Redox-Innocent Metal-Assisted Cleavage of S-S. Bond in a Disulfide-Containing Ligand.

Transcription

1 Supplementary Information for Redox-Innocent Metal-Assisted Cleavage of S-S Bond in a Disulfide-Containing Ligand. Charlène Esmieu, Maylis Orio, Laurent Le Pape, Colette Lebrun, Jacques Pécaut, Stéphane Ménage and Stéphane Torelli * CEA-iRTSV-LCBM-BioCE, Univ. Grenoble Alpes, CNRS UMR 5249, 17 rue des Martyrs, Grenoble, France. CEA, INAC-SCIB-RICC, Grenoble, France Institut des Sciences Moléculaires de Marseille, Aix Marseille Université, CNRS, Centrale Marseille, ISM2 UMR 7313, 13097, Marseille, France. Contents Figures S1 and S2. ESI mass spectra of (1) in CH 3 CN and ms2@2387 showing the formation of (4) from the fragmentation of (1). Figure S3. UV-Vis spectrum of (1) in CH 3 CN. Figure S4 and S5. ESI mass spectra of (1 ) in CH 3 CN and ms2@2396 showing the formation of (4 ) from the fragmentation of (1 ). Figure S6. 1 H NMR spectrum of (1 ) in CD 3 CN. Figures S7 and S8. Experimental spectrum and calculated ESI profiles for (2) in CH 3 CN.

2 Figures S9 and S10. Experimental and Calculated ESI patterns for (3) in CH 3 CN. Figure S11. Optimized structures of (2) and selected metrics. Figure S12. Optimized structures of (3) and selected metrics. Figure S13. Difference electron density sketch of the relevant transition for (2) (yellow = negative, red = positive). Figure S14. Difference electron density sketch of the relevant transition for (3) (yellow = negative, red = positive). Figure S15. Solid state (dotted line) and acetonitrile solution UV-vis (solid) spectra for (2) (red) and (3) (black). Figure S16. X-band EPR spectra recorded for X-ray single crystals of (1), (2) and (3) in CH 3 CN at 10 K. Figure S17. X-band EPR spectrum of (2) recorded in CH 3 CN at 10 K (black) and simulation (red). Figure S18. Changes on the UV-Vis spectrum of (1) in CH 3 CN from 0 (brown) to 14 days (blue) in the glove box. Each spectrum corresponds to 4 days except the last one. Figure S19. ESI mass spectrum of the reaction mixture upon exposure of (1) to H 2 O-only conditions after 6 days. Figure S20. Calculated ESI profiles of the reaction mixture with (1) under H 2 O-only conditions after 6 days. Figure S21. ESI mass spectrum of the reaction mixture upon exposure (1 ) to H 2 O-only conditions after 6 days. Figure S22. Calculated ESI profiles of the reaction mixture with (1 ) under H 2 O-only conditions after 6 days. Figure S23. ESI mass spectrum of as-prepared (4) in CH 3 CN in the glove box. Figure S24. UV-Vis spectra of as-prepared (4) in the glove box prior (dashed) and after (solid) addition of 1000 molar equiv. of H 2 O. Figure S25. ESI mass spectrum of as-prepared (4 ) in CH 3 CN in the glove box. Figure S26. ESI mass spectrum of the reaction mixture upon exposure of (1) to H 2 O/O 2 conditions after 6 days.

3 Figure S27. ESI mass spectrum of the reaction mixture upon exposure of (1 ) to H 2 O/O 2 conditions after 6 days. Figure S28. ESI mass spectrum of as-prepared (4) in H 2 O/O 2 conditions after 6 days. Figure S29. ESI mass spectrum of as-prepared (4 ) in H 2 O/O 2 conditions after 6 days. Figure S30. Spectral deconvolution of (1) in CH 3 CN Figure S31. Spectral deconvolution of (2) in CH 3 CN Figure S32. Spectral deconvolution of (3) Figure S33. Spectral deconvolution of as-prepared (4). Figure S34. Experimental and adjusted UV-Vis spectra of (1) in H 2 O/O 2 conditions after 6 days taking into account the contribution of (4), (2), (3) and (6). Figure S35. Experimental (black) and adjusted (dotted red) UV-Vis spectra of as-prepared (4) in H 2 O/O 2 conditions after 6 days in CH 3 CN taking into account the contribution of (4), (2), (3) and (6). Figure S36. Magnification of ESI mass spectrum of the reaction mixture upon exposure of (1) to O 2 -only conditions as a function of time ((a): 2 days, (b): 6 days and (c) 11 days), showing the predominance of (2) and the presence of (4) and (3). Figure S37. Experimental and adjusted UV-Vis spectra of (1) in O 2 -only conditions after 6 days taking into account the contribution of (4), (2), (3) and (6). Figure S38. ESI mass spectrum of as-prepared (4) in O 2 -only conditions after 6 days. Figure S39. Experimental (black) and adjusted (dotted red) UV-Vis spectra of as-prepared (4) in O 2 -only conditions after 6 days in CH 3 CN taking into account the contribution of (4), (2) and (6). Figure S40. ESI mass spectrum of the reaction mixture upon exposure of (1 ) to O 2 -only conditions after 6 days, showing the presence of (4 ) and (2 ). Figure S41. ESI mass spectrum of as-prepared (4 ) in O 2 -only conditions after 6 days. Figure S42. UV-Vis spectra recorded after 6 days for (1) (solid) an as-prepared (4) (dashed) under O 2 -only conditions. Experimental procedure for the chemical reduction of L Me(BPA)S-S. Figure S43. 1 H NMR spectrum of L Me(BPA)SH. HCl in CD 3 CN.

4 Table S1. Conversion coefficients from mass intensity to UV-Vis coefficient ratios. Table S2. Crystal data and structure refinement for (1). Table S3. Bond lengths [Å] and angles [deg] for (1). Table S4. Crystal data and structure refinement for (2). Table S5. Bond lengths [Å] and angles [deg] for (2). Table S6. Crystal data and structure refinement for (3). Table S7. Bond lengths [Å] and angles [deg] for (3). Table S8. XYZ Coordinates of DFT-optimized structure of (2) Table S9. XYZ Coordinates of DFT-optimized structure of (3) Table S10. Calculated electronic transitions of complexes (2) and (3). Table S11. Composition of the reaction mixture according to UV-Vis fitting and related conversion coefficients.

