) 2212(2) 1729(2) 2893(3) 1373(2) 3258(3) 1855(3) 3077(2) 2478(2) 4579(3) 988(3) 2469(2) 3607(3) 8678.7(17) 5847.1(16) 7031(2) 7165(2) 6088(2) 8243(3) 8425(3) 8105(2) 8047(3)

19.5(4) 17.0(5) 21.1(6) 17.8(5) 24.1(6) 20.8(6) 19.9(6) 17.2(5) 18.6(6) 22.8(6) 20.8(6) 25.9(6) 27.3(7) 27.3(7) 21.7(6) 17.5(5) 20.2(6) 23.8(6) 25.9(6) 19.7(4) 24.3(4) 17.4(5) 20.0(6) 19.9(6) 17.3(5) 21.6(6) 24.3(6) 17.1(5) 18.1(6) 25.2(6) 20.9(6) 22.2(6) 26.7(7) 22.1(6) 17.8(5) 24.8(6) 26.9(6) 20.9(6) 26.7(6) 24.4(5) 19.3(4) 16.5(5) 18.0(5) 21.3(6) 23.4(6) 26.7(6) 20.2(6) 21.3(6)

S39

C95 C98 C102 C105 C111 C115 C120 C126 C142 O16 O15 C34 C52 C60 C67 C68 C74 C79 C87 C92 C99 C114 C118 C119 C131 C132 C133 C137 C155 O18 O17 C20 C22 C24 C31 C36 C49 C53 C61 C73 C82 C108 C116 C123 C127 C139 C151 C154

813.9(10) 58.0(12) -468.9(12) -132(1) 1014.2(11) -928.9(12) 1260(1) 343.6(10) -1049.7(12) 5812.9(9) 5525.7(8) 5204.1(9) 5193.3(11) 4935.7(10) 4947.0(11) 4743.3(12) 5814.1(10) 5078.3(11) 4530.6(12) 6013.7(11) 5055.7(11) 3952.4(12) 4289.5(13) 4867.2(10) 6259.6(10) 5343.2(10) 4074.4(12) 6303.3(11) 5901.3(12) 8042.1(8) 8278.5(9) 8517.1(10) 7360.2(10) 7611.0(11) 7657.0(11) 7703.9(10) 7427.8(10) 7522.7(11) 7467.3(11) 7095.0(12) 8294.5(10) 7843.5(10) 8753.9(10) 8389.4(11) 7160.6(12) 8832.4(11) 6706.0(13) 6437.8(11)

759(3) 5067(3) -168(3) 120(3) -42(3) -959(4) 399(3) 1072(3) -1449(3) 850(2) 773(2) 2716(3) 3587(3) 5710(3) 4859(3) -404(3) 762(3) 3354(3) -161(3) -42(3) 5061(4) -1449(3) -1199(4) 117(3) 399(3) 1072(3) -947(3) 482(4) -1691(3) 2327(2) 2505(3) 3192(3) 3051(3) -393(3) -212(3) 445(3) -2533(3) -1698(3) -1878(3) 3644(3) 2501(3) 2094(3) 2838(3) 4840(3) 3264(4) 2655(3) 4058(4) 4615(3)

7684(2) 6146(2) 6334(2) 7207(2) 5854(2) 6530(3) 6949(2) 6935(2) 7559(3) 5737.7(17) 8569.4(16) 7381(2) 8330(2) 7258(2) 6302(3) 6165(2) 6734(2) 6371(3) 8075(2) 8565(2) 8263(3) 6856(3) 5992(3) 7212(2) 7469(2) 7480(2) 7893(3) 9583(3) 8609(3) 8703.2(16) 5857.4(17) 8684(2) 7404(2) 8413(2) 6444(2) 7483(2) 7289(2) 6357(2) 8320(2) 8307(3) 6843(2) 7618(2) 7558(2) 8783(3) 6357(3) 9660(2) 6205(3) 7100(3)

17.6(5) 22.1(6) 21.7(6) 17.2(5) 19.8(6) 26.0(7) 20.1(6) 18.0(5) 27.5(7) 24.4(5) 19.3(4) 16.7(5) 21.7(6) 17.4(5) 21.1(6) 23.1(6) 18.2(5) 22.1(6) 22.1(6) 20.0(6) 22.5(6) 26.4(7) 27.3(7) 17.3(5) 20.3(6) 18.4(5) 25.0(6) 24.5(6) 26.9(6) 17.9(4) 26.4(5) 17.7(5) 17.0(5) 19.6(6) 19.9(6) 17.9(6) 18.1(6) 19.3(6) 20.0(6) 22.1(6) 18.0(5) 16.2(5) 20.8(6) 22.7(6) 25.1(6) 21.1(6) 29.2(7) 25.7(7)

S40

C158 O12 O11 C25 C27 C30 C37 C47 C50 C70 C72 C75 C76 C78 C88 C100 C121 C144 C145 C146 C157 O7 O8 C26 C28 C38 C45 C57 C62 C63 C65 C66 C91 C93 C94 C96 C109 C143 C147 C159 C160 C1 C1A

6633.9(12) 2079.1(8) 1841.7(9) 2761(1) 2414.8(10) 2461.9(11) 1601.9(10) 2508.5(11) 3026.1(12) 2691.3(10) 1366.6(10) 2596.9(11) 1825.8(10) 2650.7(11) 2277.7(10) 1728.5(11) 2961.0(13) 3417.6(13) 1287.3(11) 3487.5(12) 3683.1(11) 7079.0(8) 6840.9(9) 7415.8(10) 7760.4(10) 7508.3(11) 7462.5(11) 6601.7(10) 7651.8(11) 8027.3(11) 7690.9(10) 7597.3(11) 7961.4(13) 6825.4(10) 6729.8(11) 7276.8(10) 6365.3(11) 8414.4(13) 8485.9(12) 6288.4(11) 8682.7(11) 901.6(12) 1302.6(11)

4414(3) 7328(2) 7509(3) 8053(3) 5451(3) 4785(3) 8192(3) 4603(3) 8635(3) 2470(3) 7837(3) 3294(3) 7497(3) 3117(3) 7098(3) 9845(3) 8260(3) 9057(4) 7657(3) 9420(4) 9610(3) 7324(2) 7504(3) 5442(3) 8048(3) 4604(3) 4785(3) 8186(3) 3120(3) 8642(3) 2470(3) 3295(3) 8267(3) 7506(3) 9837(3) 7096(3) 7836(3) 9054(4) 9410(4) 7657(3) 9616(3) -1699(3) 483(3)

8149(3) 714.7(16) 3562.3(17) 2008(2) 1934(2) 2974(2) 732(2) 994(2) 1116(2) 2122(2) 1853(2) 3066(2) 2571(2) 1097(2) 1795(2) 631(3) 3060(3) 3201(3) -244(2) 1259(3) 2320(3) 3699.1(16) 857.3(17) 2481(2) 2399(2) 3415(2) 1446(2) 3689(2) 3322(2) 3300(3) 2291(2) 1353(2) 1364(3) 1841(2) 3782(2) 2620(2) 2559(2) 1204(3) 3145(3) 4657(2) 2098(3) 5816(3) 4839(2)

26.7(7) 17.6(4) 26.0(5) 16.1(5) 17.1(5) 19.8(6) 18.1(5) 18.9(5) 21.7(6) 18.2(6) 20.9(6) 19.0(6) 17.4(5) 20.1(6) 16.1(5) 22.9(6) 24.5(6) 27.7(7) 20.9(6) 27.2(7) 25.8(7) 18.1(4) 26.1(5) 17.4(5) 17.0(5) 19.9(6) 19.5(5) 18.2(5) 20.2(6) 22.0(6) 17.8(5) 20.6(6) 25.1(6) 17.8(5) 22.1(6) 16.1(5) 21.2(6) 28.9(7) 27.3(7) 21.7(6) 25.8(7) 25.6(6) 23.7(6)

S41

Table 26. Anisotropic Displacement Parameters (Å2×103) for 1a. The Anisotropic displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…].

Atom O1 O2 C14 C5 C13 C9 C8 C11 C19 C10 C3 C12 C2 C4 C15 C7 C6 C18 C17 C16 O9 O10 C33 C35 C42 C46 C51 C54 C64 C69 C97 C101 C104 C117 C122 C125 C128 C129 C135 C156 O3 O4 C32 C40 C41 C43

U11

U22

U33

U23

U13

U12

21.5(9) 34.5(11) 12.6(12) 15.1(12) 19.6(13) 17.2(12) 8.8(11) 17.7(13) 26.2(14) 20.8(13) 18.0(12) 21.7(13) 15.9(12) 14.4(12) 30.1(15) 22.8(13) 20.4(13) 21.2(14) 13.1(12) 32.0(16) 33.0(11) 21.1(9) 9.9(11) 20.0(13) 13.5(12) 28.8(15) 19.9(13) 19.0(13) 15.0(12) 17.4(12) 25.3(14) 23.4(14) 21.9(14) 31.6(16) 18.2(14) 15.0(12) 15.8(12) 21.3(13) 21.9(13) 23.2(14) 21.6(9) 33.1(11) 11.2(11) 20.4(13) 19.4(13) 13.4(12)

17.8(9) 30.9(11) 13.2(12) 19.5(13) 20.0(13) 21.9(14) 16.3(13) 11.6(12) 19.1(13) 22.4(14) 13.3(12) 18.5(13) 18.1(13) 23.1(14) 20.2(14) 18.4(13) 23.2(14) 21.0(14) 13.8(13) 23.9(15) 24.4(10) 22.7(10) 12.7(12) 21.1(14) 16.9(13) 22.4(14) 21.2(14) 17.8(13) 9.3(11) 16.3(12) 21.0(13) 20.4(14) 21.4(14) 25.6(15) 20.3(14) 19.3(13) 15.2(12) 20.3(14) 27.8(15) 20.6(15) 22.6(10) 24.2(10) 12.4(12) 19.8(14) 17.2(13) 15.3(12)

14.8(9) 13.8(10) 24.6(15) 19.2(13) 16.3(13) 20.0(14) 24.8(14) 26.4(15) 21.9(15) 15.6(13) 21.6(14) 19.0(14) 16.4(13) 23.6(15) 23.8(15) 28.7(16) 20.9(14) 36.9(18) 50(2) 30.4(17) 16.3(10) 14.7(9) 28.3(15) 22.3(14) 23.2(14) 20.9(15) 21.1(14) 23.0(15) 27.2(15) 22.1(15) 22.0(14) 18.5(14) 34.4(17) 24.7(16) 43.3(19) 30.6(16) 21.4(14) 19.1(14) 21.8(15) 33.8(17) 15.1(9) 15.5(10) 28.7(15) 19.7(14) 23.1(14) 23.3(14)

-0.8(7) -2.0(9) -3.2(11) 0.2(11) 5.7(11) -6.7(11) -1.5(11) -2.1(11) -5.0(11) 1.0(11) -0.5(10) 0.3(11) -0.7(10) 1.5(11) 4.3(11) 0.0(12) 1.4(11) -1.6(13) -5.6(13) -3.2(13) 1.0(8) -2.4(8) -3.8(11) -3.2(11) -1.4(11) -4.2(12) -1.7(11) 1.1(11) -1.8(10) 1.8(11) -1.9(11) 3.9(11) -5.5(13) 2.2(12) -1.0(13) -0.1(12) 1.3(10) 5.0(11) -3.3(12) -3.6(13) 1.9(8) -0.9(8) 2.8(11) 2.3(11) 0.9(11) 0.0(11)

2.6(7) -1.4(8) 3(1) -0.7(10) -0.1(10) 1(1) 0.4(9) 1.3(10) 0.5(11) 0.1(10) -1.2(10) 0.8(10) -0.4(10) 0.6(10) 3.5(12) 3.6(11) 3(1) -9.8(12) 6.9(12) 16.0(13) 2.5(8) -0.1(7) 1.4(10) -2(1) -1(1) -1.3(11) -1.7(10) -1.7(10) -1.9(10) 1.5(10) -0.4(11) 0.8(10) 5.9(12) -14.8(12) -9.4(12) 0.3(11) -0.9(10) -0.5(10) -4.8(11) 0.2(12) -0.2(7) -2.3(8) -2.4(10) 0.8(10) 0.9(10) 0.6(10)

-1.6(7) -2.0(9) -2.6(9) 1.5(10) -0.4(10) -3.4(10) 2.5(9) -0.3(10) -0.1(11) -0.1(10) -1.6(9) -1.2(10) -2.3(10) -2.6(10) 1.7(11) -0.4(10) 1(1) 2.2(11) -2(1) -0.3(12) -3.6(9) -0.4(8) -0.4(9) -0.8(10) -4.1(9) 1.6(11) -1.2(10) -1.5(10) -3.2(9) 1.8(10) 0.4(11) -3.0(11) 0.8(11) 0.0(12) 0.3(11) 0.5(10) -0.8(10) -0.8(10) -1.0(11) -0.5(11) -0.7(8) -3.0(9) 0.0(9) -2(1) -1(1) -3.3(9)

S42

C44 C58 C83 C84 C86 C90 C107 C112 C113 C124 C134 C136 C141 C152 O13 O14 C21 C39 C48 C71 C77 C81 C89 C95 C98 C102 C105 C111 C115 C120 C126 C142 O16 O15 C34 C52 C60 C67 C68 C74 C79 C87 C92 C99 C114 C118 C119 C131

20.0(13) 28.4(15) 14.4(12) 15.9(12) 21.7(14) 20.8(13) 22.9(14) 16.2(13) 25.4(14) 17.0(12) 20.9(13) 32.9(16) 14.7(12) 25.9(15) 32.4(11) 20.3(9) 8.9(11) 15.9(12) 21.0(13) 26.4(14) 31.5(16) 19.4(13) 20.0(13) 15.6(12) 24.9(14) 26.9(14) 14.9(12) 17.1(13) 19.9(13) 11.4(12) 17.5(12) 17.3(13) 33.7(11) 20.8(9) 8.0(11) 19.9(13) 14.6(12) 19.5(13) 26.8(14) 15.5(12) 18.9(13) 25.4(14) 19.2(13) 23.4(14) 17.6(13) 32.9(16) 12.6(12) 13.3(12)

23.2(14) 25.4(15) 10.3(12) 15.6(12) 22.2(14) 19.7(14) 20.7(14) 20.3(14) 19.0(13) 16.3(13) 28.5(15) 25.6(15) 21.5(14) 18.2(14) 25.0(11) 22.3(10) 14.3(13) 15.3(12) 22.5(14) 23.1(14) 23.4(14) 19.6(14) 20.9(14) 15.3(12) 24.6(15) 18.2(13) 11.9(12) 17.1(13) 24.5(14) 20.4(13) 14.6(12) 17.7(13) 24.3(11) 23(1) 15.1(13) 25.0(15) 16.0(12) 22.9(14) 23.4(14) 15.6(12) 20.8(14) 20.2(13) 17.4(13) 23.7(15) 16.6(13) 24.0(15) 13.7(12) 20.6(13)

