Enhancing the Photochemical Stability of N,C-Chelate Polyboryl Compounds: C- C Bond Formation versus C=C Bond cis, trans-isomerization

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1 Supporting Information Enhancing the Photochemical Stability of,c-chelate Polyboryl Compounds: C- C Bond Formation versus C=C Bond cis, trans-isomerization Chul Baik, Zachary M. Hudson, Hazem Amarne, Suning Wang * Department of Chemistry, Queen s University, Kingston, Ontario, K7L 36, Canada wangs@chem.queensu.ca S1. Experimental section. Syntheses and characterization of intermediates for B1. Syntheses and characterization of intermediates for B1A. Syntheses and characterization of intermediates for B2. Syntheses and characterization of intermediates for B3. Synthesis and characterization of ligand 11. S2. Reduction potentials of A1, B1A, B1-B3. S3. UV-Vis and emission spectral change of B1A, B1-B3 with irradiation at 365 nm. S4. 1 H MR Photolysis Experiment of B(ppy)Mes 2 and B1A in C 6 D 6 upon at 365nm and rt. S5. 1 H MR photolysis experiment of B(ppy)Mes 2 and B1 in C 6 D 6 upon irradiation at 365nm. S6. Absorption and emmision spectra of phenylpyridine derivatives (ligands). S7. HOMO and LUMO orbitals of B3. S8.1. Calculated HOMO and LUMO energies and experimental HOMO-LUMO gaps. S8.2. TD-DFT calculation for the oscillator strengths. S9. The crystal structural data. S1

2 S1. Experimental section Syntheses and characterization of intermediate 1 for B1. O Pd(PPh 3 ) 4, K 2 CO 3 O + (HO) 2 B 1 PO(OEt) 2 K t OBu B1 B n-buli, B(Mes) 2 F 2 6-(2-bromophenyl)nicotinaldehyde (1). This compound was synthesized using a modified Suzuki coupling procedure. 1 A mixture of 6-bromonicotinaldehyde (1.80 g, 10 mmol), 2-bromophenylboronic acid (2.00 g, 10 mmol) and Pd(PPh 3 ) 4 (0.50 g, 0.5 mmol) were added to the degassed THF (30 ml) and degassed aqueous 1M K 2 CO 3 (25 ml). The mixture was refluxed for overnight. After work-up the crude product was purified by column chromatography (EA:Hx = 1:2, R f = 0.4) to afford compound 1 in 93% yield (2.43 g). 1 H MR (500 MHz, CD 2 Cl 2 ): (s; 1H), 9.19 (d; J = 1.5 Hz; 1H), 8.27 (dd; J = 8.0 Hz, J = 2.0 Hz; 1H), 7.85 (d; J = 8.0 Hz; 1H), 7.72 (d; J = 8.0 Hz; 1H), 7.60 (dd; J = 8.0 Hz, J = 2.0 Hz; 1H), 7.48 (m; 1H), 7.36 (m; 1H); 13 C { 1 H} MR (500 MHz, CDCl 3 ): 190.8, 163.6, 152.2, 140.5, 136.0, 134.0, 131.9, 131.0, 130.4, 128.1, 125.6, HRMS calcd. for C 12 H 8 O: m/z ; found: Syntheses and characterization of intermediate 3 for B1A. Pd(PPh 3 ) 2 Cl 2 I CuI, Et 3 Ph H 3 Pd(PPh 3 ) 4 (HO) 2 B K 2 CO 3, THF B n-buli, (mes) 2 BF B1A Et 2 O 4 2-(2-bromophenyl)-5-(phenylethynyl)pyridine (3). This compound was synthesized using a modified Sonogashira coupling procedure. 2 A mixture of 2-omo-5-iodopyridine (1.00 g, 3.52 mmol), Phenylacetylene (0.38ml, 3.52 mmol), Pd(PPh 3 ) 4 (0.19 mg, 0.18 mmol) and CuI (0.34 g, 0.18mmol) were added to the toluene (20 ml) and triethyl amine (10 ml). The mixture was stirred for overnight. After work-up the crude product was purified by column chromatography to afford S2