5 {(4)} {(1)} 2+ Relative Abundance {(1)} Relative Abundance Exp {(1)} + NL: 4.22E3 Calcd {(1) } + C 73 H 66 N 12 O 21 S 9 F 21 Cu m/z {(1)} m/z Figure S1. ESI mass spectrum of (1) in CH 3 CN.

6 {(4)} + Exp Exp Exp Calcd Calcd Calcd Calcd Figure S2. ESI mass spectrum of (1) in CH 3 CN. ms2@2387 showing the formation of (4) from the fragmentation of (1).

7 ε (M -1,cm -1 ) λ (nm) Figure S3. UV-Vis spectrum of (1) in CH 3 CN.

8 {(1 )} Exp {(1 )} {(4 )} Relative Abundance {(1 )} Calcd {(1 ) } + C 73 H 66 N 12 O 21 S 9 F 21 Zn m/z {(1 )} m/z Figure S4. ESI mass spectrum of (1 ) in CH 3 CN.

9 This experiments shows the formation of (4 ) from the fragmentation of (1 ) {(4 )} Relative Abundance Exp {(4 )} Calcd {(4 ) } + C 35 H 33 N 6 O 8 S 3 F 6 Zn m/z m/z Figure S5. ESI mass spectrum of (1 ) in CH 3 CN. ms2@2392 showing the formation of (4 ) from the fragmentation of (1 ).

10 Acetonitrile ppm Figure S6. 1 H NMR spectrum of (1 ) in CD 3 CN.

11 {(2) 2OTf Cl - } Cl - from the ionization chamber {(2)} Relative Abundance {(2) 1OTf - + 1Cl - } {(2)} m/z Figure S7. ESI mass spectrum of (2) in CH 3 CN.

12 ,9 SM: 100 7B Exp {(2)} ,9 Exp {(2)} Relative Abundance ,5 427,5 428,0 Relative Abundance ,9 1003,9 1004, ,0 428,4 429,0 429, ,0 1005,9 1006,8 1007, ,0 : , Calcd {(2)} + C 34 H 33 N 6 O 5 S 2 F 3 Cu Calcd {(2)} + C 35 H 33 N 6 O 8 S 3 F 6 Cu ,5 427,5 428, ,0 1004,0 1005, ,5 429,0 429,5 430, m/z ,0 1007, m/z 1008,0 1009,0 Figure S8. Calculated ESI profiles for (2) in CH 3 CN.

13 {(3) 1OTf Cl - } Cl - from the ionization chamber {(3)} Relative Abundance {(3) 1OTf - + 1Cl - } {(3)} m/z Figure S9. ESI mass spectrum of (3) in CH 3 CN.

14 SM: 100 7B Exp {(3)} Exp {(3)} Relative Abundance Relative Abundance Calcd 70 Calcd {(3)} {(3)} + C 35 H 33 N 6 O 9 S 3 F 6 Cu 2 60 C 34 H 33 N 6 O 6 S 2 F 3 Cu m/z m/z Figure S10. Calculated ESI profiles for (3) in CH 3 CN.

15 Figure S11. Optimized structures of (2) and selected metrics. Figure S12. Optimized structures of (3) and selected metrics.

16 nm nm Figure S13. Difference electron density sketch of the relevant transitions for (2) (yellow = negative, red = positive).

17 Figure S14. Difference electron density sketch of the relevant transition for nm (yellow = negative, red = positive). A.U (2) (3) Figure S15. Solid state (dotted line) and acetonitrile solution UV-vis (solid) spectra for (2) (red) and (3) (black) λ (nm)

18 (1) (2) (3) Magnetic Field (mt) Figure S16. X-band EPR spectra recorded for X-ray single crystals of (1), (2) and (3) in CH 3 CN at 10 K. dχ"/db [a. u.] magnetic field B [mt] Figure S17 X-band EPR spectra recorded for X-ray single crystals (2) in CH 3 CN at 10 K, (black). Microwave frequency GHz, microwave power 0.2 mw, modulation frequency 100 khz, modulation amplitude 1.2 mt, conversion time 164 ms. Simulations (red) gave g CuA = 2.315(2), 2.13(6), 2.03(1); A CuA = 530(10), 80(80), 0(6) MHz; linewidth (full width at half height) = 200(40) 200(40) 100(50) MHz; g CuB = 2.258(2), 2.126(7), 2.02(2); A CuB = 460(5), 90(90), 0(5) MHz; linewidth = 200(20) 200(50) 100(50) MHz. EasySpin cannot take into account an M I dependence of linewidth, a reason of simulation low-quality.

19 1,0 0,8 Absorbance 0,6 0,4 0,2 0, λ (nm) Figure S18. Changes on the UV-Vis spectrum of (1) in CH 3 CN from 0 (brown) to 14 days (blue) in the glove box. Each spectrum corresponds to 4 days except the last one.

20 Figure S19. ESI mass spectrum of the reaction mixture upon exposure of (1) to H 2 O-only conditions after 6 days.

21 Figure S20. Calculated ESI profiles of the reaction mixture with (1) under H 2 O-only conditions after 6 days.

22 Figure S21. ESI mass spectrum of the reaction mixture upon exposure (1 ) to H 2 O-only conditions after 6 days.

23 Figure S22. Calculated ESI profiles of the reaction mixture with (1 ) under H2O-only conditions after 6 days.

24 {(4)} Relative Abundance {(4)} m/z Figure S23. ESI mass spectrum of as-prepared (4) in CH 3 CN in the glove box.

25 Absorbance 0,5 (4) As-prepared in the glove box (4) As-prepared in the glove box molar eqs. H 2 O 0, Wavelength (nm) Figure S24. UV-Vis spectra of as-prepared (4) in the glove box prior (dashed) and after (solid) addition of 1000 molar eqs. of H 2 O.

26 {(4 )} {(4 )} Relative Abundance m/z Figure S25. ESI mass spectrum of as-prepared (4 ) in the glove box.

27 Figure S26. ESI mass spectrum of the reaction mixture upon exposure of (1) to H 2 O/O 2 conditions after 6 days.

28 {(4 )} {(4 )} Relative Abundance {(2 )} m/z Figure S27. ESI mass spectrum of the reaction mixture upon exposure of (1 ) to H 2 O/O 2 conditions after 6 days.

29 {(4)} Relative Abundance {(2)} m/z {(3)} Figure S28. ESI mass spectrum of as-prepared (4) in H 2 O/O 2 conditions after 6 days.