21.4(15) 19.0(14) 26.7(15) 22.8(15) 31.8(17) 22.3(15) 23.2(15) 43.5(19) 21.9(14) 19.9(14) 25.0(15) 22.2(15) 26.5(15) 36.0(18) 15.9(10) 15.1(9) 26.4(15) 22.8(14) 20.4(14) 20.8(14) 25.3(16) 21.7(14) 23.0(15) 21.9(14) 16.7(14) 20.0(14) 24.9(14) 25.3(15) 33.5(17) 28.4(15) 21.9(14) 48(2) 15.3(10) 14.2(9) 27.0(15) 20.2(14) 21.6(14) 21.0(14) 19.2(14) 23.4(15) 26.6(16) 20.6(14) 23.4(15) 20.5(14) 45.0(19) 24.9(16) 25.7(14) 27.1(15)

2.6(11) 5.0(12) 1.7(10) -1.1(11) 6.1(12) -4.6(11) -4.6(11) 1.5(13) -0.9(11) 1.5(11) 1.7(12) 0.5(12) 0.8(12) 4.5(12) 0.6(8) -2.7(8) -3.3(11) -1.9(11) -1.7(11) -3.6(12) 2.3(12) -4.2(11) 4.2(12) 1.6(11) 3.1(11) 2.0(11) -1.7(11) -1.6(11) -4.8(13) -0.1(11) 1.2(11) -1.4(13) 0.0(8) 2.8(8) 3.7(11) 2.0(12) 0.4(11) 1.4(11) 4.7(11) -0.3(11) -3.6(12) 0.3(11) -0.2(11) -3.0(12) 3.1(13) -1.6(12) 0.3(11) 2.2(11)

-0.1(10) 0.9(11) 0.8(10) 0(1) -6.7(12) -0.9(10) -2.7(11) 8.9(12) -0.2(11) 0.7(10) 4.5(11) 12.1(12) -0.6(10) 0.1(12) -2.3(8) -0.5(7) -1.1(9) -0.2(10) 0(1) 0.5(11) 14.6(12) 1.5(10) -1.6(10) -1.6(10) -1.7(11) 0.8(11) 2.8(10) -0.2(10) -5.1(12) -0.6(10) 0.1(10) 8.8(12) 1.4(8) 0.1(7) 0.5(9) 0.7(10) -1(1) -1.4(10) 0.1(11) 0.8(10) 1.2(11) -1.2(11) -0.5(10) 1.2(11) -9.6(12) -13.9(12) -2(1) 0.8(10)

-3.1(10) 1.2(12) -2.2(9) 1.2(9) 1.1(11) 0(1) -1.3(11) 0.7(11) 1.5(11) -0.3(10) -1.5(11) -0.5(12) 0.4(10) 0.7(11) 5.4(9) 2.0(8) 1.0(9) 3.4(10) 2(1) -1.0(11) 1.3(12) 1.3(10) 1.6(10) -1.8(9) 4.4(11) -0.7(11) 4.4(9) 3.6(10) -1.6(11) -0.2(10) 1.7(10) -0.2(10) 5.7(9) 2.1(8) -0.1(9) 2.6(11) 3.1(10) 2.3(11) -0.6(11) -1.1(10) -0.1(10) 1.3(11) 2.4(10) 3.8(11) 0.1(10) 1.7(12) 3.7(9) -0.4(10)

S43

C132 C133 C137 C155 O18 O17 C20 C22 C24 C31 C36 C49 C53 C61 C73 C82 C108 C116 C123 C127 C139 C151 C154 C158 O12 O11 C25 C27 C30 C37 C47 C50 C70 C72 C75 C76 C78 C88 C100 C121 C144 C145 C146 C157 O7 O8 C26 C28

16.0(12) 20.2(13) 20.7(13) 26.4(15) 22.8(9) 34.7(11) 19.0(12) 14.2(12) 20.3(13) 19.1(13) 9.4(11) 18.4(13) 19.7(13) 19.7(13) 25.0(14) 16.2(12) 15.6(12) 14.5(12) 23.1(13) 27.7(15) 19.6(13) 31.6(16) 14.8(13) 20.6(14) 21.4(9) 33.5(11) 14.1(12) 10.6(11) 18.3(12) 16.5(12) 18.9(13) 24.3(14) 16.5(12) 15.3(12) 19.5(13) 18.0(12) 21.1(13) 16.2(12) 21.6(13) 31.0(15) 29.5(15) 19.4(13) 21.6(14) 13.0(12) 22.4(9) 34.0(11) 10.5(11) 14.4(12)

19.3(13) 22.2(14) 29.8(15) 18.3(14) 16.9(9) 31.9(12) 17.8(13) 12.5(12) 18.1(13) 20.5(14) 19.1(14) 10.9(12) 20.3(14) 20.5(14) 19.2(13) 14.2(12) 18.5(13) 21.2(13) 18.9(13) 23.3(14) 22.7(14) 24.4(15) 14.7(13) 22.5(14) 17.2(9) 31.2(11) 10.0(11) 16.6(13) 19.6(14) 18.2(13) 20.2(14) 18.8(13) 11.2(12) 22.2(14) 19.6(14) 12.0(12) 17.4(13) 17.9(13) 17.7(13) 21.5(14) 23.0(15) 23.0(14) 25.0(15) 17.1(13) 16.8(9) 32.2(11) 17.2(13) 10.0(11)

20.0(14) 32.7(17) 23.1(15) 35.9(17) 14.1(9) 12.7(10) 16.3(13) 24.2(14) 20.6(14) 19.9(14) 25.0(14) 25.0(15) 17.9(14) 19.9(14) 22.1(15) 23.7(15) 14.5(13) 26.7(16) 26.0(15) 24.3(15) 20.8(14) 31.5(17) 48(2) 37.1(18) 14.3(9) 13.3(10) 24.2(14) 24.0(14) 21.4(14) 19.6(14) 17.4(14) 22.1(15) 27.0(15) 25.3(15) 17.8(14) 22.3(14) 21.7(14) 14.3(13) 29.4(16) 21.0(15) 30.6(17) 20.2(14) 34.9(17) 47(2) 15.3(10) 12.2(10) 24.4(14) 26.5(15)

0.3(11) 4.8(12) 1.3(12) 3.8(13) 0.4(7) 2.7(8) 2.3(10) 1.7(11) -4.1(11) 6.9(11) 0.7(11) -0.4(11) -1.6(11) 0.7(11) 4.1(11) 0.5(11) 1.2(10) -0.7(12) -1.3(12) -3.3(12) -0.8(11) 0.6(13) 5.0(13) 2.2(13) 0.0(7) -2.3(9) -1.9(10) -0.4(11) -7.9(11) -0.3(11) 5.3(11) -6.0(11) -1.6(11) 1.3(12) 1.0(11) -1(1) -2.0(11) 0(1) 1.4(12) 2.1(11) -1.8(13) 2.0(11) -4.3(13) -6.5(13) 0.2(7) 3.1(8) 0.6(11) 1.4(10)

0.2(10) 7.0(11) -4.7(11) 0.7(12) -2.3(7) 1.8(8) 0.9(10) -2.2(10) -0.3(10) -2(1) -2.7(10) -2.4(10) -0.3(10) 0.1(10) -1.6(11) -0.2(10) -0.8(9) -0.2(11) -3.9(11) -4.6(11) -2.4(10) -17.2(13) -6.7(12) 8.4(12) -2.5(7) 0.3(8) -4(1) -1.6(9) -2.5(10) -0.8(10) -0.2(10) -1.3(11) -3.1(10) -1.4(10) -0.5(10) -0.4(10) -1.2(10) -1.0(9) -3.6(11) -3.9(11) -16.0(13) -3.5(10) 8.6(12) -6.0(12) 1.8(7) -1.7(8) 2.6(9) 2(1)

-0.1(10) 0.0(11) 0.7(11) 0.4(11) -2.5(7) -2.1(9) 1.8(10) -3.7(9) -1.5(10) -2.2(10) 3.1(10) -0.2(10) -2.4(10) -0.2(10) 1.5(11) -2.3(9) -3(1) -2.9(10) -0.6(10) 1.1(11) 0.6(10) 0.3(12) -1.4(10) 3.0(11) 2.9(7) 4.2(9) 3.3(9) -0.9(9) 4.8(10) 0.2(10) 1.6(10) 1.5(11) 1.9(10) 4(1) 2.2(10) 2.4(9) 0.9(10) 3.8(10) 0.3(10) 1.2(11) 0.2(12) 1.1(10) -1.3(11) 0.9(10) 4.2(7) 3.5(9) -1.8(10) 3.2(9)

S44

C38 C45 C57 C62 C63 C65 C66 C91 C93 C94 C96 C109 C143 C147 C159 C160 C1 C1A

19.7(13) 17.8(12) 16.6(12) 20.3(13) 23.3(14) 15.7(12) 18.7(13) 30.2(15) 18.8(12) 24.3(14) 16.9(12) 16.9(13) 32.8(16) 20.8(14) 20.4(13) 13.3(13) 23.7(14) 21.4(13)

19.0(13) 21.6(14) 19.1(13) 18.7(14) 20.3(13) 11.9(12) 23.0(14) 20.6(14) 13.5(12) 17.9(13) 17.2(13) 21.0(13) 25.7(15) 23.2(15) 22.0(14) 17.9(13) 19.2(14) 27.1(15)

21.0(14) 19.0(14) 18.9(14) 21.6(14) 22.4(15) 25.8(15) 20.3(14) 24.5(15) 21.3(15) 23.9(15) 14.3(13) 25.6(15) 28.1(17) 38.0(18) 22.5(15) 46.3(19) 33.8(17) 22.8(15)

-4.8(11) 8.1(11) 0.0(11) 0.6(11) 4.6(11) 0.1(11) -1.2(11) -4.9(12) 2.5(10) -0.7(11) 1.8(10) -1.5(12) 0.9(13) 4.3(13) -1.0(11) 5.3(13) -1.7(12) -2.9(12)

-0.3(10) 1(1) -0.2(10) 0.7(10) 0.6(11) 1.5(10) 1.7(10) 3.9(12) -0.5(10) 3.1(11) 1.2(9) 0.7(11) 15.7(13) -7.9(12) 0.8(11) 6.7(12) 0.5(12) 3.4(11)

1.3(10) 3.2(10) -0.9(10) 1.6(10) 1.7(11) 1.7(10) 3.1(11) 1.7(11) 2.8(9) 1.5(10) 2.7(10) 2(1) 0.9(13) -2.1(11) -0.1(10) 2.1(10) -0.7(11) 2.1(11)

Table 27. Bond Lengths for 1a.

Atom Atom O1 C2 O1 C5 O2 C3 C14 C15 C14 C19 C14 C2 C5 C6 C5 C7 C5 C4 C13 C12 C13 C8 C9 C10 C9 C8 C8 C2 C11 C12 C11 C10 C19 C18 C3 C4 C3 C2 C15 C16 C18 C17 C17 C16 O9 C69 O10 C128 O10 C54

Length/Å 1.415(4) 1.461(3) 1.207(4) 1.384(4) 1.393(4) 1.547(3) 1.515(4) 1.526(4) 1.527(4) 1.388(4) 1.396(4) 1.386(4) 1.396(4) 1.543(4) 1.383(4) 1.394(4) 1.396(4) 1.494(4) 1.544(3) 1.399(4) 1.389(5) 1.370(5) 1.212(4) 1.430(3) 1.466(3)

Atom Atom O16 C74 O15 C132 O15 C92 C34 C79 C34 C52 C34 C132 C52 C99 C60 C99 C60 C67 C67 C79 C68 C119 C68 C118 C74 C131 C74 C132 C87 C119 C87 C133 C92 C155 C92 C137 C92 C131 C114 C133 C114 C118 C119 C132 O18 C108 O18 C20 O17 C82

Length/Å 1.211(4) 1.429(3) 1.463(3) 1.392(5) 1.395(4) 1.532(4) 1.381(4) 1.387(4) 1.392(4) 1.403(4) 1.392(4) 1.394(5) 1.495(4) 1.545(4) 1.385(5) 1.396(4) 1.519(4) 1.521(4) 1.527(4) 1.373(5) 1.383(5) 1.540(4) 1.428(3) 1.458(3) 1.196(4)

S45

C33 C33 C33 C35 C35 C42 C46 C46 C51 C54 C54 C54 C64 C64 C69 C69 C97 C104 C117 O3 O3 O4 C32 C32 C32 C40 C40 C41 C41 C41 C43 C44 C58 C58 C83 C83 C84 C84 C86 C86 C112 O13 O14 O14 C21 C21 C21 C39

C51 C129 C128 C42 C129 C101 C64 C117 C101 C125 C156 C135 C97 C128 C125 C128 C104 C122 C122 C124 C41 C84 C90 C44 C124 C43 C90 C134 C141 C152 C107 C107 C136 C83 C113 C124 C141 C124 C112 C113 C136 C95 C126 C111 C48 C89 C126 C81

1.373(5) 1.401(4) 1.537(4) 1.369(5) 1.408(4) 1.399(4) 1.385(5) 1.392(4) 1.388(4) 1.514(4) 1.521(4) 1.527(4) 1.391(4) 1.543(4) 1.502(4) 1.539(4) 1.401(4) 1.372(5) 1.387(5) 1.427(4) 1.464(3) 1.205(4) 1.385(5) 1.394(4) 1.536(4) 1.395(4) 1.405(4) 1.518(4) 1.523(4) 1.523(4) 1.376(5) 1.390(4) 1.387(4) 1.392(4) 1.390(4) 1.541(4) 1.501(4) 1.544(4) 1.376(5) 1.393(4) 1.391(5) 1.209(4) 1.426(3) 1.467(3) 1.385(5) 1.399(4) 1.535(3) 1.378(5)

C20 C20 C20 C22 C22 C22 C24 C24 C31 C31 C36 C49 C49 C73 C82 C82 C127 C151 C154 O12 O12 O11 C25 C25 C25 C27 C27 C27 C30 C37 C37 C37 C47 C50 C70 C70 C72 C76 C121 C144 C146 O7 O7 O8 C26 C26 C26 C28


1.518(4) 1.530(4) 1.531(4) 1.384(4) 1.400(4) 1.543(4) 1.380(5) 1.396(4) 1.391(4) 1.398(4) 1.542(4) 1.382(4) 1.388(4) 1.396(4) 1.504(4) 1.545(4) 1.392(4) 1.383(5) 1.382(5) 1.423(3) 1.463(3) 1.204(4) 1.385(5) 1.391(4) 1.542(4) 1.395(4) 1.402(4) 1.539(4) 1.396(4) 1.516(3) 1.525(4) 1.534(4) 1.398(4) 1.401(4) 1.377(4) 1.388(4) 1.505(4) 1.544(4) 1.396(5) 1.366(5) 1.393(5) 1.420(3) 1.461(3) 1.194(4) 1.383(4) 1.394(4) 1.545(3) 1.373(5)

S46

C39 C48 C71 C71 C77 C81 C95 C95 C102 C102 C105 C111 C111 C111 C115

C98 C98 C105 C77 C142 C89 C120 C126 C105 C115 C126 C1A C1 C120 C142

1.403(4) 1.387(4) 1.382(5) 1.396(5) 1.386(5) 1.399(4) 1.495(4) 1.546(4) 1.396(4) 1.410(5) 1.539(4) 1.516(4) 1.525(4) 1.526(4) 1.361(5)



1.400(4) 1.543(4) 1.396(4) 1.395(4) 1.505(4) 1.532(4) 1.534(4) 1.384(4) 1.388(5) 1.382(4) 1.386(5) 1.506(4) 1.549(4) 1.384(5) 1.382(5)

Table 28. Bond Angles for 1a.