3 compound 3 in 83% yield (0.75 g). 1 H MR (400 MHz, CD 2 Cl 2 ): 8.53 (d; J = 2.0 Hz; 1H), 7.69 (dd; J = 8.4 Hz, J = 2.0 Hz; 1H), 7.58 (m; 2H), 7.51 (d; J = 8.4 Hz; 1H), 7.42 (m, 3H); 13 C { 1 H} MR (CD 2 Cl 2 ): 152.6, 141.4, 141.3, 140.9, 131.9, 129.8, 129.4, 128.8, 127.9, 122.5, 120.0, 93.9, HRMS calcd. for C 13 H 8 : m/z ; found: Syntheses and characterization of intermediates 5 and 6 for B2. O 1 neo-pentylglycol p-tolylsulfonic acid O O 5 n-buli B(Mes) 2 F O O B 6 CF 3 COOH B PO(OEt) 2 (EtO) 2 OP B2 B K t OBu O B 7 2-(2-bromophenyl)-5-(5,5-dimethyl-1,3-dioxan-2-yl)pyridine (5). A mixture of compound 1 (1.30 g, 4.96 mmol), neo- Pentylglycol (0.77 g, 7.45 mmol) and p-toluenesulfonic acid (0.14 g, 0.75 mmol) were added to the benzene (20 ml). The mixture was refluxed for overnight and then cooled and washed with aqueous sodium bicarbonate (5% w/v). The combined benzene layers were then dried (MgSO 4 ), filtered and evaporated in vacuo to yield compound 5 as a white solid. Using a column chromatography (EA:Hx = 1:2, R f =0.4), the product was purified (1.36 g, 79.0%). 1 H MR (500 MHz, CD 2 Cl 2 ): 8.80 (s; 1H), 7.93 (d; J = 8.0 Hz; 1H), 7.72 (d; J = 8.0 Hz; 1H), 7.64 (d; J = 7.5 Hz; 1H), 7.55 (d; J = 7.5 Hz; 1H), 7.46 (t; J = 7.5 Hz; 1H), 7.32 (t; J = 7.5 Hz; 1H), 5.55 (s; 1H), 3.82 (d; J = 11.0 Hz; 2H), 3.73 (d; J = 11.0 Hz; 2H), 1.32 (s; 3H), 0.85 (s; 3H); 13 C { 1 H} MR (500 MHz, CD 2 Cl 2 ): 158.9, 147.9, 141.6, 134.1, 133.6, 133.4, 131.9, 130.1, 127.9, 124.5, 122.0, 100.0, 77.9, 30.5, 32.1, HRMS calcd. for C 17 H 18 O 2 : m/z ; found: Compound 6. To a stirred Et 2 O solution of compound 5 (1.35 g, 3.87 mmol) was added dropwise an n-buli solution (1.60 M in Hx, 2.91 ml, 4.65 mmol) at -78 C. The resulting solution was left to stir for 1h at -78 C. Then a solution of dimesitylboron fluoride (1.56 g, 5.81 mmol) in Et 2 O was added. The solution was slowly warmed to room temperature and stirred for overnight. After work-up the crude product was purified by column chromatography (DCM:Hx = 1:1, R f = 0.4) to afford compound 6 (1.75 g, 87%). 1 H MR (300 MHz, CD 2 Cl 2 ): 8.76 (s; 1H), 8.16 (d; J = 8.4 Hz; 1H), 8.04 (d; J = 8.0 Hz; 1H), 7.92 (d; J = 8.4 Hz; 1H), 7.75 (d; J = 7.5 Hz; 1H), 7.33 (m; 2H), 6.66 (s; 4H), 5.44 (s; 1H), 3.77 (d; J = 11.4 Hz; 2H), 3.65 (d; J = 11.4 Hz; 2H), 2.19 (s; 6H), 1.78 (s; 12H), 1.25 (s; 3H), 0.81 (s; 3H); 13 C { 1 H} MR (300 MHz, CD 2 Cl 2 ): 159.5, 144.6, 140.3, 139.3, 134.9, 134.1, 133.4, 131.3, 131.1, 130.1, 125.6, 122.2, 117.7, 98.8, 77.8, 30.4, 22.8, S3