30 (4 ) Relative Abundance (2 ) m/z Figure S29. ESI mass spectrum of as-prepared (4 ) in H 2 O/O 2 conditions after 6 days.

31 Absorbance λ (nm) Figure S30. Spectral deconvolution of (1) in CH 3 CN; measurement (black), fit (orange), components (turquoise). Band coeff. (Bc) Center (nm) Half width (Hw) (nm) (1)

32 Absorbance λ (nm) Figure S31. Spectral deconvolution of (2) in CH 3 CN; measurement (black), fit (brown), components (turquoise). Band coeff. (Bc) Center (nm) Half width (Hw) (nm) (2) F F

33 Absorbance λ (nm) Figure S32. Spectral deconvolution of (3) in CH 3 CN; measurement (black), fit (blue), components (turquoise). Band coeff. (Bc) Center (nm) Half width (Hw) (nm) (3)

34 Absorbance λ (nm) Figure S33. Spectral deconvolution of as-prepared (4) in CH 3 CN; measurement (dotted black), fit (green), components (turquoise). Band coeff.(bc) Center (nm) Half width (Hw) (nm) As-prepared (4)

35 I(4) = 0.20 Absorbance I(6) = 0.11 I(6)/I(4) = λ (nm) Figure S34. Experimental (black) and adjusted (dotted red) UV-Vis spectra of as-prepared (1) in H 2 O/O 2 conditions after 6 days taking into account the contribution of (4) (green), (2) (brown), (3) (blue) and (6) (violet). (1) in H 2 O/O 2 conditions Species Species Band Center Half width coeff.(sc) coeff.(bc) (nm) (Hw) (nm) (4) (2) (3) (6)

36 Absorbance I(4) = I(6) = 0.10 I(6)/I(4) = λ (nm) Figure S35. Experimental (black) and adjusted (dotted red) UV-Vis spectra of as-prepared (4) in H 2 O/O 2 conditions after 6 days in CH 3 CN taking into account the contribution of (4) (green), (2) (brown) and (6) (violet). As-prepared (4) in H 2 O/O 2 conditions Species Species coeff (Sc) Band coeff. (Bc) Center (nm) Half width (Hw) (nm) (4) 0.7 (2) 0.39 (6)

37 Figure S36. Magnification of ESI mass spectrum of the reaction mixture upon exposure of (1) to O 2 -only conditions as a function of time ((a): 2 days, (b): 6 days and (c) 11 days), showing the predominance of (2) and the presence of (4) and (3).

38 Absorbance I(6) = 0, I(4) = 0, I(6)/I(4) = 9,7 λ (nm) Figure S37. Experimental (black) and adjusted (dotted red) UV-Vis spectra of (1) in O 2 -only conditions after 6 days in CH 3 CN taking into account the contribution of (4) (green), (2) (brown), (3) blue) and (6) (violet). (1) in O 2 -only conditions Species Species Band coeff. Half width Center (nm) coeff.(sc) (Bc) (Hw) (nm) (2) 0.80 (4) (3) (6)

39 {(4)} Relative Abundance {(2)} m/z {(3)} Figure S38. ESI mass spectrum of as-prepared (4) in O 2 -only conditions after 6 days.

40 Absorbance I(4) = 0, I(6) = 0,04 I(6)/I(4) = 0, λ (nm) Figure S39. Experimental (black) and adjusted (dotted red) UV-Vis spectra of as-prepared (4) in O 2 -only conditions after 6 days in CH 3 CN taking into account the contribution of (4) (green), (2) (brown) and (6) (violet). As-prepared (4) in O 2 -only conditions Species Species Band Center Half width coeff. (Sc) coeff. (Bc) (nm) (Hw) (nm) (4) (2) (6)

41 {(4 )} {(4 )} Relative Abundance {(2 )} m/z Figure S40. ESI mass spectrum of the reaction mixture upon exposure of (1 ) to O 2 -only conditions after 6 days, showing the presence of (4 ) and (2 ).

42 {(4 )} Relative Abundance {(2 )} m/z Figure S41. ESI mass spectrum of as-prepared (4 ) in O 2 -only conditions after 6 days.

43 0,8 0,6 Absorbance 0,4 0,2 0, λ (nm) Figure S42. UV-Vis spectra recorded after 6 days for (1) (solid) an as-prepared (4) (dashed) under O 2 -only conditions. Experimental procedure for the chemical reduction of L Me(BPA)S-S. Reduction with nbu 3 P. Under anaerobic condition, in a schlenk tube, LMe(BPA)S-S (125 mg, mmol) was dissolved in a mixture of 1.5 ml of MeOH and 0.5 ml of THF. To the yellow solution was added water (200 µl) and nbu3p (60 µl, mmol, 2 molar eqs.). After 4 hours, the reaction was evaporated to dryness and co-evaporated with diethylether (2*50 ml). The resulting oily residue was dissolved in dietyhlether (5 ml) and gaseous HCl bubbled in the solution, resulting in the formation of a pale beige precipitate. After filtration, the solid was triturated in diethylether to remove nbu3p and nbu3po traces. The resulting hydrochloride was obtained as 113 mg of a pale beige solid (75 %).

44 1 H NMR (300 MHz, CD 3 CN, δ ppm): 8.61 (d, 3 J = 6 Hz, 4H); 8.27 (t, 3 J = 6 Hz, 4H); 7.81 (m, 8 H); 6.94 (s, 2H); 3.61 (s, 8H); 3.55 (s, 4H); 2.13 (s, 6H), see Figure S34. ESI-MS, negative mode: m/z = 544 [L Me(BPA)S- ] - As-prepared (4) and (4 ). In a glove box, mg of L Me(BPA)SK was dissolved in 5 ml of CH3CN. A solution of x mg (mmol, 2.1 molar eqs.) of Cu(OTf)2 or mg (mmol, 2.1 molar eqs.) was added. In the case of Cu(II), the reaction mixture turned violet and remained yellow for Zn(II). Upon evaporation of the solvent, violet (mg) and yellow (mg) powders were isolated. ESI-MS in acetonitrile for as-prepared-(4) (Figures S22): m/z 971 [as-prepared (4)-(OTf)] + ; m/z = 411 [as-prepared (4)-2(OTf)] 2+. ESI-MS in acetonitrile for as-prepared-(4 ) (Figures S25): m/z 975 [as-prepared (4)-(OTf)] + ; m/z = 413 [as-prepared (4)-2(OTf)] 2+. Acetonitrile δ(ppm) Figure S43. 1 H NMR spectrum of L Me(BPA)SH. HCl in CD 3 CN

45 Table S1. Conversion coefficients from mass intensity to UV-Vis coefficient ratios. sample (Sc 2 /Sc 4 ) UV-Vis = x (I 2 /I 4 ) mass (4) in O 2- only 5.9 (4) in H 2 O/O (1) in H 2 O/O (1) in O 2- only a 4 b a Average of conversion coefficients obtained in other samples as direct determination was not possible in this case. b It could be noticed that coefficients from 1 to 5 have only slight effects on the overall shape of species (6) UV-Vis spectrum; (Sc): species coefficient.