Atom Atom Atom C2 O1 C5 C15 C14 C19 C15 C14 C2 C19 C14 C2 O1 C5 C6 O1 C5 C7 C6 C5 C7 O1 C5 C4 C6 C5 C4 C7 C5 C4 C12 C13 C8 C10 C9 C8 C13 C8 C9 C13 C8 C2 C9 C8 C2 C12 C11 C10 C14 C19 C18 C9 C10 C11 O2 C3 C4 O2 C3 C2 C4 C3 C2 C11 C12 C13 O1 C2 C8 O1 C2 C3 C8 C2 C3 O1 C2 C14 C8 C2 C14 C3 C2 C14

Angle/˚ 111.60(19) 119.0(3) 122.4(3) 118.5(2) 106.1(2) 109.8(2) 111.3(3) 103.6(2) 114.3(2) 111.3(2) 120.0(3) 121.0(2) 118.8(3) 118.6(3) 122.7(2) 119.3(3) 120.5(3) 119.9(3) 127.2(2) 125.7(3) 107.1(2) 121.0(2) 109.2(2) 104.8(2) 109.6(2) 111.8(2) 109.0(2) 112.3(2)

Atom Atom Atom C132 O15 C92 C79 C34 C52 C79 C34 C132 C52 C34 C132 C99 C52 C34 C99 C60 C67 C60 C67 C79 C119 C68 C118 O16 C74 C131 O16 C74 C132 C131 C74 C132 C34 C79 C67 C119 C87 C133 O15 C92 C155 O15 C92 C137 C155 C92 C137 O15 C92 C131 C155 C92 C131 C137 C92 C131 C52 C99 C60 C133 C114 C118 C114 C118 C68 C87 C119 C68 C87 C119 C132 C68 C119 C132 C74 C131 C92 O15 C132 C34 O15 C132 C119

Angle/˚ 112.2(2) 119.2(3) 121.7(2) 119.1(3) 120.0(3) 119.6(3) 119.3(3) 120.4(3) 127.7(3) 124.8(2) 107.5(2) 120.7(3) 120.4(3) 109.1(2) 105.5(2) 111.8(3) 103.5(2) 111.5(2) 114.8(3) 121.2(3) 119.6(3) 120.3(3) 118.9(3) 116.5(2) 124.5(3) 104.7(2) 109.5(2) 110.8(3)

S47

C3 C14 C17 C16 C17 C128 C51 C51 C129 C42 C35 C64 C33 O10 O10 C125 O10 C125 C156 C46 C46 C97 O9 O9 C125 C64 C51 C122 C122 C104 C69 O10 O10 C33 O10 C33 C69 C33 C124 C90 C90 C44 C43 O3 O3 C134 O3 C134

C4 C15 C18 C17 C16 O10 C33 C33 C33 C35 C42 C46 C51 C54 C54 C54 C54 C54 C54 C64 C64 C64 C69 C69 C69 C97 C101 C104 C117 C122 C125 C128 C128 C128 C128 C128 C128 C129 O3 C32 C32 C32 C40 C41 C41 C41 C41 C41


104.0(2) 120.2(3) 119.9(3) 119.7(3) 120.6(3) 111.5(2) 119.5(3) 119.6(2) 120.9(3) 120.4(3) 119.8(3) 120.8(3) 121.0(3) 104.0(2) 109.1(2) 112.0(3) 104.7(2) 114.6(2) 111.7(2) 118.7(3) 124.5(3) 116.7(3) 127.6(3) 125.0(2) 107.4(2) 120.3(3) 119.8(3) 120.5(3) 120.1(3) 119.6(3) 104.4(2) 109.0(2) 104.5(2) 108.9(2) 110.7(2) 109.5(2) 114.1(2) 119.5(3) 112.1(2) 119.2(3) 121.8(2) 118.9(3) 119.0(3) 105.3(2) 103.6(2) 114.8(2) 109.1(2) 111.8(3)

C34 O15 C34 C119 C114 C108 O18 O18 C139 O18 C139 C123 C127 C127 C73 C36 C53 C24 C24 C31 C53 C49 C49 C158 O17 O17 C116 O18 O18 C36 O18 C36 C22 C82 C22 C154 C158 C154 C88 C50 C50 C121 C47 C47 C30 C75 O12 O12

C132 C132 C132 C132 C133 O18 C20 C20 C20 C20 C20 C20 C22 C22 C22 C24 C31 C36 C36 C36 C49 C53 C61 C73 C82 C82 C82 C108 C108 C108 C108 C108 C108 C116 C127 C151 C154 C158 O12 C25 C25 C25 C27 C27 C27 C30 C37 C37


109.7(2) 104.2(2) 108.4(2) 114.1(2) 120.5(3) 111.6(2) 105.7(2) 109.7(2) 111.5(2) 103.9(2) 114.4(2) 111.1(3) 118.8(3) 122.4(2) 118.7(2) 120.5(2) 120.0(3) 119.3(3) 119.0(2) 121.7(3) 119.4(3) 120.6(2) 120.2(3) 120.2(3) 127.1(3) 125.6(2) 107.2(2) 108.9(2) 111.4(2) 109.4(2) 104.7(2) 110.0(2) 112.2(2) 103.9(2) 120.6(3) 120.6(3) 119.3(3) 120.5(3) 111.76(19) 118.8(3) 119.0(2) 122.1(3) 119.0(3) 118.8(3) 122.2(2) 120.5(2) 105.9(2) 103.8(2)

S48

C141 C107 C107 C136 C113 C113 C58 O4 O4 C141 C112 C32 C43 C86 C83 O3 O3 C32 O3 C32 C83 C58 C84 C126 C48 C48 C89 C81 C21 C105 C142 C39 C21 O13 O13 C120 C48 C105 C71 C71 C102 O14 O14 C1A O14 C1A C1 C142

C41 C43 C44 C58 C83 C83 C83 C84 C84 C84 C86 C90 C107 C112 C113 C124 C124 C124 C124 C124 C124 C136 C141 O14 C21 C21 C21 C39 C48 C71 C77 C81 C89 C95 C95 C95 C98 C102 C105 C105 C105 C111 C111 C111 C111 C111 C111 C115

C152 C40 C32 C83 C58 C124 C124 C141 C124 C124 C113 C40 C44 C136 C86 C32 C83 C83 C84 C84 C84 C112 C41 C111 C89 C126 C126 C98 C98 C77 C71 C89 C81 C120 C126 C126 C39 C115 C102 C126 C126 C1A C1 C1 C120 C120 C120 C102

111.5(2) 119.9(3) 119.9(3) 120.8(3) 118.6(3) 116.7(2) 124.6(3) 127.7(2) 125.1(3) 107.2(2) 120.6(3) 120.9(2) 121.0(3) 119.4(3) 120.4(3) 109.5(2) 110.7(2) 109.5(2) 104.5(2) 108.3(2) 114.1(2) 120.1(3) 104.7(2) 112.0(2) 119.4(3) 119.2(2) 121.3(3) 119.4(3) 120.5(3) 121.3(3) 119.7(3) 120.6(3) 119.9(3) 127.5(2) 125.0(2) 107.4(2) 120.2(3) 119.7(3) 118.5(3) 125.1(3) 116.3(3) 105.2(2) 109.3(2) 112.2(2) 103.5(2) 114.8(2) 111.2(3) 120.9(3)

C145 O12 C145 C72 C27 C25 C78 C76 C70 O11 O11 C72 C70 O12 O12 C27 O12 C27 C25 C25 C157 C157 C144 C96 C38 C38 C45 C91 C91 C63 C26 C26 O7 O7 C159 O7 C159 C94 C65 C147 C66 C65 C28 O8 O8 C109 O7 O7

C37 C37 C37 C37 C47 C50 C70 C72 C75 C76 C76 C76 C78 C88 C88 C88 C88 C88 C88 C121 C144 C146 C157 O7 C26 C26 C26 C28 C28 C28 C38 C45 C57 C57 C57 C57 C57 C57 C62 C63 C65 C66 C91 C93 C93 C93 C96 C96


114.5(2) 109.7(2) 111.3(2) 111.2(2) 120.0(3) 121.2(3) 120.2(3) 104.0(2) 119.7(3) 127.1(3) 125.8(2) 107.2(2) 120.6(2) 109.0(2) 111.5(2) 109.6(2) 104.6(2) 109.5(2) 112.6(2) 119.8(3) 121.4(3) 119.2(3) 119.6(3) 112.0(2) 119.3(3) 118.7(2) 122.0(3) 118.1(3) 123.2(2) 118.6(3) 120.3(2) 120.4(3) 106.3(2) 109.5(2) 111.6(2) 103.6(2) 114.6(2) 110.6(3) 120.0(3) 120.6(3) 120.1(3) 119.8(3) 121.6(3) 127.2(3) 125.7(2) 107.0(2) 111.9(2) 109.0(2)

S49

C95 O14 O14 C21 O14 C21 C105 C115

A C2 C2 C2 C12 C12 C10 C10 C15 C2 C8 C12 C10 C8 C5 C5 C5 C13 C9 C13 C9 C13 C9 O2 C4 O2 C4 O2 C4 C15 C19 C15 C19 C15 C19 O2 C2

C120 C126 C126 C126 C126 C126 C126 C142

B O1 O1 O1 C13 C13 C9 C9 C14 C14 C9 C11 C11 C13 O1 O1 O1 C8 C8 C8 C8 C8 C8 C3 C3 C3 C3 C3 C3 C14 C14 C14 C14 C14 C14 C3 C3

C111 C21 C105 C105 C95 C95 C95 C77

C C5 C5 C5 C8 C8 C8 C8 C19 C19 C10 C10 C12 C12 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C4 C4

104.6(2) 109.1(2) 111.0(2) 109.6(2) 104.4(2) 108.6(2) 113.8(3) 119.8(3)

C28 O7 C28 C26 C93 C160 C160 C147

C96 C96 C96 C96 C109 C143 C147 C160

C26 C93 C93 C93 C57 C91 C63 C143

Table 29. Torsion Angles for 1a. D Angle/˚ A B C D C6 148.8(2) C79 C34 C52 C99 C7 -90.8(3) C132 C34 C52 C99 28.1(3) C4 C99 C60 C67 C79 0.9(4) C9 C52 C34 C79 C67 C2 -178.0(2) C132 C34 C79 C67 0.2(4) C13 C60 C67 C79 C34 179.1(2) C2 C132 O15 C92 C155 -0.4(4) C18 C132 O15 C92 C137 175.4(3) C18 C132 O15 C92 C131 C11 -0.7(4) C34 C52 C99 C60 0.1(4) C9 C67 C60 C99 C52 1.0(4) C13 C133 C114 C118 C68 C11 -1.5(4) C119 C68 C118 C114 C8 -132.4(2) C133 C87 C119 C68 C3 -15.1(3) C133 C87 C119 C132 C14 106.9(2) C118 C68 C119 C87 O1 -21.9(3) C118 C68 C119 C132 O1 159.2(2) O16 C74 C131 C92 C3 -136.2(2) C132 C74 C131 C92 44.9(3) C3 O15 C92 C131 C74 C14 100.4(3) C155 C92 C131 C74 C14 -78.4(3) C137 C92 C131 C74 O1 177.1(3) C92 O15 C132 C34 -4.4(3) O1 C92 O15 C132 C119 C8 -65.8(3) C92 O15 C132 C74 C8 112.6(2) C79 C34 C132 O15 C14 55.5(4) C52 C34 C132 O15 -126.0(3) C14 C79 C34 C132 C119 -166.5(3) O1 C52 C34 C132 C119 17.8(3) O1 C79 C34 C132 C74 72.7(3) C8 C52 C34 C132 C74 C8 -102.9(3) C87 C119 C132 O15 C3 -49.0(4) C68 C119 C132 O15 C3 135.4(3) C87 C119 C132 C34 C5 -160.9(3) C68 C119 C132 C34 20.7(3) C5 C87 C119 C132 C74

109.3(2) 104.8(2) 112.0(2) 109.9(2) 104.0(2) 120.2(3) 120.5(3) 119.0(3)

Angle/˚ 0.4(4) -178.3(3) 0.2(4) 0.7(4) 179.3(3) -1.0(4) -92.0(3) 147.8(2) 26.8(3) -1.2(5) 0.9(5) -1.9(5) 1.4(5) -0.2(4) 176.4(3) -0.4(4) -176.7(3) -162.4(3) 19.7(3) -27.5(3) 89.7(3) -141.9(2) -130.3(2) 108.6(2) -14.5(3) 171.7(2) -9.6(3) -66.5(3) 112.1(3) 58.6(3) -122.7(3) 35.3(3) -148.2(3) -85.7(3) 90.8(3) 152.6(3)

