Supporting Information

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1 Supporting Information Novel ne-pot Synthesis of Polysubstituted Isocoumarins from Arynes and Trifluoroacetylated β-diketones Kentaro kuma,* Koki Hirano, Yukiko Tanabe, Ryoichi Itoyama, Atsumi Miura, Noriyoshi Nagahora, and Kosei Shioji Department of Chemistry, Fukuoka University, Jonan-ku, Fukuoka (Received November 28, 2013; CL ; Copyright The Chemical Society of Japan

2 Supporting Information General: All chemicals were obtained from commercial suppliers and were used without further purification. Analytical TLC was carried out on precoated plates (Merck silica gel 60, F254) and flash column chromatography was performed with silica (Merck, mesh). NMR spectra ( 1 H at 400 MHz; 13 C at 100 MHz) were recorded in CDCl3, and chemical shifts are expressed in ppm relative to internal TMS for 1 H- and 13 C-NMR. Melting points were uncorrected. Reaction of 4,4,4-trifluoro-1-p-tolylbutan-1,3-dione with triflate 1a at rt To a solution of 4,4,4-trifluoro-1-p-tolylbutan-1,3-dione (115 mg, 0.50 mmol) and CsF (228 mg, 1.5 mmol) in acetonitrile (6.0 ml) was added triflate 1a (179 mg, 0.60 mmol) in acetonitrile (3.0 ml). After standing at rt for 16h, the reaction mixture was washed with water, dried over MgS4, filtered, and evaporated to give a pale yellow oil, which was chromatographed over silica gel by elution with hexane-dichloromethane (1:1) to afford 3-tolylisocoumarin 3a (26.1 mg, 0.18 mmol), 1-trifluoromethyl-3-tolyl-1H-isochromen-1-ol 4a (8.4 mg, 0.04 mmol), and 2-trifluoroacetyl-2 -toluylbiphenyl 5 (8.7 mg, 0.03 mmol). Tol 3a 3-p-Tolylisocoumalin 3a: colorless crystals: mp o C (lit. 1 mp o C). 1 H NMR S1

3 (CDCl3) = 2.39 (s, 3H, CH3), 6.88 (s, 1H, CH), 7.24 (d, J = 8.0 Hz, 2H, Ar), (m, 2H), 7.68 (t, J = 8.0 Hz, 1H, Ar), 7.75 (d, J = 8.0 Hz, 1H, Ar), 8.28 (d, J = 8.0 Hz, 1H, Ar). Me 3b 3-Methylisocoumarin 3b: colorless crystals: mp o C (lit. 2 mp o C) 1 H NMR (CDCl3) = 2.28 (s, 3H, Me), 6.24 (s, 1H, =CH), 7.34 (d, 1H, J = 7.6 Hz, Ar), 7.45 (t, 1H, J = 7.6 Hz, Ar), 7.65 (t, 1H, J = 7.6 hz, Ar), 8.25 (d, 1H, J = 7.6 Hz, Ar). Tol H CF 3 4a trifluoromethyl-3-p-tolyl-1h-isochromen-1-ol 4a: colorless oil. 1 H NMR (CD3CN) = 2.39 (s, 3H, Me), 6.41 (br, 1H, H), 6.57 (s, 1H, =CH), (m, 3H, Ar), 7.36 (dd, 1H, J = 7.6, 7.2 Hz, Ar), 7.47 (dd, 1H, J = 7.6, 7.2 Hz, Ar), 7.61 (d, 1H, J = 7.6 Hz, Ar), 7.70 (d, 2H, J = 7.6 Hz, Tol). 19 F NMR (CD3CN) = C NMR (CDCl3) = (Me), 44.55, (q, JCF = 23 Hz, q-c), (=CH), (q, JCF = 288 Hz, CF3), , , , , , , , , , , , (Ar). HRMS (m/z): Found: (M + ). Calcd for C17H13F32: Me H CF 3 4b Trifluoromethyl-3-methyl-1H-isochromen-1-ol 4b: colorless oil. 1 H NMR (CDCl3) = 2.02 (s, 3H, Me), 3.60 (s, 1H, H), 5.66 (s, 1H, =CH), 7.01 (d, 1H, J = 7.6 Hz, Ar), 7.24 (t, 1H, J = 7.6 Hz, Ar), 7.36 (t, 1H, J = 7.6 Hz, Ar), 7.54 (d, 1H, J = 7.6 Hz, Ar). 13 C NMR (CDCl3) = (Me), (q-c), (=CH), (q, JCF =291 Hz, CF3), , , , , , F NMR (CDCl3) = HRMS (m/z): Found: (M + ). Calcd S2