46 Table S2. Crystal data and structure refinement for (1). Empirical formula C H Cu 4 F 24 N O 24 S 10 Formula weight 2894 Crystal system Triclinic Temperature 150(2) K Wavelength Å Space group P-1 a = (6)Å α = (4) deg; b = Unit cell dimensions (10) Å, β = (4)deg; c = (13) Å γ = deg. Volume, Z Density (calculated) Absorption coefficient F(000) Crystal size Theta range for data collection Limiting indices Reflections collected Independent reflections Absorption correction Max. and min. transmission Refinement method Data / restraints / parameters Goodness-of-fit on F 2 Final R indices [I>2sigma(I)] R indices (all data) Largest diff. peak and hole (5) A 3, g/cm mm x x mm to deg -16<=h<=17, -21<=k<=22, -31<=l<= [R(int) = ] Semi-empirical from equivalents and Full-matrix least-squares on F / 95 / R1 = , wr2 = R1 = , wr2 = and e.a -3

47 Table S3. Bond lengths [Å] and angles [deg] for (1). Cu1 N (6) C64 C (12) Cu1 N (6) C65 C (12) Cu1 N (6) C66 C (11) Cu1 N (8) C68 C (11) Cu2 N (7) C69 C (12) Cu2 N (7) C70 C (13) Cu2 N (7) C71 C (14) Cu2 N (8) C72 C (14) Cu2 O1S (6) N81 C (12) Cu3 N (6) C81 C (16) Cu3 N (6) N82 C (12) Cu3 N (6) C83 C (15) Cu3 N (7) N83 C (10) Cu3 O1S (5) C85 C (13) Cu4 N (6) N84 C (10) Cu4 N (6) C87 C (12) Cu4 N (7) N91 C (14) Cu4 N (7) C91 C (2) Cu4 N (7) N92 C (9) S1 C (8) C93 C (9) S1 S (3) C93 F6S (5) N1 C (10) N93 C (3) N1 C (9) C95 C (3) N1 C (9) N94 C (9) N2 C (10) C97 C (11) N2 C (10) N95 C (9) N3 C (10) C99 C (9) N3 C (10) S11 O1S (5) N4 C (9) S11 O2S (7) N4 C (10) S11 O3S (7) N4 C (11) S11 C1S 1.797(12) N5 C (10) F1S1 C1S 1.299(13) N5 C (11) F2S1 C1S 1.349(12) N6 C (11) F3S1 C1S 1.359(13) N6 C (11) S12 O1S (7) C1 C (11) S12 O2S (11) C1 C (10) S12 O3S (11) C2 C (12) S12 C2S 1.799(2) C2 C (11) F1S2 C2S 1.184(18) C3 C (11) F2S2 C2S 1.320(18)

48 C4 C (11) F3S2 C2S 1.39(2) C4 C (11) S13 O2S (17) C5 C (11) S13 O3S (11) C6 C (10) S13 C3S 1.813(19) C10 C (10) S13 O1S (7) C11 C (11) F1S3 C3S 1.32(2) C12 C (12) F2S3 C3S 1.25(2) C13 C (13) F3S3 C3S 1.36(2) C14 C (13) S13B O4S3 1.46(4) C16 C (11) S13B O5S3 1.62(4) C17 C (11) S13B C3SB 1.70(5) C18 C (12) S13B O1S (12) C19 C (13) F4S3 C3SB 1.31(4) C20 C (12) F5S3 C3SB 1.38(5) C22 C (12) F6S3 C3SB 1.24(5) C23 C (12) O5S3 C3SB 1.87(6) C24 C (14) S14 O1S (4) C25 C (14) S14 O2S (4) C26 C (13) S14 O3S (4) C28 C (12) S14 C4S 1.783(5) C29 C (13) F1S4 C4S 1.301(3) C30 C (14) F2S4 C4S 1.326(3) C31 C (15) F3S4 C4S 1.339(3) C32 C (14) S14B O4S4 1.42(3) S41 C (8) S14B O5S4 1.53(3) N41 C (9) S14B O6S4 1.39(3) N41 C (9) S14B C4SB 1.74(3) N41 C (9) F4S4 C4SB 1.37(3) N42 C (10) F5S4 C4SB 1.32(2) N42 C (9) F6S4 C (5) N43 C (9) F6S4 C4SB 1.34(3) N43 C (9) O5S4 C (5) N44 C (9) S15 O1S (8) N44 C (9) S15 O2S (8) N44 C (9) S15 O3S (9) N45 C (9) S15 C5S 1.787(14) N45 C (10) F1S5 C5S 1.337(12) N46 C (11) F2S5 C5S 1.324(12) N46 C (11) F3S5 C5S 1.307(13) C41 C (10) S16 O1S (7) C41 C (10) S16 O2S (6) C42 C (10) S16 O3S (7)

49 C42 C (10) S16 C6S 1.811(11) C43 C (11) F1S6 C6S 1.360(12) C44 C (11) F2S6 C6S 1.314(12) C44 C (10) F3S6 C6S 1.321(12) C45 C (10) S17 O1S (7) C46 C (10) S17 O2S (8) C49 O5S (3) S17 O3S (6) C50 C (10) S17 C7S 1.775(11) C51 C (10) F1S7 C7S 1.334(14) C52 C (12) F2S7 C7S 1.326(14) C53 C (13) F3S7 C7S 1.338(11) C54 C (11) S18 O1S (7) C56 C (10) S18 O2S (6) C57 C (11) S18 O3S (6) C58 C (12) S18 C8S 1.801(10) C59 C (12) F1S8 C8S 1.341(12) C60 C (11) F2S8 C8S 1.341(11) C62 C (10) F3S8 C8S 1.313(12) C63 C (10) 1 1-X,-1-Y,1-Z; 2 1-X,-Y,1-Z N2 Cu1 N1 81.9(2) C61 C60 C (8) N3 Cu1 N1 82.4(3) N43 C61 C (8) N3 Cu1 N (3) N44 C62 C (6) N81 Cu1 N (3) N45 C63 C (7) N81 Cu1 N2 99.0(3) N45 C63 C (7) N81 Cu1 N3 96.7(3) C64 C63 C (7) N4 Cu2 O1S2 88.0(2) C65 C64 C (8) N5 Cu2 N4 82.3(3) C66 C65 C (8) N5 Cu2 N (3) C65 C66 C (8) N5 Cu2 O1S2 90.1(3) N45 C67 C (8) N6 Cu2 N4 81.5(3) N44 C68 C (6)