S50

O1 C5 C4 C3 C6 C5 C4 C3 C7 C5 C4 C3 C19 C14 C15 C16 C2 C14 C15 C16 C14 C19 C18 C17 C19 C18 C17 C16 C18 C17 C16 C15 C14 C15 C16 C17 C129 C35 C42 C101 C129 C33 C51 C101 C128 C33 C51 C101 C128 O10 C54 C125 C128 O10 C54 C156 C128 O10 C54 C135 C117 C46 C64 C97 C117 C46 C64 C128 C46 C64 C97 C104 C128 C64 C97 C104 C33 C51 C101 C42 C35 C42 C101 C51 C64 C97 C104 C122 C64 C46 C117 C122 C97 C104 C122 C117 C46 C117 C122 C104 O9 C69 C125 C54 C128 C69 C125 C54 O10 C54 C125 C69 C156 C54 C125 C69 C135 C54 C125 C69 C54 O10 C128 C33 C54 O10 C128 C69 C54 O10 C128 C64 C51 C33 C128 O10 C129 C33 C128 O10 C51 C33 C128 C69 C129 C33 C128 C69 C51 C33 C128 C64 C129 C33 C128 C64 O9 C69 C128 O10 C125 C69 C128 O10 O9 C69 C128 C33 C125 C69 C128 C33 O9 C69 C128 C64 C125 C69 C128 C64 C46 C64 C128 O10 C97 C64 C128 O10 C46 C64 C128 C33

-28.9(3) -143.9(2) 89.0(3) -0.7(4) -176.3(3) 0.0(4) 1.4(5) -2.5(5) 2.1(5) -0.3(4) 0.3(4) -178.7(3) 27.3(3) -92.4(3) 148.0(2) 0.1(4) -176.9(3) -1.0(4) 176.2(3) -1.2(4) 1.2(4) 0.5(5) 1.4(5) 0.9(5) -1.8(5) -162.2(3) 20.1(3) -28.1(3) 89.6(3) -141.8(3) -130.8(2) -14.5(3) 108.7(2) -9.2(3) 171.8(2) -122.6(3) 58.4(3) 112.0(3) -67.0(3) 178.0(3) -4.2(3) -65.7(4) 112.1(2) 57.0(4) -125.2(2) -148.4(3) 34.6(3) 91.4(3)

C68 C119 C132 C74 O16 C74 C132 O15 C131 C74 C132 O15 O16 C74 C132 C34 C131 C74 C132 C34 O16 C74 C132 C119 C131 C74 C132 C119 C118 C114 C133 C87 C119 C87 C133 C114 C108 O18 C20 C139 C108 O18 C20 C123 C108 O18 C20 C116 C61 C24 C36 C31 C61 C24 C36 C108 C53 C31 C36 C24 C53 C31 C36 C108 C61 C49 C53 C31 C36 C31 C53 C49 C53 C49 C61 C24 C36 C24 C61 C49 C127 C22 C73 C158 C108 C22 C73 C158 C20 O18 C108 C36 C20 O18 C108 C22 C20 O18 C108 C82 C24 C36 C108 O18 C31 C36 C108 O18 C24 C36 C108 C22 C31 C36 C108 C22 C24 C36 C108 C82 C31 C36 C108 C82 C127 C22 C108 O18 C73 C22 C108 O18 C127 C22 C108 C36 C73 C22 C108 C36 C127 C22 C108 C82 C73 C22 C108 C82 O17 C82 C108 O18 C116 C82 C108 O18 O17 C82 C108 C36 C116 C82 C108 C36 O17 C82 C108 C22 C116 C82 C108 C22 O17 C82 C116 C20 C108 C82 C116 C20 O18 C20 C116 C82 C139 C20 C116 C82 C123 C20 C116 C82

-31.0(4) 177.9(3) -4.1(3) -65.5(3) 112.5(2) 57.0(4) -125.0(3) 1.3(5) -0.2(5) -148.8(2) 90.9(3) -28.0(3) -0.6(4) 177.9(2) -0.6(4) -179.0(2) 0.0(4) 0.8(4) -1.2(4) 1.5(4) 1.0(4) -174.9(3) 132.5(2) -106.7(2) 14.9(3) 22.1(3) -159.5(2) -99.9(3) 78.5(3) 136.3(3) -45.2(3) 166.2(3) -18.1(4) -73.3(4) 102.4(3) 49.2(3) -135.1(3) -177.2(3) 4.6(3) 65.9(4) -112.3(2) -56.2(4) 125.6(2) 161.1(3) -20.7(3) 28.9(3) 143.7(2) -89.0(3)

S51

C97 C64 C128 C33 C46 C64 C128 C69 C97 C64 C128 C69 C51 C33 C129 C35 C128 C33 C129 C35 C42 C35 C129 C33 C124 O3 C41 C134 C124 O3 C41 C141 C124 O3 C41 C152 C90 C40 C43 C107 C90 C32 C44 C107 C124 C32 C44 C107 C136 C58 C83 C113 C136 C58 C83 C124 C44 C32 C90 C40 C124 C32 C90 C40 C43 C40 C90 C32 C40 C43 C107 C44 C32 C44 C107 C43 C113 C86 C112 C136 C58 C83 C113 C86 C124 C83 C113 C86 C112 C86 C113 C83 C41 O3 C124 C32 C41 O3 C124 C83 C41 O3 C124 C84 C90 C32 C124 O3 C44 C32 C124 O3 C90 C32 C124 C83 C44 C32 C124 C83 C90 C32 C124 C84 C44 C32 C124 C84 C113 C83 C124 O3 C58 C83 C124 O3 C113 C83 C124 C32 C58 C83 C124 C32 C113 C83 C124 C84 C58 C83 C124 C84 O4 C84 C124 O3 C141 C84 C124 O3 O4 C84 C124 C32 C141 C84 C124 C32 O4 C84 C124 C83 C141 C84 C124 C83 C83 C58 C136 C112 C86 C112 C136 C58 O4 C84 C141 C41 C124 C84 C141 C41

-85.6(3) -30.9(4) 152.1(2) 0.6(4) 179.6(2) -0.6(4) -147.7(2) -26.8(3) 92.1(3) 0.1(4) -0.3(4) 178.5(3) 0.6(5) 177.0(3) -0.6(4) -179.4(2) 0.7(4) -1.0(4) 1.1(4) -0.8(5) 0.3(5) -176.3(3) -0.3(5) 130.4(2) -108.8(2) 14.5(3) -171.8(2) 9.4(3) 66.7(3) -112.1(3) -58.3(3) 122.9(3) -35.0(3) 148.6(3) 85.9(3) -90.6(3) -152.6(3) 31.0(4) -177.9(3) 3.9(3) 65.4(3) -112.8(3) -56.9(4) 125.0(3) -1.6(5) 1.7(5) 162.3(3) -19.5(3)

C73 C22 C127 C151 C108 C22 C127 C151 C22 C127 C151 C154 C127 C151 C154 C158 C151 C154 C158 C73 C22 C73 C158 C154 C47 C27 C30 C75 C88 C27 C30 C75 C88 O12 C37 C145 C88 O12 C37 C72 C88 O12 C37 C100 C30 C27 C47 C78 C88 C27 C47 C78 C121 C25 C50 C146 C88 C25 C50 C146 O12 C37 C72 C76 C145 C37 C72 C76 C100 C37 C72 C76 C78 C70 C75 C30 C27 C30 C75 C70 C37 C72 C76 O11 C37 C72 C76 C88 C75 C70 C78 C47 C27 C47 C78 C70 C37 O12 C88 C27 C37 O12 C88 C25 C37 O12 C88 C76 C47 C27 C88 O12 C30 C27 C88 O12 C47 C27 C88 C25 C30 C27 C88 C25 C47 C27 C88 C76 C30 C27 C88 C76 C50 C25 C88 O12 C121 C25 C88 O12 C50 C25 C88 C27 C121 C25 C88 C27 C50 C25 C88 C76 C121 C25 C88 C76 O11 C76 C88 O12 C72 C76 C88 O12 O11 C76 C88 C27 C72 C76 C88 C27 O11 C76 C88 C25 C72 C76 C88 C25 C50 C25 C121 C144 C88 C25 C121 C144 C25 C121 C144 C157

0.3(5) 176.0(3) -1.8(5) 1.9(5) -0.6(5) -0.8(5) -0.5(4) -178.7(2) -148.9(2) -28.1(3) 90.8(3) -0.5(4) 177.9(2) 0.0(4) -175.4(2) 28.7(3) 143.6(2) -89.2(3) -0.2(4) 0.8(4) 160.6(3) -20.4(3) -0.7(4) 1.1(4) 132.1(2) -106.8(2) 15.1(3) 22.4(3) -159.3(2) -99.8(3) 78.4(3) 136.3(2) -45.5(3) -18.4(3) 166.4(2) 102.3(3) -72.9(3) -135.6(3) 49.2(3) -176.7(3) 4.2(3) 66.6(3) -112.5(2) -55.6(4) 125.4(2) 0.8(4) 176.0(3) -1.9(4)

S52

O3 C41 C141 C84 C134 C41 C141 C84 C152 C41 C141 C84 C89 C21 C48 C98 C126 C21 C48 C98 C105 C71 C77 C142 C98 C39 C81 C89 C48 C21 C89 C81 C126 C21 C89 C81 C39 C81 C89 C21 C21 C48 C98 C39 C81 C39 C98 C48 C77 C71 C105 C102 C77 C71 C105 C126 C115 C102 C105 C71 C115 C102 C105 C126 C126 O14 C111 C1A C126 O14 C111 C1 C126 O14 C111 C120 C105 C102 C115 C142 O13 C95 C120 C111 C126 C95 C120 C111 O14 C111 C120 C95 C1A C111 C120 C95 C1 C111 C120 C95 C111 O14 C126 C21 C111 O14 C126 C105 C111 O14 C126 C95 C48 C21 C126 O14 C89 C21 C126 O14 C48 C21 C126 C105 C89 C21 C126 C105 C48 C21 C126 C95 C89 C21 C126 C95 C71 C105 C126 O14 C102 C105 C126 O14 C71 C105 C126 C21 C102 C105 C126 C21 C71 C105 C126 C95 C102 C105 C126 C95 O13 C95 C126 O14 C120 C95 C126 O14 O13 C95 C126 C21 C120 C95 C126 C21 O13 C95 C126 C105 C120 C95 C126 C105 C102 C115 C142 C77 C71 C77 C142 C115

27.4(3) 141.7(2) -89.8(3) 0.0(4) 178.9(3) -1.6(4) -0.4(4) -0.7(4) -179.5(2) 0.9(4) 0.5(4) -0.3(4) -0.1(4) 176.8(3) 0.9(4) -176.3(2) -147.9(2) 91.5(3) -27.1(3) 0.0(4) 162.5(3) -19.9(3) 27.8(3) 141.9(2) -89.4(3) 130.7(2) -108.4(2) 14.6(3) 9.5(3) -171.7(2) -112.3(3) 66.5(3) 122.8(3) -58.4(3) 148.4(3) -34.7(3) -91.0(3) 86.0(3) 30.9(4) -152.1(2) -178.3(3) 4.1(3) 65.4(4) -112.3(3) -57.0(4) 125.3(2) -1.6(4) 2.4(4)

C25 C50 C146 C157 C121 C144 C157 C146 C50 C146 C157 C144 C45 C26 C38 C62 C96 C26 C38 C62 C38 C26 C45 C66 C96 C26 C45 C66 C96 O7 C57 C159 C96 O7 C57 C94 C96 O7 C57 C109 C26 C38 C62 C65 C91 C28 C63 C147 C96 C28 C63 C147 C38 C62 C65 C66 C62 C65 C66 C45 C26 C45 C66 C65 C63 C28 C91 C143 C96 C28 C91 C143 C57 O7 C96 C28 C57 O7 C96 C26 C57 O7 C96 C93 C91 C28 C96 O7 C63 C28 C96 O7 C91 C28 C96 C26 C63 C28 C96 C26 C91 C28 C96 C93 C63 C28 C96 C93 C38 C26 C96 O7 C45 C26 C96 O7 C38 C26 C96 C28 C45 C26 C96 C28 C38 C26 C96 C93 C45 C26 C96 C93 O8 C93 C96 O7 C109 C93 C96 O7 O8 C93 C96 C28 C109 C93 C96 C28 O8 C93 C96 C26 C109 C93 C96 C26 O8 C93 C109 C57 C96 C93 C109 C57 O7 C57 C109 C93 C159 C57 C109 C93 C94 C57 C109 C93 C28 C91 C143 C160 C28 C63 C147 C160 C63 C147 C160 C143 C91 C143 C160 C147

0.3(4) 2.1(5) -1.3(4) 0.6(4) -177.8(2) 0.5(4) 178.9(3) 148.9(2) -90.3(3) 27.8(3) -1.5(4) -1.0(4) 175.1(3) 1.2(4) -0.1(4) -0.8(4) -0.1(4) -176.0(3) 106.9(2) -132.2(2) -14.6(3) -166.1(3) 18.0(3) 73.1(3) -102.7(3) -48.9(3) 135.3(2) -22.2(3) 159.4(2) 100.3(3) -78.1(3) -136.5(3) 45.1(3) 177.7(3) -4.8(3) 56.3(4) -126.2(2) -65.4(4) 112.1(2) -161.8(3) 20.8(3) -28.7(3) -144.1(2) 88.6(3) 1.4(5) 0.9(4) 0.4(5) -1.5(5)

S53

Table 30. Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement Parameters (Å2×103) for 1a.