4 for C11H9F32: Small amount of 2-(acetylmethyl)phenyl trifluoromethyl ketone (isomer of 4b) was observed in its 1 H and 13 C NMR spectra. F 3 C p-tol 5 2-trifluoroacetyl-2 -p-toluylbiphenyl 5: colorless oil: 1 H NMR (CDCl3) = 2.41 (s, 3H, CH3), 4.37 (s, 2H, CH2), 7.05 (d, J = 7.6 Hz, 1H, Ar), 7.22 (d, 1H, J = 8.0 Hz, Ar), (m, 5H, Ar), 7.37 (t, 1H, J = 7.6 Hz, Ar), 7.47 (t, 1H, J = 7.6 Hz, Ar), 7.65 (d, 2H, J = 8.4 Hz, Ar), 7.81 (d, 1H, J = 7.6 Hz, Ar). 19 F NMR (CDCl3) = (s, CF3). 13 C NMR (CDCl3) = (Me), (CH2), (q, JCF = 290.8Hz, CF3), , , , , , , , , , , , , , , , (Ar), (q, JCF =34.6 Hz, C=), (C=). HRMS (m/z): Found: (M + ). Calcd for C23H17F32: (M + ). F 3 C H 6 7,12-Dihydro-7-hydroxy-7-trifluoromethyldibenzo[a,d]cycloocten-5(6H)-one 6: colorless solid; mp oc; 1 H NMR (CDCl3) = 3.06 (d, 1H, J = 14.0 Hz, CHH), 3.94 (d, 1H, J = 16.0 Hz, CHH), 4.58 (d, 1H, J = 14.0 Hz, CHH), 4.95 (d, 1H, J = 16.0 Hz, CHH), 7.12 (d, 1H, J = 7.4 Hz, Ar), (m, 3H, Ar), 7.43 (d, 1H, J = 7.4 Hz, Ar), 7.50 (t, 1H, J = 7.4 Hz, Ar), 7.60 (d, 1H, J = 7.6 Hz, Ar), 7.95 (d, 1H, J = 7.6 Hz, Ar). 19 F NMR (CDCl3) = (CF3). 13 C NMR (CDCl3) = (CH2), (CH2), (q, JCF = 30.5 Hz) C-H), (q, JCF = Hz, CF3), , , , , , , , , , , , , (Ar), (C=). Reaction of 4,4,4-trifluoro-1-p-tolylbutan-1,3-dione with triflate 1a in refluxing acetonitrile To a solution of 4,4,4-trifluoro-1-p-tolylbutan-1,3-dione (115 mg, 0.50 mmol) and CsF (228 mg, S3

5 1.5 mmol) in Acetonitrile (7 ml) was added triflate 1a (253 mg, 0.85 mmol) in acetonitrile (3 ml). After refluxing for 5 h, the reaction mixture was washed with water, dried over MgS4, filtered, and evaporated to give pale yellow oil, which was chromatographed over silica gel by elution with hexane-dichloromethane (1:1) to afford 3-tolylisocoumarin 3a (51.5 mg, mmol) and 5a (17.5 mg, mmol). Reaction of 4a with CsF To a suspension of CsF (3.0 mg, 0.02 mmol) in CD3CN (0.4 ml), a solution of 4a (4.3 mg, 0.02 mmol) in CD3CN (0.2 ml) was added. After standing for 7 h at 70 o C, 1 H NMR of the reaction mixture was measured. Isocoumarin 3a and CHF3 3 were formed almost quantitatively. 1 HNMR Chart After 2 hr at 70 o C S4