4 HRMS calcd. for C 35 H 40 BO 2 : m/z 517,3152; found: Syntheses and characterization of intermediate 8 for B3. (EtO) 2 OP PO(OEt) 2 PO(OEt) 2 O K t OBu 8 B (HO) 2 B Pd(PPh 3 ) 4, K 2 CO 3 B n-buli, B(Mes) 2 F B3 B 9 1,3,5-tris((E)-2-(6-bromopyridin-3-yl)vinyl)benzene (8). A mixture of 1,3,5-Tris(diethoxy phosphorylmethyl)benzene (1.13 g, 1.70 mmol) and 6-omo-3-pyridinecarboxaldehyde (1.00 g, 5.37 mmol) in THF (50 ml) was slowly added to a THF solution of potassium tert-butoxide (0.72 g, 6.44 mmol). Then, The solution was stirred overnight. After work-up the crude product was purified by column chromatography to afford compound 8 in 27% yield (0.29 g). 1 H MR (300 MHz, CD 2 Cl 2 ): 8.54 (d; J = 2.1 Hz; 3H), 7.71 (dd; J = 2,1 Hz, 8.4 Hz; 3H), 7.69 (s; 3H), 7.55 (d; J = 8.4 Hz; 3H), 7.29 (d; J = 16.5 Hz; 3H), 7.19 (d; J = 16.5 Hz; 3H); 13 C { 1 H} MR (CD 2 Cl 2 ): 148.9, 141.1, 137.9, 132.5, 128.5, 125.0, 123.8, 115.3, HRMS calcd. for C 27 H : m/z ; found: Synthesis of ligand 11 (EtO) 2 OP PO(OEt) 2 PO(OEt) 2 O K t OBu 10 (HO) 2 B Pd(PPh 3 ) 4,K 2 CO ,4-bis((E)-2-(6-bromopyridin-3-yl)vinyl)benzene (10). A mixture of 1,4-Bis(diethoxyphosphoryl methyl)benzene (0.70g, 1.85 mmol) and 6-bromonicotinaldehyde (0.76 g, 4.07 mmol) in THF (50 ml) was slowly added to a THF solution of potassium tert-butoxide (0.55 g, 4.88 mmol). Then, the solution was stirred overnight. After work-up the crude product was S4

5 purified by column chromatography to afford compound 10 in 31% yield (0.25 g). 1 H MR (300 MHz, CD 2 Cl 2 ): 8.50 (d; J = 2.1 Hz; 2H), 7.78 (dd; J = 8.4 Hz, J = 2.1 Hz; 2H), 7.60 (s; 4H), 7.52 (d; J = 8.4 Hz; 2H), 7.24 (d; J = 16.5 Hz; 2H), 7.12 (d; J = 16.5 Hz; 2H). HRMS calcd. for C 20 H : m/z ; found: ,4-bis((E)-2-(6-(2-bromophenyl)pyridin-3-yl)vinyl)benzene (11). A mixture of Compound 10 (0.22 g, 0.49 mmol), 2- omophenyl boronic acid (0.20 g, 0.99 mmol) and Pd(PPh 3 ) 4 (55 mg, 0.05 mmol) were added to the degassed THF (100 ml) and degassed aqueous 1M K 2 CO 3 (50ml). The mixture was refluxed for overnight. After work-up the crude product was purified by column chromatography (DCM:EA = 40:1, R f =0.1) to afford compound 4 in 42% yield (0.12 g). 1 H MR (300 MHz, CD 2 Cl 2 ): 8.86 (d; J = 2.1 Hz; 2H), 8.00 (dd; J = 7.8 Hz, J = 2,1 Hz; 2H), 7.74 (d; J = 7.2 Hz; 2H), 7.68 (d; J = 7.2 Hz; 2H), 7.65 (s; 4H), 7.62 (d; J = 7.8 Hz; 2H), 7.50 (t; J = 7.2 Hz; 2H), 7.35 (m; 2H), 7.33 (d; J = 16.2 Hz; 2H), 7.25 (d; J = 16.2 Hz; 2H); HRMS calcd. for C 32 H : m/z ; found: S2. Reduction potentials of A1, B1A, B1-B3. Compound A1 B1A B1 B2 B3 Potential (V) vs FeCp 2 +/0 in DMF , , S3. UV-Vis absorption (left) and Emission Spectral change (right) with 365 nm Irradiation. S1.1 Spectra of B1. S5

6 S1.2 Spectra of B1A. S1.3 Spectra of B2. S1.4 Spectra of B3. S6

7 S4. 1 H MR Photolysis Experiment of B(ppy)Mes 2 and B1A in C 6 D 6 upon at 365 nm and rt. The representative peaks that allow the direct comparison of conversion rate of B1A to B1A, A1 to A1 are highlighted. X Hpy B X H py Me B Me' X=H,A1 X = Ph-CC-, B1A X=H,A1' X=Ph-CC-,B1A' S7