Atom H13 H9 H11 H19 H10 H12 H4A H4B H15 H7A H7B H7C H6A H6B H6C H18 H17 H16 H35 H42 H46 H51 H97 H101 H104 H117 H122 H12D H12E H129 H13I H13J H13K H15G H15H H15I H40 H43 H44 H58 H86 H90 H107 H112

x

y

z

U(eq)

2645 2717 2337 2227 2497 2399 3980 3944 2330 3194 3707 3195 3902 4156 3647 1460 1128 1578 5255 5268 5156 4843 5510 5076 6273 5906 6477 3637 3657 5040 3750 3497 4025 4422 3901 4407 10254 10269 9841 10158 11270 10038 10076 11475

25 340 -3526 3517 -2130 -2424 1984 3672 2865 5001 5394 5146 1617 3186 2829 4809 5108 4222 10291 11708 4783 8163 5160 10633 3870 3444 3045 6255 4591 7779 6528 4960 5303 3095 2766 3016 10282 11708 8173 4789 3875 7776 10640 3039

5299 8602 7181 5403 8759 5467 6810 7142 8664 4972 5595 6260 4838 4738 4090 5658 7422 8915 3779 2206 3833 419 631 507 940 4125 2683 1848 2245 3685 -102 -226 -805 169 776 1460 623 2226 4005 577 3477 738 3897 1735

22 24 22 27 24 24 24 24 30 35 35 35 32 32 32 32 31 35 25 21 29 25 27 25 31 33 33 26 26 24 36 36 36 39 39 39 24 21 26 29 30 25 27 32

S54

H113 H13L H13M H13N H136 H14D H14E H15J H15K H15L H39 H48 H71 H77 H81 H89 H98 H102 H115 H12F H12G H142 H52 H60 H67 H68 H79 H87 H99 H114 H118 H13A H13B H133 H13C H13D H13E H15A H15B H15C H24 H31 H49 H53 H61 H73 H11A H11B

10512 9015 8488 8767 10904 8659 8636 9417 8900 9410 -154 276 -37 -787 -132 80 49 -390 -1153 1462 1482 -1358 5279 4848 4868 4965 5081 4609 5043 3645 4213 6483 6461 3852 6382 6618 6093 5691 6220 5722 7644 7716 7338 7496 7398 7226 8945 8983

5168 5249 4997 6534 3444 4583 6247 3022 2762 3081 6709 3165 -219 -1565 5279 2780 5637 161 -1149 -410 1254 -1948 3174 6707 5283 -221 2777 178 5628 -1955 -1563 1252 -412 -1131 1516 -69 330 -1904 -2229 -1983 34 345 -3527 -2133 -2428 3525 3679 1991

3782 5226 4617 4537 288 2169 2563 2973 3613 4264 7206 5410 8831 9124 8783 8684 5507 5627 5948 7250 6856 7681 9009 7224 5623 5577 5736 8779 8902 6736 5294 7561 7167 8478 9511 9657 10225 9240 8663 7951 9107 5811 7226 5664 8951 9015 7274 7604

27 37 37 37 32 25 25 40 40 40 22 26 28 32 24 26 26 26 31 24 24 33 26 21 25 28 27 26 27 32 33 24 24 30 37 37 37 40 40 40 24 24 22 23 24 27 25 25

S55

H12A H12B H12C H127 H13F H13G H13H H151 H154 H158 H30 H47 H50 H70 H72A H72B H75 H78 H10A H10B H10C H121 H144 H14A H14B H14C H146 H157 H38 H45 H62 H63 H65 H66 H91 H94A H94B H94C H10D H10E H143 H147 H15D H15E H15F H160 H1A H1B

8184 8703 8200 7332 8642 9152 8903 6581 6129 6457 2403 2476 2895 2782 1175 1137 2623 2719 1927 1414 1924 2791 3544 1478 968 1217 3661 3993 7475 7404 7721 7896 7780 7624 7790 6916 6416 6938 6137 6173 8538 8662 6207 5975 6483 8991 721 1220

5140 5403 5011 2872 2815 3192 1617 4216 5120 4794 5341 5026 8502 1477 8677 6990 2856 2560 10153 10404 10013 7867 9216 7821 8193 6619 9809 10111 5032 5343 2567 8522 1476 2858 7878 10014 10401 10130 6986 8676 9205 9787 6627 8219 7787 10125 -1986 -2237

8163 8797 9451 5750 10328 9692 9577 5496 6996 8753 3606 298 408 2182 2138 1806 3758 469 1259 600 -30 3669 3909 -912 -274 -163 654 2427 4109 814 3952 4008 2231 661 757 4453 3787 3164 2603 2278 493 3752 4564 4702 5323 1994 6473 5769

34 34 34 30 32 32 32 35 31 32 24 23 26 22 25 25 23 24 34 34 34 29 33 31 31 31 33 31 24 23 24 26 21 25 30 33 33 33 25 25 35 33 33 33 33 31 38 38

S56

693 1102 1628 1360

H1C H1AA H1AB H1AC

-1918 271 -20 1531

5183 4193 4792 4890

38 36 36 36

Crystal structure determination of 1b. Crystal Data for C18H16F2O2 (M =302.31 g/mol): N/A, space group P-1 (no. 2), a = 6.39427(18) Å, b = 10.2276(3) Å, c = 12.2323(4) Å, α = 111.528(3)°, β = 96.335(3)°, γ = 94.273(2)°, V = 733.88(4) Å3, Z = 2, T = 100(2) K, μ(CuKα) = 0.881 mm-1, Dcalc = 1.368 g/cm3, 14359 reflections measured (7.86° ≤ 2Θ ≤ 144.98°), 2892 unique (Rint = 0.0206, Rsigma = N/A) which were used in all calculations. The final R1 was 0.0330 (>2sigma(I)) and wR2 was 0.0861 (all data).

Table 31. Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for 1b. Ueq is defined as 1/3 of of the trace of the orthogonalised UIJ tensor.

Atom F1 F2 O1 O2 C2 C15 C14 C16 C8 C18 C13 C10 C3 C12 C6 C7 C17 C11 C4 C19 C5 C9

x

y

z

U(eq)

2715.7(12) -5715.7(12) 1856.3(11) -2209.7(12) 97.4(16) -977.4(17) -1561.7(16) -2374.4(18) 872.7(16) -5003.4(18) -613.9(17) 3625.1(17) -709.7(16) -2.0(18) 419.7(19) 4051.8(18) -4351.5(18) 2109.0(18) 762.4(18) -3584.3(17) 1777.3(17) 2989.3(17)

4796.1(7) 5877.6(8) 9347.0(7) 9644.4(8) 8632.3(11) 6789.4(11) 7894.4(11) 6091.2(11) 7572.6(10) 7602.4(12) 6546.2(11) 6712.7(12) 9811.0(11) 5606.2(11) 11281.4(12) 11566.3(11) 6532.7(12) 5719.8(11) 11151.9(11) 8281.9(11) 10881.6(10) 7656.3(11)

9485.0(6) 3218.7(6) 7157.7(6) 8916.7(6) 7430.0(9) 5378.1(9) 6322.7(9) 4332.3(10) 7947.6(9) 5157.7(10) 8016.8(9) 8922.4(9) 8442.4(9) 8537.5(9) 6706.9(10) 7840.9(10) 4250.8(10) 8978.8(9) 8737.0(9) 6206.6(10) 7613.3(9) 8408.3(9)

27.60(18) 30.10(18) 16.38(17) 19.92(18) 15.0(2) 17.8(2) 15.6(2) 20.5(2) 15.2(2) 22.3(2) 17.2(2) 20.2(2) 15.9(2) 19.3(2) 23.4(2) 22.0(2) 21.1(2) 19.5(2) 19.8(2) 19.1(2) 17.4(2) 17.8(2)

S57

Table 32. Anisotropic Displacement Parameters (Å2×103) for 1b. The Anisotropic displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…].


U11

U22

U33

U23

U13

U12

35.3(4) 31.6(4) 18.3(4) 19.2(4) 15.0(5) 21.0(5) 18.0(5) 29.0(6) 18.4(5) 17.1(5) 17.1(5) 19.1(5) 17.7(5) 23.9(6) 27.6(6) 24.0(6) 24.9(6) 28.3(6) 26.8(6) 20.2(5) 22.7(5) 17.9(5)

27.2(4) 29.2(4) 12.1(3) 23.8(4) 14.6(5) 16.5(5) 14.7(5) 15.5(5) 13.6(5) 26.8(6) 16.9(5) 22.8(5) 17.7(5) 16.2(5) 21.1(5) 16.2(5) 19.9(5) 17.7(5) 14.0(5) 19.5(5) 11.6(5) 17.1(5)

27.4(4) 20.3(3) 17.8(4) 16.2(4) 14.6(5) 16.8(5) 14.1(5) 14.9(5) 11.7(5) 23.0(6) 15.8(5) 16.1(5) 12.1(5) 17.7(5) 23.2(6) 23.7(6) 15.2(5) 13.9(5) 16.6(5) 16.5(5) 17.1(5) 15.5(5)

17.2(3) 4.8(3) 4.0(3) 6.1(3) 4.7(4) 7.0(4) 5.9(4) 3.7(4) 2.5(4) 10.6(5) 4.0(4) 4.6(4) 5.6(4) 5.8(4) 11.0(5) 6.1(4) 6.6(4) 6.3(4) 3.0(4) 5.2(4) 4.3(4) 3.5(4)

4.5(3) -9.6(3) 5.3(3) 4.6(3) 3.2(4) 3.8(4) 2.1(4) 3.4(4) 2.8(4) 0.5(4) 2.7(4) 0.2(4) -0.3(4) 5.4(4) 2.5(5) 3.0(4) -3.8(4) 3.8(4) 5.0(4) 3.4(4) 3.5(4) 1.4(4)

11.4(3) -7.5(3) 0.6(3) 4.4(3) 0.9(4) 3.1(4) -0.2(4) 0.7(4) 2.9(4) 0.3(4) 2.1(4) 4.8(4) 4.3(4) 1.0(4) 2.7(4) -0.9(4) -7.0(4) 8.1(4) 2.5(4) 2.7(4) 1.8(4) -0.2(4)

Table 33. Bond Lengths for 1b.

Atom Atom F1 C11 F2 C17 O1 C2 O1 C5 O2 C3 C2 C8 C2 C14 C2 C3 C15 C16 C15 C14 C14 C19 C16 C17

Length/Å 1.3629(12) 1.3612(12) 1.4314(12) 1.4671(12) 1.2069(13) 1.5284(14) 1.5307(14) 1.5464(14) 1.3880(15) 1.3971(14) 1.3882(15) 1.3793(17)

Atom Atom C8 C9 C8 C13 C18 C17 C18 C19 C13 C12 C10 C11 C10 C9 C3 C4 C12 C11 C6 C5 C7 C5 C4 C5

Length/Å 1.3913(15) 1.3954(15) 1.3713(17) 1.3954(15) 1.3904(15) 1.3767(16) 1.3927(15) 1.5056(15) 1.3772(16) 1.5242(15) 1.5162(15) 1.5270(14)

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Table 34. Bond Angles for 1b.

Atom Atom Atom C2 O1 C5 O1 C2 C8 O1 C2 C14 C8 C2 C14 O1 C2 C3 C8 C2 C3 C14 C2 C3 C16 C15 C14 C19 C14 C15 C19 C14 C2 C15 C14 C2 C17 C16 C15 C9 C8 C13 C9 C8 C2 C13 C8 C2 C17 C18 C19 C12 C13 C8 C11 C10 C9 O2 C3 C4

Angle/˚ 110.85(7) 109.89(8) 110.65(8) 111.00(8) 104.18(8) 106.81(8) 114.02(8) 121.10(10) 118.88(10) 123.46(9) 117.64(9) 117.86(10) 119.50(10) 121.78(9) 118.62(9) 118.16(10) 120.75(10) 118.44(10) 127.61(10)

Atom Atom Atom O2 C3 C2 C4 C3 C2 C11 C12 C13 F2 C17 C18 F2 C17 C16 C18 C17 C16 F1 C11 C10 F1 C11 C12 C10 C11 C12 C3 C4 C5 C14 C19 C18 O1 C5 C7 O1 C5 C6 C7 C5 C6 O1 C5 C4 C7 C5 C4 C6 C5 C4 C8 C9 C10

Angle/˚ 125.08(9) 107.27(8) 117.99(10) 118.53(10) 118.34(10) 123.13(10) 118.84(10) 118.14(10) 123.02(10) 103.45(8) 120.85(10) 106.24(8) 110.22(8) 111.21(9) 103.13(8) 114.11(9) 111.46(9) 120.29(10)

Table 35. Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement Parameters (Å2×103) for 1b.

Atom H15 H16 H18 H13 H10 H12 H6A H6B H6C H7A H7B H7C H4A H4B H19 H9

x

y

z

U(eq)

370 -1990 -6354 -2030 5041 -988 998 409 -1003 4883 4092 4620 1825 -15 -3999 3984

6517 5350 7868 6490 6752 4921 10985 12289 10821 11265 12578 11290 11309 11965 9004 8345

5451 3707 5076 7711 9221 8586 5975 7006 6569 8387 8174 7106 9417 8903 6836 8373

21 25 27 21 24 23 35 35 35 33 33 33 24 24 23 21

S59

Crystal structure determination of 2a. Crystal Data for C36H36O4 (M =532.65 g/mol): N/A, space group P-1 (no. 2), a = 10.4200(6) Å, b = 12.3397(8) Å, c = 12.9401(10) Å, α = 66.774(7)°, β = 74.799(6)°, γ = 78.019(5)°, V = 1465.29(17) Å3, Z = 2, T = 100(2) K, μ(CuKα) = 0.611 mm-1, Dcalc = 1.207 g/cm3, 14073 reflections measured (7.58° ≤ 2Θ ≤ 145°), 5735 unique (Rint = 0.0453, Rsigma = N/A) which were used in all calculations. The final R1 was 0.1450 (>2sigma(I)) and wR2 was 0.4351 (all data).

Table 36. Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for 2a. Ueq is defined as 1/3 of of the trace of the orthogonalised UIJ tensor.

Atom O2 O3 O1 O4 C22 C26 C21 C32 C14 C23 C4 C8 C9 C19 C25 C31 C3 C7 C2 C27 C20 C29 C24 C30 C5

x

y

z

U(eq)

5542(5) 3230(4) 7893(4) 6330(5) 3977(6) 1497(6) 5158(6) 2572(6) 8160(6) 2824(6) 7816(6) 9965(6) 10501(6) 8411(7) 5039(6) 801(7) 6498(6) 6449(8) 6572(6) 937(7) 4677(6) -954(7) 5199(7) -411(7) 8461(6)

7453(4) 11447(4) 5342(4) 10245(4) 10163(6) 10891(6) 10539(5) 9448(5) 6718(6) 10460(5) 7347(6) 6162(6) 5208(6) 5805(6) 12614(6) 11997(6) 6906(5) 4796(6) 5615(6) 10149(6) 11371(5) 11600(8) 10871(7) 12354(7) 6423(6)

1171(4) 2370(4) 2650(4) 1152(4) 1335(5) 1830(5) 1487(5) 3414(6) 3480(6) 2245(5) 1400(5) 2006(5) 1650(6) 4487(6) 1421(6) 1769(5) 1588(5) 1825(8) 2406(6) 1523(7) 2154(6) 1116(6) 3257(6) 1399(6) 2395(5)

29.2(11) 22.0(9) 22.3(10) 31.9(11) 23.3(13) 21.3(12) 21.9(13) 21.7(13) 23.1(13) 21.9(13) 23.2(13) 22.2(13) 27.4(14) 28.1(14) 28.7(15) 27.2(14) 22.0(13) 36.7(18) 23.1(13) 36.5(17) 23.1(13) 36.7(17) 32.7(16) 33.6(16) 22.2(13)

S60


1898(6) 2924(7) 8209(7) 7695(7) 10839(7) 5496(7) 2579(8) 7739(8) 11891(8) 7491(8) 1893(7) 1573(7) -268(8) 12195(7) 12735(7)

9740(6) 8258(6) 5990(7) 7843(6) 6904(6) 5493(7) 7385(7) 7118(7) 5019(7) 8036(7) 7687(7) 8879(7) 10481(8) 6717(7) 5767(8)

4368(6) 3556(6) 5504(6) 3511(6) 1965(6) 3477(7) 4635(7) 5522(6) 1253(6) 4529(7) 5570(7) 5424(6) 1203(8) 1559(7) 1196(6)

27.2(14) 30.7(15) 31.9(15) 31.9(15) 31.1(15) 36.5(17) 39.8(18) 37.5(17) 38.4(18) 40.0(18) 38.7(18) 35.1(16) 44(2) 38.4(18) 39.3(19)

Table 37. Anisotropic Displacement Parameters (Å2×103) for 2a. The Anisotropic displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…].