6 1 H and 19 F NMR of RM after 2h 1 H NMR after 2h at 70 o C δ = 6.80 (q, J= 79.2 Hz) 19 F NMR 70 2h δ = (d, J= 79.2 Hz) ref. 3 δ = (d, J= 79.2 Hz) Reaction of 4,4,4-trifluoro-1-phenylbutan-1,3-dione with triflate 1a in refluxing acetonitrile To a solution of 4,4,4-trifluoro-1-phenylbutan-1,3-dione (108 mg, 0.50 mmol) and CsF (228 mg, 1.50 mmol) in acetonitrile (7 ml) was added triflate 1a (253 mg, 0.85 mmol) in acetonitrile (3 ml). After refluxing for 6h, the reaction mixture was washed with water, dried over MgS4, filtered, and evaporated to give pale yellow oil, which was chromatographed over silica gel by elution with hexane-dichloromethane (1:1) to afford 3-phenylisocoumarin 3b (71.1 mg, 0.32 mmol). ther reactions were carried out in a similar manner. 3c 3-Phenylisocoumarin 3c: colorless solid; mp o C (lit. 4 mp o C). 1 H NMR (CDCl3) = 6.98 (s, 1H, CH), (m, 5H, Ar), 7.73 (t, J = 9.2 Hz, 1H, Ar), 7.90 (d, J = 7.6 Hz, 2H, Ar), 8.33 (d, J = 7.6 Hz, 1H, Ar). 13 C NMR (CDCl3) = (=CH), , , , , , , , , , , (Ar), (C=). S5

7 3d 3-(4-methoxyphenyl)isocoumarin 3d: colorless solid; mp o C (lit. 4 mp o C). 1 H NMR (CDCl3) = 3.86 (s, 3H, Me), 6.84 (s, 1H, CH), 6.97 (d, J = 8.4 Hz, 1H, Ar), (m, 2H, Ar), 7.69 (t, J = 7.4 Hz, 1H, Ar), 7.82 (d, J = 8.4 Hz, Ar), 8.28 (d, J = 9.6 Hz, 1H). Cl 3e 3-(4-Chlorophenyl)isocoumarin 3e: colorless solid; mp o C (lit. 5 mp o C) 1 H NMR (CDCl3) = 6.91 (s, 1H, =CH), 7.41 (d, 2H, J = 8.0 Hz, Ar), 7.50 (dt, J = 8.0 Hz, 8.8 Hz, 2H, Ar), 7.72 (t, J = 7.6 Hz, 1H, Ar), 7.80 (d, J = 8.0 Hz, 2H, Ar), 8.28 (d, J = 8.0 Hz, 1H, Ar). Me p-tol Me 3f 6,7-Dimethyl-(4-methylphenyl)isocoumarin 3f: colorless solid; Mp o C. 1 H NMR (CDCl3) = 2.38 (s, 3H, CH3), 2.39 (s, 3H, CH3), 2.40 (s, 3H, CH3), 6.84 (s, 1H, CH), (m, 4H, Ar), 7.76 (d, J = 8.0 Hz, 2H, Ar), 8.06 (s, 1H, Ar). 13 C NMR (CDCl3) = (Me), (Me), (Me), , , , , , , , , , , , (Ar), (C=). HRMS (m/z): Found: (M + ). Calcd for C18H162: (M + ). S6