8 S6. 1 H MR Photolysis Experiment of B(ppy)Mes 2 and B1 in C 6 D 6 upon Irradiation at 365nm. 1 H MR spectral change of B(ppy)Mes 2 (3eq) and B1 (1eq) in C 6 D 6 under 2 upon irradiation at 365 nm. The chemical shifts of the H 2 proton of py (H py ) and the protons from the mesityl groups are highlighted. violet: B(ppy)Mes 2, red: B(ppy)Mes 2, green: trans-b1, yellow: cis-b1. S7. Absorption and Emission Spectra of omo-phenylpyridine Derivatives (ligands). ormalized Intensity UV 2 PL 11 UV 11 PL 9 UV 9 PL Wavelength (nm) S8

9 S8. HOMO and LUMO orbital of B3 with 0.02 iso-contour values for all surfaces. HOMO LUMO Table 8.1. Calculated HOMO and LUMO energies and experimental HOMO-LUMO gaps Compound HOMO (ev) LUMO (ev) HOMO-LUMO Gap (nm) Optical Energy Gap (nm) a B(ppy)Mes trans-b cis-b All trans-b trans,cis-b ot Available All trans-b trans,trans,cis-b ot Available B1A a 1.0 x 10-5 M in toluene. S9

10 S8.2. TD-DFT Calculation 3 for the Oscillator Strengths. TD-DFT Singlet Transition Energies (Eex) and Oscillator Strengths (f) for B(ppy)Mes 2. (HOMO = 108) stats E ex (nm) f Transition Weights configuration coefficients Energy Level S10

11 TD-DFT Singlet Transition Energies (Eex) and Oscillator Strengths (f) for B1. (HOMO = 135) stats E ex (nm) f configuration Transition Weights coefficients Energy Level S11

12 TD-DFT Singlet Transition Energies (Eex) and Oscillator Strengths (f) for B1A. (HOMO = 134) stats E ex (nm) f configuration Transition Weights coefficients Energy Level S12

13 TD-DFT Singlet Transition Energies (Eex) and Oscillator Strengths (f) for B2. (HOMO = 249) stats E ex (nm) f configuration Transition Weights coefficients Energy Level S13

14 References. 1. Wu, J.; Watson, M. D.; Zhang, L.; Wang, Z.; Mullen, K. J. Am. Chem. Soc. 2004, 126, Grave, C.; Lentz, D.; Schafer, A.; Samor, P.; Rabe, J. P.; Franke, P.; Schluter, A. D. J. Am. Chem. Soc. 2003, 125, Gaussian 03, Revision C.02, M. J. Fisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheesman, Jr. J. A. Montgamery, T. Vreven, K.. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani,. Rega, G. A. Petersson, H. akatsuji, M. Hada, M. Ehra, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. akajima, Y. Honda, O. Kitao, H. akai, M. Li, X. Klene, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jarmillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. anayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Bonzales and J. A. Pople, Gaussian, Inc., Wallingford CT, S14

15 S9. The crystal structural data. Table S9.1. Crystal data Compound B1 B2 B3 B1A Formula C 37 H 36 B C 68 H 66 2 B 2 /2CH 2 Cl 2 C 99 H 96 3 B 3 C 37 H 34 B/0.5C 6 H 14 FW Crystal system Monoclinic Monoclinic Monoclinic Monoclinic Space Group P2 1 /n P2 1 /c P-1 P2 1 /n a, Å (16) (11) (4) (3) b, Å (15) (8) (4) (3) c, Å (16) (9) (6) (3) α º (4) 90 βº (1) (4) (3) (2) γ,º (3) 90 V, Å (6) (3) 4660(2) (11) Z D calc, g cm T, K µ, mm θ max, º Reflns measured Reflns used Parameters R [I>2σ I)]: R 1 a wr 2 b R (all data): a R b wr GOF on F a R 1 = F 0 - F c / F 0 b wr 2 = [ w[(f 2 0 -F 2 c ) 2 ]/ [w(f 2 0 ) 2 ]] 1/2, w = 1/[σ 2 (F 2 0 ) + (0.075P) 2 ], where P = [Max (F 2 0,0) + 2F 2 c ]/3 S15