Atom O2 O3 O1 O4 C22 C26 C21 C32 C14 C23 C4 C8 C9 C19 C25 C31 C3 C7 C2 C27 C20 C29 C24 C30 C5 C37 C33

U11

U22

U33

U23

U13

U12

21(2) 12(2) 15(2) 18(2) 24(3) 10(3) 16(3) 10(3) 15(3) 21(3) 17(3) 19(3) 16(3) 21(3) 13(3) 24(3) 18(3) 30(4) 16(3) 22(4) 14(3) 14(3) 21(3) 22(3) 16(3) 20(3) 28(4)

25(2) 20(2) 22(2) 35(3) 22(3) 29(3) 21(3) 24(3) 27(3) 19(3) 30(3) 25(3) 25(3) 27(3) 24(3) 31(3) 24(3) 29(4) 24(3) 25(3) 21(3) 60(5) 42(4) 47(4) 24(3) 30(3) 23(3)

41(3) 37(2) 33(2) 48(3) 25(3) 25(3) 27(3) 32(3) 30(3) 29(3) 23(3) 23(3) 37(4) 36(4) 45(4) 24(3) 27(3) 66(5) 33(3) 62(5) 39(4) 34(4) 41(4) 30(3) 28(3) 32(3) 37(4)

-9(2) -14.8(18) -12.0(18) -24(2) -9(2) -8(2) -8(2) -11(3) -13(3) -12(2) -8(3) -7(2) -10(3) -10(3) -10(3) -12(3) -14(3) -27(4) -13(3) -11(3) -15(3) -13(3) -22(3) -16(3) -11(3) -12(3) -12(3)

-11.7(19) -2.2(17) -7.1(17) -7(2) -3(2) -3(2) -5(2) -6(2) -5(2) -7(2) -5(2) -5(2) -2(3) -7(3) -3(3) -5(2) -3(2) -28(4) -7(2) -16(3) -7(2) -8(3) -10(3) -6(3) -4(2) -5(3) 0(3)

0.5(18) -3.6(16) -1.5(16) 1.7(19) -7(2) -7(2) -2(2) 0(2) -5(2) -1(2) -5(2) -4(2) 1(2) -4(3) -3(2) 6(3) -1(2) 6(3) -1(2) -4(3) -1(2) -5(3) 4(3) 7(3) -3(2) -1(3) -1(3)

S61

C18 C15 C13 C6 C34 C17 C10 C16 C35 C36 C28 C12 C11

31(4) 35(4) 33(4) 22(4) 35(4) 43(4) 31(4) 46(5) 22(4) 26(4) 29(4) 23(4) 15(3)

38(4) 31(4) 32(4) 35(4) 27(4) 48(4) 37(4) 35(4) 43(4) 41(4) 56(5) 50(5) 55(5)

26(3) 33(4) 32(4) 41(4) 48(4) 32(4) 34(4) 45(4) 35(4) 33(4) 60(5) 43(4) 33(4)

-10(3) -14(3) -14(3) -4(3) -7(3) -25(3) -8(3) -24(3) 1(3) -10(3) -23(4) -10(3) -1(3)

-7(3) -13(3) -7(3) -3(3) -3(3) -14(3) 3(3) -18(4) -2(3) -3(3) -16(4) -11(3) -4(3)

-3(3) 3(3) -9(3) -4(3) -4(3) 2(3) 2(3) 12(3) -5(3) -1(3) -16(4) -14(3) -3(3)

Table 38. Bond Lengths for 2a.

Atom Atom O2 C3 O3 C23 O3 C20 O1 C2 O1 C5 O4 C21 C22 C21 C22 C23 C26 C31 C26 C27 C26 C23 C21 C20 C32 C33 C32 C37 C32 C23 C14 C15 C14 C19 C14 C5 C4 C3 C4 C5 C8 C9 C8 C13

Length/Å 1.205(8) 1.447(7) 1.449(7) 1.434(7) 1.455(7) 1.214(8) 1.485(9) 1.543(8) 1.389(9) 1.402(9) 1.531(8) 1.519(9) 1.387(9) 1.391(9) 1.534(9) 1.385(9) 1.391(9) 1.526(9) 1.508(8) 1.545(8) 1.390(9) 1.397(9)

Atom Atom C8 C5 C9 C10 C19 C18 C25 C20 C31 C30 C3 C2 C7 C2 C2 C6 C27 C28 C20 C24 C29 C30 C29 C28 C37 C36 C33 C34 C18 C17 C15 C16 C13 C12 C34 C35 C17 C16 C10 C11 C35 C36 C12 C11

Length/Å 1.522(8) 1.408(10) 1.378(10) 1.517(9) 1.392(10) 1.525(9) 1.519(9) 1.514(9) 1.357(11) 1.512(9) 1.384(11) 1.393(12) 1.369(10) 1.396(10) 1.383(11) 1.384(10) 1.378(10) 1.380(12) 1.381(11) 1.372(12) 1.386(11) 1.390(12)

Table 39. Bond Angles for 2a.

Atom Atom Atom C23 O3 C20 C2 O1 C5

Angle/˚ 110.7(4) 110.8(4)

Atom Atom Atom C6 C2 C7 O1 C2 C3

Angle/˚ 111.4(6) 105.0(5)

S62

C21 C31 C31 C27 O4 O4 C22 C33 C33 C37 C15 C15 C19 O3 O3 C26 O3 C26 C32 C3 C9 C9 C13 C8 C18 C26 O2 O2 C4 O1 O1

C22 C26 C26 C26 C21 C21 C21 C32 C32 C32 C14 C14 C14 C23 C23 C23 C23 C23 C23 C4 C8 C8 C8 C9 C19 C31 C3 C3 C3 C2 C2


103.5(5) 118.2(6) 122.0(6) 119.8(6) 127.2(6) 123.8(6) 109.0(5) 118.5(6) 123.2(6) 118.2(6) 118.4(6) 123.9(6) 117.6(6) 107.6(5) 110.0(5) 107.7(5) 103.7(5) 112.3(5) 115.3(5) 103.6(5) 118.3(6) 121.1(6) 120.5(6) 119.7(7) 122.0(6) 120.3(7) 127.2(6) 124.9(6) 107.9(5) 112.1(5) 107.7(5)

C6 C7 C28 O3 O3 C24 O3 C24 C25 C30 C29 O1 O1 C8 O1 C8 C14 C36 C32 C19 C16 C12 C35 C16 C11 C17 C34 C37 C27 C13 C10



109.5(5) 111.0(6) 121.4(7) 111.8(5) 106.5(5) 112.3(6) 103.9(5) 110.6(5) 111.3(5) 119.0(6) 120.5(7) 106.4(5) 109.2(5) 110.3(5) 103.8(5) 111.5(5) 115.1(5) 121.2(6) 119.9(7) 118.9(7) 119.9(7) 121.3(7) 121.0(7) 119.9(7) 121.4(7) 120.8(7) 118.7(7) 120.7(7) 120.5(7) 120.6(7) 118.7(7)

Table 40. Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement Parameters (Å2×103) for 2a.

Atom H22A H22B H4A H4B H9 H19 H25A H25B H25C H31 H7A H7B

x

y

z

U(eq)

4107 3802 7679 8369 9943 8725 4727 5994 4626 1147 7122 5578

9319 10600 8133 7372 4696 5047 12881 12607 13142 12503 4914 4969

1472 568 1439 662 1673 4474 715 1256 1827 1975 1135 1638

28 28 28 28 33 34 43 43 43 33 55 55

S63

H7C H27 H29 H24A H24B H24C H30 H37 H33 H18 H15 H13 H6A H6B H6C H34 H17 H10 H16 H35 H36 H28 H12 H11

6569 1402 -1765 4851 6159 4917 -860 1664 3389 8386 7520 10498 5598 4630 5577 2814 7590 12245 7184 1651 1133 -638 12755 13651

3985 9415 11837 11389 10808 10099 13104 10535 8042 5367 8468 7536 4699 5660 6045 6588 7257 4373 8795 7102 9096 9957 7232 5641

2335 1539 871 3683 3081 3707 1343 4286 2934 6167 2849 2217 4023 3281 3806 4724 6202 1024 4544 6283 6051 1040 1526 921

55 44 44 49 49 49 40 33 37 38 38 37 55 55 55 48 45 46 48 46 42 53 46 47

Crystal structure determination of 2b. Crystal Data for C18H16F2O2 (M =302.31 g/mol): N/A, space group P21/a (no. 14), a = 12.0353(5) Å, b = 10.1663(5) Å, c = 12.0412(6) Å, β = 96.450(4)°, V = 1463.97(12) Å3, Z = 4, T = 100(2) K, μ(MoKα) = 0.105 mm1 , Dcalc = 1.372 g/cm3, 6184 reflections measured (5.26° ≤ 2Θ ≤ 54.98°), 3272 unique (Rint = 0.0263, Rsigma = N/A) which were used in all calculations. The final R1 was 0.0416 (>2sigma(I)) and wR2 was 0.0937 (all data).

S64

Table 41. Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for 2b. Ueq is defined as 1/3 of of the trace of the orthogonalised UIJ tensor.


x

y

z

U(eq)

819.2(8) 6525.2(7) 2585.4(9) 1396(1) 3571.8(13) 4604.3(13) 1433.0(12) 2355.1(12) 1061.7(13) 4385.2(13) 1625.7(12) 3446.4(12) 1446.5(13) 1938.5(12) 2011.3(12) 5418.9(13) 1803.9(14) 1698.2(13) 1173.5(12) 3536.5(14) 2424.3(13) 5504.9(12)

4673.7(10) 6894.5(10) 3002.8(10) 3995.9(12) 6208.9(15) 6809.2(15) 4723.7(15) 4384.3(14) 3432.1(16) 4718.2(15) 5707.7(16) 5149.6(15) 3366.3(15) 4450.6(15) 5626.3(15) 5309.8(16) 1416.4(16) 3855.5(16) 4603.8(16) 2676.4(18) 2722.1(15) 6331.0(15)

6996.1(7) 2607.0(8) 2539.2(8) -120.7(9) 2020.4(12) 1974.6(13) 1806.9(12) 2752.4(12) 5392.6(13) 3418.1(13) 5538.5(13) 2719.3(12) 4347.5(13) 3898.4(12) 4500.9(12) 3392.5(13) 1211.6(14) 859.9(13) 5964.6(12) 862.2(14) 1358.9(12) 2655.2(13)

25.8(2) 25.6(2) 16.1(2) 26.9(3) 16.3(3) 18.3(3) 16.2(3) 14.1(3) 19.6(3) 17.1(3) 17.9(3) 14.1(3) 17.8(3) 14.3(3) 16.5(3) 18.5(3) 21.4(4) 17.7(3) 17.8(3) 24.2(4) 16.6(3) 17.4(3)

Table 42. Anisotropic Displacement Parameters (Å2×103) for 2b. The Anisotropic displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…].

Atom F1 F2 O1 O2 C9 C10 C4 C5 C18 C13 C16 C8 C19 C14 C15 C12

U11

U22

U33

U23

U13

U12

28.6(5) 16.7(5) 21.2(5) 36.6(7) 17.4(7) 22.6(8) 14.5(7) 15.8(7) 18.9(8) 19.7(7) 16.2(7) 14.8(7) 18.1(7) 11.7(7) 16.4(7) 15.6(7)

34.0(6) 27.7(5) 13.8(5) 28.9(7) 18.6(8) 16.4(8) 19.2(8) 12.5(7) 20.1(8) 15.0(7) 19.9(8) 15.2(7) 16.5(8) 17.6(8) 16.1(8) 20.4(8)

16.3(5) 32.6(6) 13.3(5) 13.8(6) 12.7(7) 16.6(8) 14.4(7) 13.9(7) 20.5(8) 16.3(8) 17.1(8) 12.5(7) 18.6(8) 13.1(7) 16.7(8) 18.8(8)

0.2(4) 0.3(4) -1.9(4) 0.1(5) 0.5(6) 2.0(6) 0.3(6) -0.5(6) 5.4(6) 2.0(6) -4.0(6) -3.2(6) -1.5(6) 0.5(6) 0.7(6) -1.4(6)

9.5(4) 3.7(4) 1.5(4) -2.9(5) 0.5(6) 4.8(6) 0.1(6) 1.4(5) 5.1(6) 0.7(6) -0.2(6) 2.2(5) 1.9(6) -0.9(5) 1.0(6) -1.8(6)

4.2(4) -6.6(4) 1.1(4) -0.5(6) 2.3(6) -0.9(7) -0.1(6) 0.8(6) 0.9(7) 1.7(6) 2.4(6) 1.8(6) 0.2(6) 1.1(6) 0.0(6) 3.1(6)

S65

C6 C3 C17 C7 C2 C11

26.5(9) 16.2(7) 14.7(7) 21.9(8) 19.7(8) 13.7(7)

18.1(8) 19.8(8) 27.1(9) 29.3(9) 18.0(8) 19.0(8)

19.4(8) 17.1(8) 11.9(7) 22.4(9) 12.3(7) 20.1(8)

-3.0(6) -0.7(6) 0.9(6) -6.1(7) -2.6(6) -4.8(6)

2.3(6) 1.6(6) 2.9(5) 6.6(6) 2.5(6) 4.7(6)

-3.6(7) -6.2(6) 5.1(7) -1.4(7) -2.0(6) -2.9(6)

Table 43. Bond Lengths for 2b.

Atom Atom F1 C17 F2 C11 O1 C2 O1 C5 O2 C3 C9 C8 C9 C10 C10 C11 C4 C3 C4 C5 C5 C14 C5 C8

Length/Å 1.3597(17) 1.3621(17) 1.4412(17) 1.4598(17) 1.2043(18) 1.385(2) 1.391(2) 1.372(2) 1.504(2) 1.537(2) 1.522(2) 1.531(2)

Atom Atom C18 C17 C18 C19 C13 C12 C13 C8 C16 C17 C16 C15 C19 C14 C14 C15 C12 C11 C6 C2 C3 C2 C7 C2

Length/Å 1.375(2) 1.390(2) 1.385(2) 1.401(2) 1.372(2) 1.383(2) 1.389(2) 1.396(2) 1.377(2) 1.524(2) 1.528(2) 1.527(2)

Table 44. Bond Angles for 2b.