8 Me Me Me 3g Compound 3g: colorless solid; mp o C. 1 H NMR δ = 2.25 (s, 3H, CH3), 2.33 (s, 3H, Me), 2.35 (s, 3H, Me), 6.16 (s, 1H, CH), 7.08 (s, 1H, Ar), 7.97 (s, 1H, Ar). 13 C NMR δ = (Me), (Me), (Me), (=CH), , , , , , , (Ar), (C=). HRMS (m/z): Found: (M + ). Calcd for C12H122: (M + ). Me Me Me 3h 6,7-Dimethoxy-3-methylisocoumarin 3h: colorless solid; mp o C (lit. 6 mp o C). 1 H NMR (CDCl3) δ = 2.27 (s, 3H, CH3), 3.97 (s, 3H, Me), 3.98 (s, 3H, Me), 6.19 (s, 1H, CH2), 6.71 (s, 1H, Ar), 7.61 (s, 1H, Ar). 13 C-NMR (CDCl3) δ = (Me), (Me), (Me), , , , 113,71, , , , (Ar), (C=). 3i 6,7-Methylenedioxy-3-methylisocoumarin 3i: colorless solid; mp o C (lit. 7 mp o C). 1 H NMR δ = 2.26 (s, 3H, CH3), 6.08 (s, 2H, CH2), 6.15 (s, 1H, Ar), 6.71 (s, 1H, Ar), 7.58 (s, 1H, Ar). 3j 6,7-Methylenedioxy-3-phenylisocoumrin 3j: colorless solid; mp o C (lit. 1 mp S7

9 o C). 1 H NMR δ = 6.12 (s, 2H, CH2), 6.86 (d, J = 7.2 Hz, 1H, Ar), 6.87 (s, 1H, CH), (m, 3H, Ar), 7.66 (s, 1H, Ar), 7.85 (d, J = 8.0 Hz, 2H, Ar). 13 C NMR (CDCl3) = (=CH), (CH2), , , (Ph), (Ph), (Ph), , , , , (Ar), (C=). F F 3k 6,7-Difluoro-3-methylisocoumarin 3k: colorless solid; mp o C. 1 H NMR δ = 2.29 (s, 3H, CH3), 6.20 (s, 1H, CH), 7.12 (dd, J = 7.2 Hz, 1H, Ar), 8.03 (dd, J = 8.0 Hz, 1H, Ar). 19 F NMR δ = (ddd, J = 7.0, 10.0, and 21.1 Hz), (ddd, J = 8.3, 10.0, and 21.1 Hz). 13 C NMR (CDCl3) = (Me), (=CH), (d, JCF = 19 Hz, Ar), , (d, JCF = 15 Hz, Ar), , (dd, JCF = 559 and 19 Hz), (dd, JCF = 547 and 15Hz, Ar), (Ar), (C=). HRMS (m/z): Found: M + : Calcd for C10H6F22: M + : Ph Me 3l 8-Methoxyl-3-phenylisocoumarin 3l: colorless solid; mp o C (lit. 8 mp o C). 1 H NMR δ = 4.02 (s, 3H, Me), 6.85 (s, 1H, CH), 6.94 (d, J = 8.0 Hz, 1H, Ar), 7.03 (d, J = 8.0 Hz, 1H, Ar), (m, 3H, Ar), 7.61 (t, J = 8.0 Hz, 1H, Ar), 7.88 (d, J = 8.0 Hz, 2H, Ar). HRMS (m/z): Found: M + : Calcd for C16H143: M + +1: Two Step Synthesis of Thunberginol A To a solution of 4,4,4-trifluoro-1-(3,4-dimethoxyphenyl)butan-1,3-dione 2f (83 mg, 0.30 mmol) and CsF (228 mg, 1.50 mmol) in acetonitrile (6 ml) was added 3-methoxy-2-trimethylsilylphenyl triflate 1f (128 mg, 0.39 mmol) in acetonitrile (3 ml). After refluxing for 4 h, the reaction mixture was washed with water, extracted with ethyl acetate (7 ml S8