16 Table 9.2. Comparison of key bond lengths (Å) and angles ( ) for B1-B3, B1A Bond length (Å) B-C (mesityl) B-C (phenyl) B- -CH=CH- (-C C- for B1A) B (2) 1.626(3) 1.648(2) 1.352(3) 1.653(2) B (5) 1.624(5) 1.648(4) 1.326(4) 1.646(5) B (5) 1.641(5) 1.628(5) 1.616(5) 1.635(5) 1.645(5) 1.642(4) 1.629(4) 1.615(4) 1.343(4) 1.313(4) 1.326(4) 1.656(5) 1.633(5) 1.668(5) B1A 1.650(4) 1.650(4) 1.631(4) 1.642(3) 1.201(4) Bong angle ( ) C(Mes)-B-C (Mes) C(ph)-B-C (Mes) -B-C (ppy) -B-C (Mes) B (14) (14) (13) 95.68(13) (13) (13) B (3) 123.2(3) 103.5(3) 95.4(3) 102.4(3) 115.4(3) B (3) 117.7(3) 115.6(3) 121.6(3) 103.3(3) 123.2(3) 99.6(3) 122.2(3) 102.3(3) 95.4(2) 95.5(3) 95.7(3) 101.9(3) 115.5(3) 104.5(3) 114.8(3) 105.2(3) 114.5(3) B1A 115.3(2) 122.7(2) (19) 95.44(18) (18) (19) S16

17 S9.3. The crystal structural data of B1. Table 1. Crystal data and structure refinement for B1. Identification code baik2 Empirical formula C37 H36 B Formula weight Temperature 180(2) K Wavelength Å Crystal system Monoclinic Space group P2(1)/n Unit cell dimensions a = (16) Å α= 90. b = (15) Å β= (10). c = (16) Å γ = 90. Volume (6) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1080 Crystal size 0.20 x 0.20 x 0.05 mm 3 Theta range for data collection 1.75 to Index ranges -19<=h<=19, -18<=k<=17, -19<=l<=19 Reflections collected Independent reflections 6950 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 6950 / 0 / 358 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 S17

18 Table 2. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for B1. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) B(1) 1190(1) 5545(1) 3199(1) 40(1) (1) 1266(1) 5239(1) 2175(1) 41(1) C(1) 1129(1) 4468(1) 3563(1) 42(1) C(2) 1083(1) 4096(1) 4399(1) 49(1) C(3) 1137(1) 3126(1) 4549(2) 58(1) C(4) 1269(1) 2503(1) 3885(2) 61(1) C(5) 1334(1) 2840(1) 3059(2) 54(1) C(6) 1264(1) 3810(1) 2905(1) 45(1) C(7) 1290(1) 4284(1) 2068(1) 44(1) C(8) 1304(1) 3905(1) 1230(1) 56(1) C(9) 1282(1) 4505(2) 516(1) 58(1) C(10) 1253(1) 5486(1) 620(1) 50(1) C(11) 1230(1) 5815(1) 1474(1) 45(1) C(12) 1220(1) 6140(2) -125(1) 54(1) C(13) 1428(1) 7074(1) -57(1) 50(1) C(14) 1321(1) 7799(1) -760(1) 47(1) C(15) 886(1) 7598(1) -1642(1) 53(1) C(16) 769(1) 8294(2) -2280(2) 63(1) C(17) 1067(1) 9224(2) -2040(2) 67(1) C(18) 1470(2) 9416(2) -1205(2) 74(1) C(19) 1596(1) 8707(2) -552(2) 62(1) C(20) 324(1) 6289(1) 3051(1) 36(1) C(21) -590(1) 5979(1) 2966(1) 41(1) C(22) -1305(1) 6623(1) 2918(1) 46(1) C(23) -1167(1) 7593(1) 2930(1) 45(1) C(24) -287(1) 7896(1) 2952(1) 43(1) C(25) 447(1) 7281(1) 2996(1) 38(1) C(26) -850(1) 4941(1) 2904(2) 59(1) C(27) -1951(1) 8277(2) 2896(2) 64(1) C(28) 1358(1) 7754(1) 2967(1) 49(1) C(29) 2142(1) 5958(1) 3818(1) 39(1) C(30) 3035(1) 5852(1) 3642(1) 41(1) S18