Atom Atom Atom C2 O1 C5 C8 C9 C10 C11 C10 C9 C3 C4 C5 O1 C5 C14 O1 C5 C8 C14 C5 C8 O1 C5 C4 C14 C5 C4 C8 C5 C4 C17 C18 C19 C12 C13 C8 C17 C16 C15 C9 C8 C13 C9 C8 C5 C13 C8 C5 C14 C19 C18 C19 C14 C15 C19 C14 C5

Angle/˚ 110.90(11) 121.59(14) 118.04(14) 103.46(12) 106.89(11) 107.70(11) 111.85(12) 102.78(11) 112.18(12) 114.63(12) 118.11(15) 121.09(14) 118.45(15) 118.20(14) 124.28(13) 117.49(13) 120.93(14) 118.80(14) 121.07(13)

Atom Atom Atom C15 C14 C5 C16 C15 C14 C11 C12 C13 O2 C3 C4 O2 C3 C2 C4 C3 C2 F1 C17 C16 F1 C17 C18 C16 C17 C18 O1 C2 C6 O1 C2 C7 C6 C2 C7 O1 C2 C3 C6 C2 C3 C7 C2 C3 F2 C11 C10 F2 C11 C12 C10 C11 C12

Angle/˚ 120.10(13) 120.86(15) 118.31(14) 127.39(15) 124.85(14) 107.76(12) 118.51(14) 118.67(14) 122.83(14) 107.29(12) 111.45(12) 111.57(13) 104.25(12) 111.10(13) 110.90(13) 118.75(14) 118.54(14) 122.71(14)

S66

Table 45. Torsion Angles for 2b.

A C8 C2 C2 C2 C3

B C9 O1 O1 O1 C4

C C10 C5 C5 C5 C5

D C11 C14 C8 C4 O1

Angle/˚ -0.7(2) 150.48(11) -89.18(13) 32.22(14) -31.36(14)

A C4 C17 C19 C5 C8

B C5 C16 C14 C14 C13

C C14 C15 C15 C15 C12

D C15 C14 C16 C16 C11

Angle/˚ -90.09(16) 0.3(2) 1.5(2) 179.31(13) -0.4(2)

C3 C4 C5 C14 -145.83(12) C5 C4 C3 O2

-159.72(16)

85.19(15) C5 C4 C3 C2 2.3(2) C15 C16 C17 F1

20.94(15) 178.42(13)

C3 C4 C5 C8 C10 C9 C8 C13 C10 C9 C8 C5 C12 C13 C8 C9

-175.59(14) C15 C16 C17 C18 -1.7(2) C19 C18 C17 F1

-1.7(2) -178.81(13)

C12 C13 C8 C5

176.32(14) C19 C18 C17 C16

O1 C5 C8 C9

123.46(15) C5 O1 C2 C6

-137.00(12)

C14 C5 C8 C9

-119.38(16) C5 O1 C2 C7

100.59(14)

9.8(2) C5 O1 C2 C3 -54.40(17) O2 C3 C2 O1 62.77(17) C4 C3 C2 O1

-19.10(15) 178.35(14) -2.29(16)

C4 C5 C8 C13 -168.09(13) O2 C3 C2 C6

-66.4(2)

0.5(2) C4 C3 C2 C6 -1.9(2) O2 C3 C2 C7

112.97(14) 58.3(2)

C18 C19 C14 C5

-179.69(14) C4 C3 C2 C7

-122.34(13)

O1 C5 C14 C19

-24.27(18) C9 C10 C11 F2

178.95(13)

C4 C5 C8 C9 O1 C5 C8 C13 C14 C5 C8 C13

C17 C18 C19 C14 C18 C19 C14 C15

C8 C5 C14 C19 -141.91(14) C9 C10 C11 C12 C4 C5 C14 C19

87.67(17) C13 C12 C11 F2

O1 C5 C14 C15 C8 C5 C14 C15

157.97(12) C13 C12 C11 C10 40.32(18)

1.3(2)

-1.6(2) -178.39(13) 2.1(2)

Table 46. Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement Parameters (Å2×103) for 2b.

Atom H9 H10 H4A H4B H18 H13 H16 H19

x

y

z

U(eq)

2951 4682 698 1462 738 4313 1672 1373

6526 7514 4527 5646 2704 4023 6493 2586

1571 1497 2023 1604 5696 3907 5938 3943

20 22 19 19 24 21 22 21

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H15 H12 H6A H6B H6C H7A H7B H7C

2323 6039 2263 1637 1120 3933 3399 3977

6364 5025 728 1229 1470 3486 2557 1957

4201 3861 1562 429 1550 1021 68 1185

20 22 32 32 32 36 36 36

Crystal structure determination of 1d. Crystal Data for C36H28F4N4O4 (M =656.62 g/mol): N/A, space group Ia (no. 9), a = 11.7280(9) Å, b = 9.6480(8) Å, c = 14.5670(10) Å, β = 100.043(6)°, V = 1623.0(2) Å3, Z = 2, T = 213(2) K, μ(MoKα) = 0.104 mm1 , Dcalc = 1.344 g/cm3, 6329 reflections measured (5.08° ≤ 2Θ ≤ 52°), 2987 unique (Rint = 0.0311, Rsigma = N/A) which were used in all calculations. The final R1 was 0.0259 (>2sigma(I)) and wR2 was 0.0524 (all data).

Table 47. Crystal data and structure refinement for 1d. Identification code 1d Empirical formula C36H28F4N4O4 Formula weight 656.62 Temperature/K 213(2) Crystal system N/A Space group Ia a/Å 11.7280(9) b/Å 9.6480(8) c/Å 14.5670(10) α/° 90.00 β/° 100.043(6) γ/° 90.00 Volume/Å3 1623.0(2) Z 2 3 ρcalcg/cm 1.344 μ/mm-1 0.104 F(000) 680.0 3 Crystal size/mm 0.20 × 0.20 × 0.20

S68

Radiation MoKα (λ = 0.71073) 2Θ range for data collection/° 5.08 to 52 Index ranges -14 ≤ h ≤ 14, -11 ≤ k ≤ 11, -17 ≤ l ≤ 17 Reflections collected 6329 Independent reflections 2987 [Rint = 0.0311, Rsigma = N/A] Data/restraints/parameters 2987/2/217 Goodness-of-fit on F2 0.735 Final R indices [I>=2σ (I)] R1 = 0.0259, wR2 = 0.0502 Final R indices [all data] R1 = 0.0437, wR2 = 0.0524 Largest diff. peak/hole / e Å-3 0.11/-0.09

Table 48. Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for 1d. Ueq is defined as 1/3 of of the trace of the orthogonalised UIJ tensor.

Atom C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 N1 N2 O1 O2 F1 F2

x

y

z

U(eq)

1728.4(15) 1640.0(16) 2730.2(15) 3570.5(16) 1741.7(14) 2392.3(18) 2383.1(19) 1702.8(19) 1047.6(18) 1064.9(17) 762.6(15) -371.6(16) -1269.5(17) -1029.3(19) 71.7(19) 968.3(17) 4498.9(18) 4066.3(19) 2947.7(14) 3069.4(16) 2806.2(10) 789.8(10) 1688.6(12) -1917.7(11)

1852.1(15) 3428.1(16) 3962.5(16) 2868.8(17) 1036.2(16) -157.8(19) -967(2) -563(2) 594(2) 1401.9(19) 1387.8(16) 1394.7(17) 1005.3(19) 578.6(19) 546.5(19) 973.0(18) 2574(2) 3134.4(19) 5292.5(16) 6436.0(18) 1686.0(11) 4042.6(11) -1361.1(13) 156.5(14)

8281.4(13) 8445.6(13) 8344.2(13) 8150.0(14) 9188.0(12) 9347.4(14) 10131.1(15) 10747.9(15) 10628.4(14) 9841.1(13) 7513.8(13) 7653.4(15) 6968.6(15) 6127.4(14) 5948.8(14) 6638.2(13) 8979.8(16) 7274.5(16) 8462.8(11) 8570.6(13) 7966.6(9) 8617.8(9) 11526.8(9) 5455.6(8)

39.4(4) 41.3(4) 42.9(5) 45.4(5) 39.1(4) 54.0(5) 63.5(6) 56.4(5) 60.8(6) 52.3(5) 38.7(4) 45.8(5) 50.2(5) 54.1(5) 56.7(6) 48.7(5) 69.4(6) 66.6(7) 47.4(4) 64.9(5) 45.8(3) 52.7(4) 86.3(4) 80.9(4)

Table 49. Anisotropic Displacement Parameters (Å2×103) for 1d. The Anisotropic displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…].

Atom C1 C2 C3 C4

U11

U22

U33

U23

U13

U12

41.9(10) 48.7(11) 51.1(12) 44.9(11)

34.3(9) 36.5(9) 32.2(9) 38.4(10)

45.2(12) 41.2(11) 47.0(13) 54.2(13)

-4.8(8) -3.7(8) -3.7(8) -4.7(9)

16.3(9) 15(1) 12.8(10) 12.0(11)

1.6(8) 2.8(9) -4.6(8) -2.8(8)

S69

C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 N1 N2 O1 O2 F1 F2

45.2(11) 65.7(13) 78.8(15) 68.5(13) 75.2(15) 67.4(13) 48.7(11) 51.3(12) 48.5(12) 67.9(15) 73.7(16) 56.5(12) 57.6(13) 69.5(14) 55.7(10) 86.3(13) 44.7(7) 52.4(8) 113.6(11) 82.3(9)

33.1(9) 45.0(11) 51.1(11) 58.0(14) 68.4(15) 46.4(11) 29.1(9) 45.4(10) 54.0(11) 54.9(12) 60.0(13) 48.2(11) 55.2(13) 57.2(13) 44.3(11) 39.9(10) 39.0(7) 39.2(6) 88.3(9) 109.5(10)

39.7(11) 55.7(14) 61.1(15) 41.4(13) 43.2(14) 46.2(14) 40.3(12) 43.4(13) 48.3(14) 35.9(12) 39.7(14) 45.6(14) 91(2) 84.3(18) 45.1(10) 75.1(14) 58.8(9) 70.3(10) 58.9(9) 46.7(8)

-3.5(8) 1.2(9) 13.8(11) 9.7(10) 2.3(11) -1.9(9) 0.2(8) -4.9(9) 2.3(10) 5.4(9) -4.3(10) -1.2(9) -10.5(12) -3.6(11) -3.3(8) -6.4(9) -7.8(6) -5.7(6) 28.8(7) 1.3(7)

9.6(9) 22.6(12) 13.7(13) 6.1(11) 22.8(12) 18.3(12) 13.3(10) 15.5(11) 9.2(12) -1.5(12) 19.4(13) 20.3(11) 1.2(14) 44.8(14) 16.6(8) 32.4(11) 23.2(7) 21.0(8) 20.6(8) -0.4(7)

-1.4(8) 8.5(10) 17.5(11) -6.1(11) 8.5(11) 11.9(9) 0.8(8) -5.0(9) -7.6(10) -17.7(10) -6.2(11) -1.5(9) 3.9(10) -7.3(11) -6.8(8) -14.6(9) -2.6(6) 5.5(6) 7.5(8) -31.7(8)

Table 50. Bond Lengths for 1d.

Atom C1 C1 C1 C1 C2 C2 C3 C3 C4 C4 C4 C5 C5

Atom Length/Å Atom Atom Length/Å 1.384(3) O1 1.4269(19) C6 C7 1.514(3) 1.358(3) C11 C7 C8 1.535(2) 1.349(3) C5 C8 C9 1.546(2) 1.374(2) C2 C8 F1 1.390(3) O2 1.2230(18) C9 C10 1.410(2) 1.380(2) C3 C11 C12 1.314(2) 1.397(2) N1 C11 C16 1.504(2) 1.371(3) C4 C12 C13 1.447(2) 1.368(3) O1 C13 C14 1.506(3) 1.361(3) C17 C14 C15 1.513(2) 1.361(2) C18 C14 F2 1.379(2) 1.384(3) C6 C15 C16 1.387(2) C10 N1 N2 1.1200(18)

Table 51. Bond Angles for 1d.

Atom Atom Atom O1 C1 C11 O1 C1 C5 C11 C1 C5 O1 C1 C2 C11 C1 C2

Angle/˚ 108.67(13) 110.01(14) 112.19(13) 104.32(12) 110.10(14)

Atom Atom Atom C10 C5 C1 C5 C6 C7 C8 C7 C6 C9 C8 C7 C9 C8 F1

Angle/˚ 122.59(15) 121.74(18) 118.29(19) 122.60(18) 118.78(18)

S70

C5 O2 O2 C3 N1 N1 C2 O1 O1 C3 O1 C3 C17 C6 C6



111.23(14) 129.11(15) 126.00(15) 104.89(13) 120.14(14) 126.26(15) 113.52(14) 100.54(13) 109.72(15) 112.77(16) 107.14(15) 113.60(16) 112.22(17) 117.59(17) 119.70(15)

C7 C8 C5 C12 C12 C16 C13 C14 C15 C15 F2 C14 C15 N2 C1

C8 C9 C10 C11 C11 C11 C12 C13 C14 C14 C14 C15 C16 N1 O1

F1 C10 C9 C16 C1 C1 C11 C12 F2 C13 C13 C16 C11 C3 C4

118.62(19) 118.73(17) 121.05(17) 117.39(18) 120.39(15) 122.20(15) 121.96(17) 118.84(18) 119.23(18) 121.9(2) 118.86(19) 118.73(18) 121.15(17) 176.03(18) 114.02(11)

Table 52. Torsion Angles for 1d.