10 x 3). The combined extract was dried over MgS4, filtered, and evaporated to give pale yellow oil, which was chromatographed over silica gel by elution with hexane-dichloromethane (1:1) to afford 3-(3,4-dimethoxyphenyl)-8-methoxyisocoumarin 3m (50.1 mg, 0.16 mmol). This isocoumarin 3m (39 mg, 0.16 mmol) in dichloromethane (10 ml) was treated with BBr3 (1.13 mmol) in dichloromethane (1.05 ml) at -78 o C. After stirring for 1 h, the reaction mixture was warmed to rt. After stirring for 15h, the reaction mixture was washed with water, dried over sodium sulfate, filtered, and evaporated to give pale yellow oil, which was chmatographed over silica gel by elution with dichloromethane to give 3-(3,4-dihydoroxyphenyl)-8-hydroxyisocoumarin 7 (Thunberginol A) (38 mg, 0.14 mmol). Me Me Me 3m 3-(3,4-Dimethoxyphenyl)-8-methoxyisocoumarin 3m: colorless solid; mp o C (lit. 9 mp o C) 1 H NMR δ = 3.93 (s, 3H, Me), 3.98 (s, 3H, Me), 4.01 (s, 3H, Me), 6.74 (s, 1H, CH), (m, 2H, Ar), 6.99 (d, J = 7.6 Hz, 1H, Ar), 7.35 (s, 1H, Ar), 7.46 (d, J = 8.4 Hz, 1H, Ar), 7.60 (t, J = 8.4 Hz, 1H, Ar). 13 C NMR (CDCl3) δ = 56.22, 56.41, 56.54, , , , , , , , , , , , , , , H H H 7 Thunberginol A 7: colorless solid; mp o C (lit. 9 mp o C): 1 H NMR (d-dms) δ = 6.83 (d, J = 8.4 Hz, 1H, Ar), 6.90 (d, J = 8.4 Hz, 1H, Ar), (m, 2H, CH, Ar), 7.25 (s, 1H, Ar), 7.66 (t, J = 8.0 Hz, 1H, Ar), 9.28 (br, 1H, H), 9.55 (br, 1H, H), (br, 1H, H). 13 C NMR (CDCl3) δ =101.33, , , , , , , , , , , , , , S9

11 8 Xyridine A 8: colorless solid; mp o C (lit. 10 mp o C) 1 H NMR δ = 0.98 (t, J = 7.6 Hz, 3H, CH3), 1.72 (sext, J = 7.6 Hz, 2H, CH2), 2.48 (t, J = 7.6 Hz, 2H, CH2), 6.08 (s, 2H, CH2), 6.15 (s, 1H, CH), 6.72 (s, 1H, Ar), 7.59 (s, 1H, Ar). References 1. Z. Y. Ge, X. D. Fei, T. Yang, Y. M. Zhu, J. K. Shen, J. rg. Chem., 2012, 77, T. Sakamoto, M. Annaka, Y. Kondo, H. Yamanaka, Chem. Pharm. Bull., 1986, 34, Y. Zeng, L. Zhang, Y. Zhao, C. Ni, J. Zhao, J. Hu, J. Am. Chem. Soc. 2013, 135, E. Marchal, P. Uriac, B. Legouin, L. Toupet, P. van de Weghe, Tetrahedron 2007, 63, M. Hellal, J. J. Bourguignon, F. J. J. Bihel, Tetrahedron Lett. 2008, 49, D. E. Korte, J. rg. Chem., 1977, 42, V. Kavala, C. C. Wang, D. K. Barange, C. W. Kuo, C. F. Yao, J. rg. Chem. 2012, 77, C. N. Lewis, P. L. Spargo, J. Staunton, Synthesis, 1986, A. C. Tadd, M. R. Fielding, M. C. Willis, Chem. Commun. 2009, 44, A. Saeed, J. Heterocyclic Chem. 2003, 40, S10