50 N6 Cu2 O1S2 92.1(3) N46 C69 C (7) N82 Cu2 N (3) N46 C69 C (8) N82 Cu2 N5 99.2(3) C70 C69 C (8) N82 Cu2 N6 97.2(3) C69 C70 C (10) N82 Cu2 O1S2 88.9(3) C72 C71 C (9) N41 Cu3 O1S3 94.2(2) C71 C72 C (9) N42 Cu3 N (2) N46 C73 C (10) N42 Cu3 O1S3 94.0(2) C81 N81 Cu (9) N43 Cu3 N (2) N81 C81 C (13) N43 Cu3 N (3) C83 N82 Cu (9) N43 Cu3 O1S3 90.2(2) N82 C83 C (12) N83 Cu3 N (3) C85 N83 Cu (7) N83 Cu3 N (3) N83 C85 C (10) N83 Cu3 N (3) C87 N84 Cu (7) N83 Cu3 O1S3 89.7(2) N84 C87 C (10) N44 Cu4 N (2) N91 C91 C (16) N45 Cu4 N (2) N92 C93 C94 174(2) N45 Cu4 N (3) N92 C93 F6S (10) N45 Cu4 N (2) C94 C93 F6S4 2 83(10) N46 Cu4 N (3) N93 C95 C96 177(2) N46 Cu4 N (3) C97 N94 Cu (7) N84 Cu4 N (3) N94 C97 C (10) N84 Cu4 N (3) N95 C99 C (3)

51 N84 Cu4 N (3) O1S1 S11 O2S (4) N84 Cu4 N (3) O1S1 S11 C1S 103.6(4) C1 S1 S (2) O2S1 S11 C1S 102.1(6) C7 N1 Cu (5) O3S1 S11 O1S (4) C10 N1 Cu (4) O3S1 S11 O2S (5) C10 N1 C (6) O3S1 S11 C1S 103.6(5) C10 N1 C (6) F1S1 C1S S (9) C16 N1 Cu (4) F1S1 C1S F2S (9) C16 N1 C (6) F1S1 C1S F3S (11) C11 N2 Cu (5) F2S1 C1S S (8) C15 N2 Cu (6) F2S1 C1S F3S (10) C15 N2 C (7) F3S1 C1S S (8) C17 N3 Cu (5) O1S2 S12 C2S 104.0(7) C17 N3 C (7) O2S2 S12 O1S (5) C21 N3 Cu (6) O2S2 S12 C2S 104.0(8) C8 N4 Cu (5) O3S2 S12 O1S (7) C22 N4 Cu (5) O3S2 S12 O2S (8) C22 N4 C (6) O3S2 S12 C2S 102.9(8) C28 N4 Cu (5) S12 O1S2 Cu (4) C28 N4 C (6) F1S2 C2S S (12) C28 N4 C (6) F1S2 C2S F2S (16) C23 N5 Cu (6) F1S2 C2S F3S (15) C27 N5 Cu (6) F2S2 C2S S (10)

52 C27 N5 C (8) F2S2 C2S F3S (14) C29 N6 Cu (6) F3S2 C2S S (11) C29 N6 C (8) O2S3 S13 O3S (9) C33 N6 Cu (7) O2S3 S13 C3S 105.2(10) C2 C1 S (6) O2S3 S13 O1S (9) C6 C1 S (6) O3S3 S13 C3S 103.8(8) C6 C1 C (7) O3S3 S13 O1S (6) C1 C2 C (8) O1S3 S13 C3S 105.9(7) C3 C2 C (7) F1S3 C3S S (13) C3 C2 C (8) F1S3 C3S F3S (15) C2 C3 C (7) F2S3 C3S S (14) C3 C4 C (8) F2S3 C3S F1S (15) C3 C4 C (8) F2S3 C3S F3S (17) C5 C4 C (8) F3S3 C3S S (12) C6 C5 C (8) O4S3 S13B O5S3 137(2) C1 C6 C (7) O4S3 S13B C3SB 110(2) C5 C6 C (7) O5S3 S13B C3SB 68.5(19) C5 C6 C (7) O1S3 S13B O4S (17) N1 C7 C (6) O1S3 S13B O5S (15) C6 C8 N (6) O1S3 S13B C3SB 105.7(17) N1 C10 C (6) S13B O5S3 C3SB 57.9(19) N2 C11 C (7) S13B C3SB O5S3 53.7(17) N2 C11 C (7) F4S3 C3SB S13B 119(4)

53 C12 C11 C (7) F4S3 C3SB F5S3 100(3) C11 C12 C (8) F4S3 C3SB O5S3 101(3) C14 C13 C (8) F5S3 C3SB S13B 110(3) C13 C14 C (8) F5S3 C3SB O5S3 159(3) N2 C15 C (9) F6S3 C3SB S13B 112(3) N1 C16 C (6) F6S3 C3SB F4S3 109(4) N3 C17 C (7) F6S3 C3SB F5S3 105(4) N3 C17 C (8) F6S3 C3SB O5S3 73(3) C18 C17 C (8) O1S4 S14 O2S C19 C18 C (9) O1S4 S14 C4S C18 C19 C (8) O2S4 S14 C4S C21 C20 C (9) O3S4 S14 O1S N3 C21 C (9) O3S4 S14 O2S C23 C22 N (7) O3S4 S14 C4S N5 C23 C (7) F1S4 C4S S N5 C23 C (9) F1S4 C4S F2S C24 C23 C (8) F1S4 C4S F3S C25 C24 C (9) F2S4 C4S S C24 C25 C (9) F2S4 C4S F3S C25 C26 C (10) F3S4 C4S S N5 C27 C (10) S13 O1S3 Cu (4) N4 C28 C (7) S13B O1S3 Cu (6) N6 C29 C (8) O4S4 S14B O5S