A B C O1 C1 C2 C11 C1 C2 C5 C1 C2 O1 C1 C2

D Angle/˚ O2 171.15(18) 54.7(2) O2 O2 -70.3(2) -8.3(2) C3

A F1 C6 C1 C8

B C8 C5 C5 C9

C C9 C10 C10 C10

D Angle/˚ C10 179.8(2) 0.2(3) C9 C9 176.21(19) -0.1(3) C5

C11 C1 C2 C3 -124.78(15) O1 C1 C11 C12 177.58(14) C5 C1 C2 C3 110.21(17) 2.0(3) O2 C2 C3 N1

C5 C1 C11 C12 55.72(19) C2 C1 C11 C12 -68.74(18)

C1 C2 C3 N1 -178.56(17) O1 C1 C11 C16 -4.05(19) O2 C2 C3 C4 178.87(19) C1 C2 C3 C4

-1.6(2)

C5 C1 C11 C16 -125.92(16) C2 C1 C11 C16 109.63(17)

N1 C3 C4 O1 -172.64(18) C16 C11 C12 C13 C2 C3 C4 O1 N1 C3 C4 C17

10.7(2) 70.6(3)

C1 C11 C12 C13 178.80(16) 1.0(3) C11 C12 C13 C14

C2 C3 C4 C17 -106.09(19) C12 C13 C14 C15 N1 C3 C4 C18

-58.5(3)

C2 C3 C4 C18

124.8(2)

O1 C1 C5 C6 C11 C1 C5 C6

-30.3(2) 90.8(2)

0.4(2)

C12 C13 C14 F2

-0.8(3) 178.26(17)

F2 C14 C15 C16 -179.75(16) C13 C14 C15 C16 C14 C15 C16 C11

-0.7(3) 2.1(3)

C2 C1 C5 C6 -145.40(17) C12 C11 C16 C15

-1.9(2)

O1 C1 C5 C10 153.72(15) C1 C11 C1 C5 C10 -85.2(2) C2 38.6(2) C2 C1 C5 C10 C4 -0.4(3) C10 C5 C6 C7 C11

C11 C3 C3 C1

C16 N1 N1 O1

C15 179.70(16) -4(3) N2 N2 180(100) C4 133.81(14) S71

C1 C5 C6 C7 -176.53(19) C5 C1 O1 C4 -103.01(17) C5 C6 C7 C8 C6 C7 C8 C9 C6 C7 C8 F1

0.5(3) -0.5(3) 180.0(2)

16.4(2) C2 C1 O1 C4 C3 C4 O1 C1 -16.73(19) C17 C4 O1 C1 102.28(17)

C7 C8 C9 C10

0.3(3)

C18 C4 O1 C1 -135.65(15)

Table 53. Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement Parameters (Å2×103) for 1d.

Atom H6 H7 H9 H10 H12 H13 H15 H16 H17A H17B H17C H18A H18B H18C

x

y

z

U(eq)

2854 2836 588 611 -533 -2037 220 1729 5014 4144 4936 4596 4479 3442

-430 -1774 848 2209 1675 1031 241 984 1863 2257 3414 2393 4010 3171

8913 10234 11069 9750 8235 7075 5368 6515 8819 9496 9159 7188 7332 6742

65 76 73 63 55 60 68 58 104 104 104 100 100 100

Crystal structure determination of 2d. Crystal Data for C18H14F2N2O2 (M =328.31 g/mol): N/A, space group P-1 (no. 2), a = 8.9700(10) Å, b = 9.3620(10) Å, c = 11.391(2) Å, α = 102.30(2)°, β = 111.08(2)°, γ = 103.46(2)°, V = 820.37(19) Å3, Z = 2, T = 213(2) K, μ(MoKα) = 0.103 mm-1, Dcalc = 1.329 g/cm3, 6487 reflections measured (4.06° ≤ 2Θ ≤ 51.98°), 2979 unique (Rint = 0.0718, Rsigma = N/A) which were used in all calculations. The final R1 was 0.0507 (>2sigma(I)) and wR2 was 0.1446 (all data).

S72

Table 54. Crystal data and structure refinement for 2d. Identification code 2d Empirical formula C18H14F2N2O2 Formula weight 328.31 Temperature/K 213(2) Crystal system N/A Space group P-1 a/Å 8.9700(10) b/Å 9.3620(10) c/Å 11.391(2) α/° 102.30(2) β/° 111.08(2) γ/° 103.46(2) Volume/Å3 820.37(19) Z 2 3 ρcalcg/cm 1.329 μ/mm-1 0.103 F(000) 340.0 3 Crystal size/mm 0.30 × 0.20 × 0.20 Radiation MoKα (λ = 0.71073) 2Θ range for data collection/° 4.06 to 51.98 Index ranges -11 ≤ h ≤ 11, -10 ≤ k ≤ 11, -13 ≤ l ≤ 13 Reflections collected 6487 Independent reflections 2979 [Rint = 0.0718, Rsigma = N/A] Data/restraints/parameters 2979/0/217 Goodness-of-fit on F2 0.783 Final R indices [I>=2σ (I)] R1 = 0.0507, wR2 = 0.1211 Final R indices [all data] R1 = 0.0871, wR2 = 0.1446 Largest diff. peak/hole / e Å-3 0.26/-0.24

Table 55. Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for 2d. Ueq is defined as 1/3 of of the trace of the orthogonalised UIJ tensor.

Atom C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16

x

y

z

U(eq)

8(3) -589(3) -1863(3) -2102(3) -769(3) -1144(3) -1831(4) -2136(3) -1772(4) -1097(3) 1936(3) 2895(3) 4659(4) 5402(3) 4515(4) 2763(3)

2305(3) 3695(3) 3615(3) 2128(3) 1110(3) -456(3) -1567(3) -1076(3) 452(4) 1551(3) 2780(3) 2569(4) 3095(4) 3827(4) 4049(4) 3532(3)

6742(2) 6870(2) 5648(2) 4628(2) 7271(2) 6668(2) 7138(3) 8219(3) 8848(3) 8369(2) 7299(2) 8454(2) 8966(3) 8306(3) 7162(3) 6659(2)

36.9(6) 39.3(6) 42.3(6) 41.7(6) 37.2(6) 46.0(7) 51.2(7) 49.5(7) 54.8(8) 47.4(7) 38.8(6) 55.7(8) 67.1(9) 57.9(8) 56.4(8) 47.9(7)

S73

C17 C18 N1 N2 O1 O2 F1 F2

-1958(4) -3758(4) 75(3) 602(3) -676(2) -2628(3) -2829(2) 7142(2)

2446(4) 874(4) 4933(3) 6039(3) 1671(2) 4521(3) -2157(2) 4368(3)

3414(2) 4271(3) 7923(2) 8779(2) 5300.5(14) 5419.6(18) 8674.2(16) 8826.1(19)

56.7(8) 64.3(8) 44.9(5) 65.5(7) 40.0(4) 62.2(6) 74.0(6) 84.9(6)

Table 56. Anisotropic Displacement Parameters (Å2×103) for 2d. The Anisotropic displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…].

Atom C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 N1 N2 O1 O2 F1 F2

U11

U22

U33

U23

U13

U12

44.1(14) 49.4(14) 49.7(15) 44.0(14) 42.7(14) 60.9(17) 66.3(18) 57.5(17) 72.8(19) 67.4(17) 39.1(13) 50.8(17) 50.6(18) 38.8(16) 50.0(17) 46.1(16) 67.8(19) 47.1(17) 57.5(13) 88.3(19) 46(1) 76.2(14) 102.7(14) 45.1(11)

40.2(16) 39.3(16) 48.4(18) 50.2(18) 39.9(17) 47.1(19) 43.5(18) 51(2) 56(2) 40.7(17) 43.0(16) 74(2) 91(3) 67(2) 65(2) 55.5(19) 71(2) 69(2) 46.7(15) 55.4(18) 47.7(12) 72.2(16) 61.7(13) 105.7(18)

32.6(11) 38.1(12) 47.8(14) 38.7(12) 37.7(12) 47.6(13) 56.9(15) 50.8(14) 47.0(14) 43.8(13) 38.6(12) 48.8(15) 59.9(17) 68.5(18) 64.7(17) 49.6(14) 44.7(14) 74.7(19) 44.4(12) 53.4(14) 35.5(8) 64.4(12) 71.6(10) 104.0(14)

12.7(10) 13.9(11) 25.5(12) 19.8(11) 16.3(11) 20.4(12) 20.5(12) 29.5(13) 20.4(13) 13.9(11) 11.3(10) 28.1(14) 36.5(16) 20.1(15) 24.1(14) 22.4(12) 29.4(14) 28.9(16) 20.2(12) 9.8(13) 15.5(7) 35.6(10) 35.6(9) 40.0(12)

21.5(10) 27.2(11) 32.3(12) 21.3(11) 23.3(10) 35.0(12) 34.8(14) 29.6(13) 39.5(14) 35.1(13) 22.0(11) 25.1(13) 17.1(14) 24.0(14) 35.6(14) 26.1(12) 30.2(13) 25.5(14) 30.8(10) 34.1(13) 24.8(7) 38.3(10) 53.6(10) 29.6(10)

16.1(11) 15.9(11) 22.6(13) 18.9(12) 16.3(11) 25.7(13) 24.3(14) 15.4(13) 16.5(15) 17.1(13) 14.7(11) 19.6(15) 25.3(17) 19.0(14) 17.2(14) 16.5(13) 28.5(16) 13.1(15) 22.7(11) 27.0(14) 18.3(8) 45.9(12) 13.8(10) 24.2(10)

Table 57. Bond Lengths for 2d.

Atom Atom C1 O1 C1 C2 C1 C5 C1 C11 C2 N1 C2 C3

Length/Å 1.455(2) 1.517(4) 1.525(3) 1.524(3) 1.308(3) 1.421(4)

Atom Atom C6 C7 C7 C8 C8 F1 C8 C9 C9 C10 C11 C12

Length/Å 1.387(4) 1.365(4) 1.358(3) 1.358(4) 1.382(4) 1.373(4)

S74

C3 C3 C4 C4 C4 C5 C5

O2 C4 O1 C18 C17 C6 C10

1.222(3) 1.526(4) 1.447(3) 1.517(4) 1.518(3) 1.382(4) 1.387(3)

C11 C12 C13 C14 C14 C15 N1

C16 C13 C14 C15 F2 C16 N2

1.394(3) 1.393(4) 1.358(4) 1.349(4) 1.372(3) 1.383(4) 1.121(3)

Table 58. Bond Angles for 2d.

Atom Atom Atom O1 C1 C2 O1 C1 C5 C2 C1 C5 O1 C1 C11 C2 C1 C11 C5 C1 C11 N1 C2 C3 N1 C2 C1 C3 C2 C1 O2 C3 C2 O2 C3 C4 C2 C3 C4 O1 C4 C18 O1 C4 C17 C18 C4 C17 O1 C4 C3 C18 C4 C3 C17 C4 C3 C6 C5 C10 C6 C5 C1

Angle/˚ 99.96(17) 109.70(19) 112.97(18) 107.52(16) 112.4(2) 113.31(19) 121.3(2) 125.8(2) 112.6(2) 129.0(3) 125.6(2) 105.4(2) 110.2(2) 107.80(19) 112.5(2) 104.15(18) 110.8(2) 111.0(2) 118.1(2) 120.19(19)

Atom Atom Atom C10 C5 C1 C5 C6 C7 C8 C7 C6 F1 C8 C9 F1 C8 C7 C9 C8 C7 C8 C9 C10 C9 C10 C5 C12 C11 C16 C12 C11 C1 C16 C11 C1 C11 C12 C13 C14 C13 C12 C15 C14 C13 C15 C14 F2 C13 C14 F2 C14 C15 C16 C15 C16 C11 N2 N1 C2 C4 O1 C1

Angle/˚ 121.7(2) 121.4(2) 118.2(3) 119.2(2) 118.6(3) 122.2(2) 119.2(2) 120.8(2) 118.7(2) 122.1(2) 119.1(2) 120.2(3) 118.6(3) 123.3(3) 118.2(3) 118.5(3) 117.9(3) 121.1(2) 175.9(3) 112.35(16)

Table 59. Torsion Angles for 2d.

A B C O1 C1 C2 C5 C1 C2 C11 C1 C2 O1 C1 C2 C5 C1 C2 C11 C1 C2 N1 C2 C3 C1 C2 C3 N1 C2 C3 C1 C2 C3

D Angle/˚ A B C D Angle/˚ N1 -158.1(2) C7 C8 C9 C10 1.1(4) N1 85.4(3) C8 C9 C10 C5 -0.9(4) 0.3(4) N1 -44.3(3) C6 C5 C10 C9 C3 15.1(2) C1 C5 C10 C9 -178.8(2) C3 -101.4(2) O1 C1 C11 C12 -141.6(3) C3 128.8(2) C2 C1 C11 C12 109.3(3) O2 -8.2(4) C5 C1 C11 C12 -20.2(3) O2 178.3(2) O1 C1 C11 C16 42.0(3) C4 171.5(2) C2 C1 C11 C16 -67.0(3) C4 -2.0(3) C5 C1 C11 C16 163.4(2) S75

O2 C3 C4 O1 C2 C3 C4 O1 O2 C3 C4 C18 C2 C3 C4 C18 O2 C3 C4 C17 C2 C3 C4 C17 O1 C1 C5 C6 C2 C1 C5 C6 C11 C1 C5 C6 O1 C1 C5 C10 C2 C1 C5 C10 C11 C1 C5 C10 C10 C5 C6 C7 C1 C5 C6 C7 C5 C6 C7 C8 C6 C7 C8 F1 C6 C7 C8 C9 F1 C8 C9 C10

167.5(2) -12.2(2) -74.0(3) 106.3(2) 51.7(3) -127.9(2) 35.0(3) 145.6(2) -85.1(3) -145.9(2) -35.4(3) 93.9(3) 0.1(4) 179.2(2) 0.1(4) 179.1(2) -0.7(4) -178.7(3)

C16 C11 C12 C13 C1 C11 C12 C13 C11 C12 C13 C14 C12 C13 C14 C15 C12 C13 C14 F2 C13 C14 C15 C16 F2 C14 C15 C16 C14 C15 C16 C11 C12 C11 C16 C15 C1 C11 C16 C15 C3 C2 N1 N2 C1 C2 N1 N2 C18 C4 O1 C1 C17 C4 O1 C1 C3 C4 O1 C1 C2 C1 O1 C4 C5 C1 O1 C4 C11 C1 O1 C4

-0.2(4) -176.6(3) 0.5(5) -1.2(5) 178.9(3) 1.5(5) -178.6(2) -1.1(4) 0.5(4) 177.0(2) -14(4) 159(4) -95.5(2) 141.4(2) 23.4(2) -23.5(2) 95.4(2) -141.0(2)

Table 60. Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement Parameters (Å2×103) for 2d.

Atom H6 H7 H9 H10 H12 H13 H15 H16 H17A H17B H17C H18A H18B H18C

x

y

z

U(eq)

-928 -2079 -1977 -858 2358 5323 5071 2119 -2112 -845 -2826 -3883 -4699 -3751

-775 -2630 758 2609 2068 2946 4539 3690 1485 3190 2867 -61 1231 649

5923 6722 9600 8793 8901 9752 6721 5872 2783 3683 3001 3624 3895 5065

55 61 66 57 67 81 68 57 85 85 85 96 96 96

S76