12 1 H NMR spectra of Isocoumarins and other important compounds. 3a 3b S11

13 4a 4b S12

14 5 6 S13

15 3c 3d S14

16 3e f PM S15

17 3g h PPM S16

18 i PPM j S17

19 k PPM S18

20 l PPM m PPM S19

21 PPM PPM S20

22 Figure 1. RTEP Drawing of 7,12-Dihydro-7-hydroxy-7-trifluoromethyldibenzo[a,d]cycloocten-5(6H)-one (6). S21

23 Table 1. Crystal data and structure refinement for 7,12-Dihydro-7-hydroxy-7-trifluoromethyldibenzo[a,d]cycloocten-5(6H)-one (6). Identification code Empirical formula C17 H13 F3 2 Formula weight Temperature 113(2) K Wavelength Å Crystal system triclinic Space group P-1 Unit cell dimensions a = 8.816(3) Å = (5). b = (4) Å = (3). c = (5) Å = (4). Volume (8) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 632 Crystal size 0.35 x 0.20 x 0.15 mm 3 Theta range for data collection 3.04 to Index ranges -10<=h<=10, -14<=k<=14, -17<=l<=17 Reflections collected Independent reflections 5380 [R(int) = ] Completeness to theta = % Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 5380 / 0 / 399 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 S22

24 Table 2. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) C(1) 1757(2) 2328(1) 3105(1) 17(1) (1) 2984(1) 1647(1) 2874(1) 21(1) C(2) 198(2) 1486(1) 2687(1) 17(1) C(3) -24(2) 549(1) 3209(1) 17(1) (2) 559(1) -403(1) 2970(1) 23(1) C(4) -1035(2) 721(1) 3946(1) 18(1) C(5) -1375(2) 1861(1) 4496(1) 20(1) C(6) -666(2) 3098(1) 4479(1) 24(1) C(7) 1086(2) 3320(1) 4819(1) 20(1) C(8) 2172(2) 2975(1) 4221(1) 17(1) C(9) 1746(2) 3308(1) 2580(1) 22(1) F(1) 1383(1) 2812(1) 1596(1) 30(1) F(2) 711(1) 4089(1) 2823(1) 32(1) F(3) 3136(1) 3984(1) 2793(1) 30(1) C(10) -1687(2) -358(1) 4064(1) 22(1) C(11) -2692(2) -325(2) 4693(1) 27(1) C(12) -3030(2) 798(2) 5240(1) 30(1) C(13) -2366(2) 1871(2) 5146(1) 26(1) C(14) 1650(2) 3891(1) 5832(1) 27(1) C(15) 3215(2) 4141(1) 6242(1) 29(1) C(16) 4279(2) 3826(1) 5646(1) 27(1) C(17) 3757(2) 3247(1) 4649(1) 22(1) C(18) -2631(2) 2431(1) -1421(1) 17(1) (3) -3105(1) 1473(1) -2324(1) 20(1) C(19) -1452(2) 1998(1) -710(1) 18(1) C(20) -2169(2) 953(1) -422(1) 20(1) (4) -2202(2) -93(1) -960(1) 33(1) C(21) -2765(2) 1154(1) 503(1) 18(1) S23

25 C(22) -3100(2) 2284(1) 1081(1) 17(1) C(23) -3048(2) 3449(1) 797(1) 19(1) C(24) -4292(2) 3301(1) -112(1) 16(1) C(25) -4121(2) 2843(1) -1090(1) 16(1) C(26) -1772(2) 3499(1) -1636(1) 21(1) F(4) -2663(1) 3894(1) -2295(1) 30(1) F(5) -1281(1) 4472(1) -822(1) 31(1) F(6) -511(1) 3183(1) -2000(1) 28(1) C(27) -3004(2) 103(1) 787(1) 24(1) C(28) -3549(2) 160(2) 1627(1) 27(1) C(29) -3891(2) 1266(2) 2197(1) 28(1) C(30) -3673(2) 2308(2) 1923(1) 24(1) C(31) -5747(2) 3600(1) 68(1) 20(1) C(32) -6996(2) 3483(1) -684(1) 22(1) C(33) -6816(2) 3068(1) -1650(1) 22(1) C(34) -5394(2) 2754(1) -1847(1) 19(1) S24