19 C(31) 3786(1) 6205(1) 4233(1) 50(1) C(32) 3711(1) 6669(2) 5013(1) 55(1) C(33) 2851(1) 6745(1) 5204(1) 50(1) C(34) 2079(1) 6393(1) 4640(1) 42(1) C(35) 3239(1) 5338(1) 2835(2) 57(1) C(36) 4535(2) 7048(2) 5649(2) 86(1) C(37) 1193(1) 6526(1) 4973(1) 51(1) Table 3. Bond lengths [Å] and angles [ ] for B1. B(1)-C(1) 1.626(3) C(20)-C(25) 1.416(2) B(1)-C(20) 1.646(2) C(21)-C(22) 1.392(2) B(1)-(1) 1.648(2) C(21)-C(26) 1.512(2) B(1)-C(29) 1.653(2) C(22)-C(23) 1.383(2) (1)-C(11) 1.337(2) C(23)-C(24) 1.376(2) (1)-C(7) 1.357(2) C(23)-C(27) 1.508(2) C(1)-C(2) 1.394(3) C(24)-C(25) 1.388(2) C(1)-C(6) 1.412(2) C(25)-C(28) 1.522(2) C(2)-C(3) 1.387(3) C(29)-C(34) 1.417(2) C(3)-C(4) 1.386(3) C(29)-C(30) 1.417(2) C(4)-C(5) 1.369(3) C(30)-C(31) 1.389(2) C(5)-C(6) 1.388(2) C(30)-C(35) 1.511(3) C(6)-C(7) 1.451(3) C(31)-C(32) 1.383(3) C(7)-C(8) 1.390(3) C(32)-C(33) 1.374(3) C(8)-C(9) 1.376(3) C(32)-C(36) 1.510(3) C(9)-C(10) 1.394(3) C(33)-C(34) 1.391(2) C(10)-C(11) 1.391(3) C(34)-C(37) 1.516(2) C(10)-C(12) 1.459(3) C(12)-C(13) 1.352(3) C(1)-B(1)-C(20) (14) C(13)-C(14) 1.469(3) C(1)-B(1)-(1) 95.68(13) C(14)-C(19) 1.363(3) C(20)-B(1)-(1) (13) C(14)-C(15) 1.408(3) C(1)-B(1)-C(29) (13) C(15)-C(16) 1.371(3) C(20)-B(1)-C(29) (14) C(16)-C(17) 1.411(3) (1)-B(1)-C(29) (13) C(17)-C(18) 1.329(3) C(11)-(1)-C(7) (15) C(18)-C(19) 1.400(3) C(11)-(1)-B(1) (14) C(20)-C(21) 1.415(2) C(7)-(1)-B(1) (14) S19

20 C(2)-C(1)-C(6) (16) C(21)-C(20)-C(25) (14) C(2)-C(1)-B(1) (16) C(21)-C(20)-B(1) (14) C(6)-C(1)-B(1) (15) C(25)-C(20)-B(1) (14) C(3)-C(2)-C(1) (18) C(22)-C(21)-C(20) (15) C(4)-C(3)-C(2) 121.1(2) C(22)-C(21)-C(26) (15) C(5)-C(4)-C(3) (18) C(20)-C(21)-C(26) (15) C(4)-C(5)-C(6) (19) C(23)-C(22)-C(21) (15) C(5)-C(6)-C(1) (18) C(24)-C(23)-C(22) (15) C(5)-C(6)-C(7) (18) C(24)-C(23)-C(27) (16) C(1)-C(6)-C(7) (15) C(22)-C(23)-C(27) (16) (1)-C(7)-C(8) (17) C(23)-C(24)-C(25) (16) (1)-C(7)-C(6) (15) C(24)-C(25)-C(20) (14) C(8)-C(7)-C(6) (17) C(24)-C(25)-C(28) (15) C(9)-C(8)-C(7) (18) C(20)-C(25)-C(28) (14) C(8)-C(9)-C(10) (18) C(34)-C(29)-C(30) (15) C(11)-C(10)-C(9) (18) C(34)-C(29)-B(1) (14) C(11)-C(10)-C(12) (18) C(30)-C(29)-B(1) (15) C(9)-C(10)-C(12) (18) C(31)-C(30)-C(29) (17) (1)-C(11)-C(10) (17) C(31)-C(30)-C(35) (15) C(13)-C(12)-C(10) (18) C(29)-C(30)-C(35) (15) C(12)-C(13)-C(14) (18) C(32)-C(31)-C(30) (17) C(19)-C(14)-C(15) (18) C(33)-C(32)-C(31) (17) C(19)-C(14)-C(13) (18) C(33)-C(32)-C(36) 120.9(2) C(15)-C(14)-C(13) (17) C(31)-C(32)-C(36) (19) C(16)-C(15)-C(14) (19) C(32)-C(33)-C(34) (19) C(15)-C(16)-C(17) 119.4(2) C(33)-C(34)-C(29) (16) C(18)-C(17)-C(16) 120.0(2) C(33)-C(34)-C(37) (16) C(17)-C(18)-C(19) 120.9(2) C(29)-C(34)-C(37) (15) C(14)-C(19)-C(18) 120.8(2) Table 4. Anisotropic displacement parameters (Å 2 x 10 3 )for B1. The anisotropic displacement factor exponent takes the form: -2π 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 S20