54 N6 C29 C (9) O4S4 S14B C4SB C30 C29 C (9) O5S4 S14B C4SB C31 C30 C (11) O6S4 S14B O4S C32 C31 C (10) O6S4 S14B O5S C31 C32 C (11) O6S4 S14B C4SB N6 C33 C (11) C4SB F6S4 C (3) C41 S41 S (2) C49 1 O5S4 S14B 156(4) C47 N41 Cu (4) F4S4 C4SB S14B C50 N41 Cu (4) F5S4 C4SB S14B C50 N41 C (5) F5S4 C4SB F4S C56 N41 Cu (4) F5S4 C4SB F6S C56 N41 C (5) F6S4 C4SB S14B C56 N41 C (5) F6S4 C4SB F4S C51 N42 Cu (5) O1S5 S15 C5S 103.2(6) C51 N42 C (7) O2S5 S15 O1S (6) C55 N42 Cu (6) O2S5 S15 C5S 103.4(6) C57 N43 Cu (5) O3S5 S15 O1S (5) C61 N43 Cu (5) O3S5 S15 O2S (7) C61 N43 C (7) O3S5 S15 C5S 104.0(5) C48 N44 Cu (4) F1S5 C5S S (9) C62 N44 Cu (4) F2S5 C5S S (9) C62 N44 C (5) F2S5 C5S F1S (9) C68 N44 Cu (5) F3S5 C5S S (8)

55 C68 N44 C (6) F3S5 C5S F1S (10) C68 N44 C (6) F3S5 C5S F2S (12) C63 N45 Cu (5) O1S6 S16 O2S (4) C63 N45 C (7) O1S6 S16 C6S 104.0(5) C67 N45 Cu (5) O2S6 S16 C6S 102.3(5) C69 N46 Cu (5) O3S6 S16 O1S (4) C73 N46 Cu (7) O3S6 S16 O2S (4) C73 N46 C (8) O3S6 S16 C6S 103.7(5) C42 C41 S (5) F1S6 C6S S (7) C46 C41 S (6) F2S6 C6S S (7) C46 C41 C (7) F2S6 C6S F1S (10) C41 C42 C (7) F2S6 C6S F3S (9) C43 C42 C (7) F3S6 C6S S (8) C43 C42 C (7) F3S6 C6S F1S (9) C44 C43 C (7) O1S7 S17 O2S (6) C43 C44 C (7) O1S7 S17 O3S (4) C43 C44 C (8) O1S7 S17 C7S 102.9(5) C45 C44 C (8) O2S7 S17 O3S (4) C44 C45 C (7) O2S7 S17 C7S 103.0(6) C41 C46 C (7) O3S7 S17 C7S 103.7(5) C41 C46 C (6) F1S7 C7S S (8) C45 C46 C (6) F1S7 C7S F3S (10) C42 C47 N (6) F2S7 C7S S (9)

56 C46 C48 N (6) F2S7 C7S F1S (11) O5S4 1 C49 C44 114(10) F2S7 C7S F3S (9) N41 C50 C (6) F3S7 C7S S (8) N42 C51 C (6) O1S8 S18 C8S 104.1(5) N42 C51 C (7) O2S8 S18 O1S (4) C52 C51 C (7) O2S8 S18 O3S (4) C51 C52 C (8) O2S8 S18 C8S 103.5(4) C54 C53 C (8) O3S8 S18 O1S (4) C55 C54 C (8) O3S8 S18 C8S 103.4(5) N42 C55 C (8) F1S8 C8S S (8) C57 C56 N (6) F2S8 C8S S (7) N43 C57 C (6) F2S8 C8S F1S (9) N43 C57 C (7) F3S8 C8S S (8) C58 C57 C (7) F3S8 C8S F1S (9) C57 C58 C (8) F3S8 C8S F2S (9) C58 C59 C (8) 1 1-X,-1-Y,1-Z; 2 1-X,-Y,1-Z

57 Table S4. Crystal data and structure refinement for (2). Empirical formula Formula weight Crystal system Temperature Wavelength Space group Unit cell dimensions Volume, Z Density (calculated) Absorption coefficient F(000) Crystal size Theta range for data collection Limiting indices Reflections collected Independent reflections Absorption correction Max. and min. transmission Refinement method Data / restraints / parameters Goodness-of-fit on F 2 Final R indices [I>2sigma(I)] R indices (all data) Largest diff. peak and hole C42 H46 Cu2 F9 N7 O13 S Monoclinic 150(2) K Å P 21/c a = (3)Å α = 90 deg; b = (14) Å β = (4)deg; c = (11) Å γ = 90 deg (5) A 3, g/cm mm x x mm 3.46 to deg -17<=h<=15, -22<=k<=28, -31<=l<= [R(int) = ] Semi-empirical from equivalents and Full-matrix least-squares on F / 45 / R1 = , wr2 = R1 = , wr2 = and e.a -3

58 Table S5. Bond lengths [Å] and angles [deg] for (2). Cu1 O (2) C19 C (6) Cu1 N (3) C20 C (5) Cu1 N (3) C22 C (4) Cu1 N (3) C23 C (4) Cu1 N (3) C24 C (5) Cu2 O (2) C25 C (5) Cu2 O (2) C26 C (5) Cu2 N (3) C28 C (4) Cu2 N (3) C29 C (5) Cu2 N (3) C30 C (5) S1 O (2) C31 C (6) S1 O (2) C32 C (5) S1 C (3) N41 C (4) N1 C (4) C41 C (5) N1 C (4) S2 O (3) N1 C (4) S2 O (3) N2 C (4) S2 O (3) N2 C (5) S2 C2S 1.827(4) N3 C (5) F1S2 C2S 1.327(5) N3 C (4) F2S2 C2S 1.327(4) N4 C (4) F3S2 C2S 1.325(5) N4 C (4) S3 O (3) N4 C (4) S3 O (3) N5 C (4) S3 O (3)