26 Table 3. Bond lengths [Å] and angles [ ] for C(1)-(1) (16) C(14)-H(10) C(1)-C(8) (19) C(15)-C(16) 1.382(2) C(1)-C(9) 1.537(2) C(15)-H(11) C(1)-C(2) (19) C(16)-C(17) 1.382(2) (1)-H(1) C(16)-H(12) C(2)-C(3) (19) C(17)-H(13) C(2)-H(2) C(18)-(3) (16) C(2)-H(3) C(18)-C(25) (19) C(3)-(2) (16) C(18)-C(26) 1.537(2) C(3)-C(4) (19) C(18)-C(19) (19) C(4)-C(10) 1.401(2) (3)-H(14) C(4)-C(5) 1.404(2) C(19)-C(20) 1.518(2) C(5)-C(13) 1.394(2) C(19)-H(15) C(5)-C(6) 1.522(2) C(19)-H(16) C(6)-C(7) 1.515(2) C(20)-(4) (17) C(6)-H(4) C(20)-C(21) 1.491(2) C(6)-H(5) C(21)-C(27) 1.403(2) C(7)-C(14) 1.404(2) C(21)-C(22) 1.406(2) C(7)-C(8) 1.405(2) C(22)-C(30) 1.399(2) C(8)-C(17) 1.399(2) C(22)-C(23) 1.516(2) C(9)-F(3) (17) C(23)-C(24) (19) C(9)-F(2) (17) C(23)-H(17) C(9)-F(1) (17) C(23)-H(18) C(10)-C(11) 1.375(2) C(24)-C(31) 1.400(2) C(10)-H(6) C(24)-C(25) (19) C(11)-C(12) 1.386(2) C(25)-C(34) 1.402(2) C(11)-H(7) C(26)-F(4) (17) C(12)-C(13) 1.383(2) C(26)-F(6) (17) C(12)-H(8) C(26)-F(5) (17) C(13)-H(9) C(27)-C(28) 1.376(2) C(14)-C(15) 1.377(2) C(27)-H(19) S25

27 C(28)-C(29) 1.383(2) C(28)-H(20) C(29)-C(30) 1.382(2) C(29)-H(21) C(30)-H(22) C(31)-C(32) 1.377(2) C(31)-H(23) C(32)-C(33) 1.386(2) C(32)-H(24) C(33)-C(34) 1.383(2) C(33)-H(25) C(34)-H(26) S26

28 (1)-C(1)-C(8) (11) (1)-C(1)-C(9) (11) C(8)-C(1)-C(9) (11) (1)-C(1)-C(2) (11) C(8)-C(1)-C(2) (11) C(9)-C(1)-C(2) (11) C(1)-(1)-H(1) C(3)-C(2)-C(1) (11) C(3)-C(2)-H(2) C(1)-C(2)-H(2) C(3)-C(2)-H(3) C(1)-C(2)-H(3) H(2)-C(2)-H(3) (2)-C(3)-C(4) (12) (2)-C(3)-C(2) (12) C(4)-C(3)-C(2) (12) C(10)-C(4)-C(5) (13) C(10)-C(4)-C(3) (12) C(5)-C(4)-C(3) (13) C(13)-C(5)-C(4) (13) C(13)-C(5)-C(6) (13) C(4)-C(5)-C(6) (13) C(7)-C(6)-C(5) (12) C(7)-C(6)-H(4) C(5)-C(6)-H(4) C(7)-C(6)-H(5) C(5)-C(6)-H(5) H(4)-C(6)-H(5) C(14)-C(7)-C(8) (14) C(14)-C(7)-C(6) (13) C(8)-C(7)-C(6) (13) C(17)-C(8)-C(7) (13) C(17)-C(8)-C(1) (12) C(7)-C(8)-C(1) (13) F(3)-C(9)-F(2) (12) F(3)-C(9)-F(1) (11) S27

29 F(2)-C(9)-F(1) (12) F(3)-C(9)-C(1) (12) F(2)-C(9)-C(1) (12) F(1)-C(9)-C(1) (12) C(11)-C(10)-C(4) (14) C(11)-C(10)-H(6) C(4)-C(10)-H(6) C(10)-C(11)-C(12) (14) C(10)-C(11)-H(7) C(12)-C(11)-H(7) C(13)-C(12)-C(11) (14) C(13)-C(12)-H(8) C(11)-C(12)-H(8) C(12)-C(13)-C(5) (14) C(12)-C(13)-H(9) C(5)-C(13)-H(9) C(15)-C(14)-C(7) (15) C(15)-C(14)-H(10) C(7)-C(14)-H(10) C(14)-C(15)-C(16) (15) C(14)-C(15)-H(11) C(16)-C(15)-H(11) C(17)-C(16)-C(15) (15) C(17)-C(16)-H(12) C(15)-C(16)-H(12) C(16)-C(17)-C(8) (14) C(16)-C(17)-H(13) C(8)-C(17)-H(13) (3)-C(18)-C(25) (11) (3)-C(18)-C(26) (11) C(25)-C(18)-C(26) (11) (3)-C(18)-C(19) (11) C(25)-C(18)-C(19) (11) C(26)-C(18)-C(19) (12) C(18)-(3)-H(14) C(20)-C(19)-C(18) (12) S28

30 C(20)-C(19)-H(15) C(18)-C(19)-H(15) C(20)-C(19)-H(16) C(18)-C(19)-H(16) H(15)-C(19)-H(16) (4)-C(20)-C(21) (13) (4)-C(20)-C(19) (13) C(21)-C(20)-C(19) (12) C(27)-C(21)-C(22) (13) C(27)-C(21)-C(20) (13) C(22)-C(21)-C(20) (13) C(30)-C(22)-C(21) (13) C(30)-C(22)-C(23) (13) C(21)-C(22)-C(23) (13) C(22)-C(23)-C(24) (11) C(22)-C(23)-H(17) C(24)-C(23)-H(17) C(22)-C(23)-H(18) C(24)-C(23)-H(18) H(17)-C(23)-H(18) C(31)-C(24)-C(25) (13) C(31)-C(24)-C(23) (12) C(25)-C(24)-C(23) (13) C(34)-C(25)-C(24) (13) C(34)-C(25)-C(18) (12) C(24)-C(25)-C(18) (12) F(4)-C(26)-F(6) (12) F(4)-C(26)-F(5) (12) F(6)-C(26)-F(5) (11) F(4)-C(26)-C(18) (12) F(6)-C(26)-C(18) (12) F(5)-C(26)-C(18) (12) C(28)-C(27)-C(21) (14) C(28)-C(27)-H(19) C(21)-C(27)-H(19) C(27)-C(28)-C(29) (14) S29

31 C(27)-C(28)-H(20) C(29)-C(28)-H(20) C(30)-C(29)-C(28) (14) C(30)-C(29)-H(21) C(28)-C(29)-H(21) C(29)-C(30)-C(22) (14) C(29)-C(30)-H(22) C(22)-C(30)-H(22) C(32)-C(31)-C(24) (13) C(32)-C(31)-H(23) C(24)-C(31)-H(23) C(31)-C(32)-C(33) (13) C(31)-C(32)-H(24) C(33)-C(32)-H(24) C(34)-C(33)-C(32) (14) C(34)-C(33)-H(25) C(32)-C(33)-H(25) C(33)-C(34)-C(25) (13) C(33)-C(34)-H(26) C(25)-C(34)-H(26) Symmetry transformations used to generate equivalent atoms: S30