59 N5 C (4) S3 C3S 1.825(4) N6 C (4) F1S3 C3S 1.325(5) N6 C (4) F2S3 C3S 1.322(4) C1 C (4) F3S3 C3S 1.340(5) C1 C (4) S4 O (4) C2 C (4) S4 O (3) C2 C (4) S4 O (4) C3 C (5) S4 C4S 1.827(6) C4 C (5) S4B O (10) C4 C (4) S4B O (10) C5 C (4) S4B O (10) C6 C (4) S4B C4S 1.620(18) C10 C (5) F1S4 C4S 1.273(6) C11 C (5) F2S4 C4S 1.315(5) C12 C (7) F3S4 C4S 1.343(6) C13 C (7) O51 C (9) C14 C (6) O51 C (7) C16 C (5) C51 C (11) C17 C (5) C52 C (11) C18 C (6) C53 C (10) N4 Cu1 O (10) N3 C17 C (3) N5 Cu1 O (10) C18 C17 C (3) N5 Cu1 N (10) C17 C18 C (4) N6 Cu1 O (10) C18 C19 C (4)

60 N6 Cu1 N (10) C21 C20 C (4) N6 Cu1 N (11) N3 C21 C (4) N6 Cu1 N (11) N4 C22 C (2) N41 Cu1 O (10) N5 C23 C (3) N41 Cu1 N (11) N5 C23 C (3) N41 Cu1 N (11) C24 C23 C (3) O3 Cu2 O (10) C25 C24 C (3) O3 Cu2 N (11) C24 C25 C (3) N1 Cu2 O (10) C27 C26 C (3) N2 Cu2 O (11) N5 C27 C (3) N2 Cu2 O (12) N4 C28 C (3) N2 Cu2 N (12) N6 C29 C (3) N2 Cu2 N (12) N6 C29 C (3) N3 Cu2 O (10) C30 C29 C (3) N3 Cu2 O (11) C29 C30 C (4) N3 Cu2 N (11) C32 C31 C (4) O1 S1 C (13) C31 C32 C (3) O2 S1 O (14) N6 C33 C (3) O2 S1 C (14) C41 N41 Cu (3) S1 O1 Cu (13) N41 C41 C (4) S1 O2 Cu (14) O11 S2 O (17) C7 N1 Cu (19) O11 S2 O (15) C10 N1 Cu (2) O11 S2 C2S (17) C10 N1 C (2) O12 S2 O (16) C16 N1 Cu (19) O12 S2 C2S (19)

61 C16 N1 C (3) O13 S2 C2S (19) C16 N1 C (3) F1S2 C2S S (3) C11 N2 Cu (2) F2S2 C2S S (3) C11 N2 C (3) F2S2 C2S F1S (4) C15 N2 Cu (3) F3S2 C2S S (3) C17 N3 Cu (2) F3S2 C2S F1S (3) C17 N3 C (3) F3S2 C2S F2S (3) C21 N3 Cu (3) O21 S3 O (19) C8 N4 Cu (19) O21 S3 O (19) C22 N4 Cu (19) O21 S3 C3S (18) C22 N4 C (2) O22 S3 O (17) C22 N4 C (2) O22 S3 C3S (18) C28 N4 Cu (18) O23 S3 C3S (19) C28 N4 C (3) F1S3 C3S S (3) C23 N5 Cu (2) F1S3 C3S F3S (3) C27 N5 Cu (2) F2S3 C3S S (3) C27 N5 C (3) F2S3 C3S F1S (3) C29 N6 Cu (2) F2S3 C3S F3S (3) C33 N6 Cu (2) F3S3 C3S S (3) C33 N6 C (3) O31 S4 C4S 103.7(2) C2 C1 S (2) O32 S4 O (2) C2 C1 C (3) O32 S4 C4S 101.5(2) C6 C1 S (2) O33 S4 O (3) C1 C2 C (3) O33 S4 O (2) C1 C2 C (3) O33 S4 C4S 105.2(3)

62 C3 C2 C (3) O34 S4B O36 121(3) C4 C3 C (3) O34 S4B C4S 113(2) C3 C4 C (3) O35 S4B O34 117(3) C3 C4 C (3) O35 S4B O36 105(3) C5 C4 C (3) O35 S4B C4S 85.7(18) C4 C5 C (3) O36 S4B C4S 109.4(19) C1 C6 C (3) F1S4 C4S S (4) C5 C6 C (3) F1S4 C4S S4B 135.5(9) C5 C6 C (3) F1S4 C4S F2S (5) N1 C7 C (3) F1S4 C4S F3S (5) N4 C8 C (3) F2S4 C4S S (3) N1 C10 C (3) F2S4 C4S S4B 97.2(6) N2 C11 C (3) F2S4 C4S F3S (4) N2 C11 C (4) F3S4 C4S S (4) C12 C11 C (4) F3S4 C4S S4B 100.3(9) C13 C12 C (4) C54 O51 C (5) C12 C13 C (4) O51 C51 C (6) C13 C14 C (4) C53 C52 C (8) N2 C15 C (4) C52 C53 C (6) N1 C16 C (3) O51 C54 C (6) N3 C17 C (3)

63 Table S6. Crystal data and structure refinement for (3). Empirical formula Formula weight Crystal system Temperature Wavelength Space group Unit cell dimensions Volume, Z Density (calculated) Absorption coefficient F(000) Crystal size Theta range for data collection Limiting indices Reflections collected Independent reflections Absorption correction Max. and min. transmission Refinement method Data / restraints / parameters Goodness-of-fit on F 2 Final R indices [I>2sigma(I)] R indices (all data) Largest diff. peak and hole C40 H39 Cu2 F9 N8 O11.58 S Monoclinic 150(2) K Å P 21/n 1 a = (10) Å α = 90 deg; b = (13) Å β = (8) deg; c = (14) Å γ = 90 deg (6) A 3, g/cm mm x 0.93 x 0.59 mm to deg -16<=h<=15, -23<=k<=23, -25<=l<= [R(int) = ] Semi-empirical from equivalents and Full-matrix least-squares on F / 6 / R1 = , wr2 = R1 = , wr2 = and e.a -3

64 Table S7. Bond lengths [Å] and angles [deg] for (3). Cu1 O (3) C19 C (8) Cu1 N (4) C20 C (8) Cu1 N (4) C23 C (7) Cu1 N (4) C24 C (7) Cu1 N (4) C25 C (8) Cu2 O (4) C26 C (8) Cu2 N (4) C27 C (7) Cu2 N (4) C29 C (7) Cu2 N (4) C30 C (7) Cu2 N (4) C31 C (8) S1 O (6) C32 C (8) S1 O (4) C33 C (7) S1 O (3) N41 C (6) S1 C (5) C41 C (7) N1 C (6) N42 C (6) N1 C (6) C43 C (8) N1 C (6) S11 O1S (5) N2 C (6) S11 O2S (5) N2 C (6) S11 O3S (4) N2 C (6) S11 C1S 1.793(8) N3 C (6) F1S1 C1S 1.327(7) N3 C (6) F2S1 C1S 1.302(7) N4 C (6) F3S1 C1S 1.359(8) N4 C (7) S12 O1S (4)

65 N5 C (6) S12 O2S (5) N5 C (6) S12 O3S (4) N6 C (6) S12 C2S 1.802(7) N6 C (6) F1S2 C2S 1.323(8) C1 C (7) F2S2 C2S 1.327(7) C1 C (7) F3S2 C2S 1.329(8) C2 C (7) F1S3 C3S 1.356(10) C2 C (7) F1S3 C3SB 1.22(2) C3 C (7) F2S3 C3S 1.316(9) C4 C (7) F2S3 C3SB 1.55(3) C4 C (7) O1S3 S (6) C5 C (6) O1S3 S13B 1.428(12) C6 C (7) S13 O2S (9) C10 C (7) S13 O3S (12) C11 C (7) S13 C3S 1.817(10) C12 C (8) F3S3 C3S 1.324(11) C13 C (8) S13B O4S (18) C14 C (8) S13B O5S3 1.42(3) C16 C (7) S13B C3SB 1.85(3) C17 C (8) F4S3 C3SB 1.28(3) C18 C (8)

66 N2 Cu1 O (14) N1 C16 C (4) N5 Cu1 O (14) N4 C17 C (4) N5 Cu1 N (16) N4 C17 C (5) N5 Cu1 N (16) C18 C17 C (5) N5 Cu1 N (16) C17 C18 C (5) N6 Cu1 O (14) C20 C19 C (6) N6 Cu1 N (15) C19 C20 C (5) N6 Cu1 N (16) N4 C21 C (5) N41 Cu1 O (14) N2 C23 C (4) N41 Cu1 N (16) N5 C24 C (4) N1 Cu2 O (15) N5 C24 C (5) N3 Cu2 O (15) C25 C24 C (5) N3 Cu2 N (16) C24 C25 C (5) N3 Cu2 N (17) C27 C26 C (5) N4 Cu2 O (16) C28 C27 C (5) N4 Cu2 N (16) N5 C28 C (5) N42 Cu2 O (16) N2 C29 C (4) N42 Cu2 N (17) N6 C30 C (4) N42 Cu2 N (18) N6 C30 C (5) N42 Cu2 N (18) C31 C30 C (5) O1 S1 O (3) C32 C31 C (5) O1 S1 O (3) C31 C32 C (5) O1 S1 C (3) C34 C33 C (5) O2 S1 O (2) N6 C34 C (5) O2 S1 C (2) C41 N41 Cu (4)

67 O3 S1 C (2) N41 C41 C (6) S1 O2 Cu (2) C43 N42 Cu (5) S1 O3 Cu (19) N42 C43 C (6) C7 N1 Cu (3) O1S1 S11 O3S (3) C10 N1 Cu (3) O1S1 S11 C1S 103.0(4) C10 N1 C (4) O2S1 S11 O1S (3) C16 N1 Cu (3) O2S1 S11 O3S (3) C16 N1 C (4) O2S1 S11 C1S 103.0(3) C16 N1 C (4) O3S1 S11 C1S 103.2(3) C8 N2 Cu (3) F1S1 C1S S (5) C23 N2 Cu (3) F1S1 C1S F3S (6) C23 N2 C (4) F2S1 C1S S (5) C29 N2 Cu (3) F2S1 C1S F1S (6) C29 N2 C (4) F2S1 C1S F3S (6) C29 N2 C (4) F3S1 C1S S (5) C11 N3 Cu (3) O1S2 S12 C2S 101.9(3) C15 N3 Cu (3) O2S2 S12 O1S (3) C15 N3 C (4) O2S2 S12 O3S (3) C17 N4 Cu (3) O2S2 S12 C2S 104.2(3) C21 N4 Cu (4) O3S2 S12 O1S (3) C21 N4 C (5) O3S2 S12 C2S 103.5(3) C24 N5 Cu (3) F1S2 C2S S (5) C28 N5 Cu (3) F1S2 C2S F2S (6) C28 N5 C (4) F1S2 C2S F3S (6) C30 N6 Cu (3) F2S2 C2S S (4)

68 C34 N6 Cu (3) F2S2 C2S F3S (6) C34 N6 C (4) F3S2 C2S S (5) C2 C1 S (4) O1S3 S13 O2S (4) C2 C1 C (4) O1S3 S13 O3S (6) C6 C1 S (3) O1S3 S13 C3S 106.4(4) C1 C2 C (4) O2S3 S13 O3S (7) C3 C2 C (4) O2S3 S13 C3S 102.6(5) C3 C2 C (4) O3S3 S13 C3S 104.4(6) C4 C3 C (5) F1S3 C3S S (6) C3 C4 C (5) F2S3 C3S F1S (7) C5 C4 C (4) F2S3 C3S S (6) C5 C4 C (5) F2S3 C3S F3S (7) C4 C5 C (5) F3S3 C3S F1S (7) C1 C6 C (4) F3S3 C3S S (7) C5 C6 C (4) O1S3 S13B C3SB 104.8(10) C5 C6 C (4) O4S3 S13B O1S (10) N1 C7 C (4) O4S3 S13B O5S (15) N2 C8 C (4) O4S3 S13B C3SB 104.2(14) N1 C10 C (4) O5S3 S13B O1S (14) N3 C11 C (4) O5S3 S13B C3SB 97.5(15) N3 C11 C (5) F1S3 C3SB F2S (19) C12 C11 C (5) F1S3 C3SB S13B 111.0(17) C13 C12 C (5) F1S3 C3SB F4S3 116(2) C12 C13 C (5) F2S3 C3SB S13B 94.5(15) C13 C14 C (5) F4S3 C3SB F2S (18)

69 N3 C15 C (5) F4S3 C3SB S13B 109(2)

70 Table S8. XYZ Coordinates of DFT-optimized structure of (2) Cu Cu S O O O H H N N N N N N C C C H C C H C C H H C H H C H

71 H H C H H C C H C H C H C H C H H C C H C H C H C H C H H C C

72 H C H C H C H C H H C C H C H C H C H N C C H H H S F F F O O