21 B(1) 34(1) 38(1) 46(1) -3(1) 6(1) -2(1) (1) 34(1) 40(1) 47(1) -2(1) 5(1) 2(1) C(1) 30(1) 40(1) 52(1) 1(1) 0(1) -2(1) C(2) 44(1) 45(1) 57(1) 3(1) 3(1) -4(1) C(3) 53(1) 51(1) 65(1) 16(1) 0(1) -5(1) C(4) 54(1) 39(1) 82(2) 6(1) -4(1) -3(1) C(5) 48(1) 40(1) 70(1) -3(1) 2(1) 0(1) C(6) 32(1) 39(1) 62(1) -1(1) 1(1) -1(1) C(7) 34(1) 41(1) 56(1) -6(1) 4(1) 0(1) C(8) 53(1) 46(1) 67(1) -15(1) 10(1) 3(1) C(9) 59(1) 62(1) 53(1) -10(1) 12(1) 4(1) C(10) 42(1) 57(1) 49(1) -4(1) 5(1) 8(1) C(11) 41(1) 44(1) 50(1) 0(1) 6(1) 6(1) C(12) 51(1) 68(1) 44(1) -3(1) 9(1) 9(1) C(13) 40(1) 60(1) 50(1) -4(1) 6(1) -2(1) C(14) 39(1) 51(1) 54(1) -1(1) 14(1) 6(1) C(15) 50(1) 51(1) 57(1) 0(1) 6(1) -5(1) C(16) 55(1) 66(1) 63(1) 9(1) 1(1) -7(1) C(17) 50(1) 62(1) 88(2) 24(1) 12(1) 0(1) C(18) 67(1) 46(1) 116(2) -11(1) 33(2) -13(1) C(19) 47(1) 74(2) 64(1) -16(1) 11(1) -12(1) C(20) 33(1) 36(1) 40(1) 1(1) 5(1) -2(1) C(21) 35(1) 40(1) 45(1) 1(1) 2(1) -3(1) C(22) 32(1) 51(1) 55(1) 4(1) 8(1) -2(1) C(23) 41(1) 45(1) 49(1) 7(1) 11(1) 6(1) C(24) 45(1) 35(1) 51(1) 5(1) 11(1) 1(1) C(25) 37(1) 37(1) 40(1) 3(1) 8(1) -3(1) C(26) 38(1) 44(1) 91(2) 2(1) 1(1) -10(1) C(27) 48(1) 58(1) 89(2) 8(1) 23(1) 12(1) C(28) 41(1) 41(1) 66(1) 10(1) 12(1) -4(1) C(29) 35(1) 33(1) 48(1) 6(1) 4(1) -2(1) C(30) 35(1) 34(1) 54(1) 7(1) 6(1) -1(1) C(31) 33(1) 57(1) 57(1) 14(1) 4(1) -6(1) C(32) 44(1) 70(1) 45(1) 13(1) -2(1) -16(1) C(33) 51(1) 55(1) 42(1) 6(1) 5(1) -12(1) C(34) 41(1) 42(1) 42(1) 6(1) 5(1) -5(1) S21

22 C(35) 37(1) 51(1) 86(2) -16(1) 16(1) 0(1) C(36) 58(1) 139(2) 54(1) -2(1) -1(1) -40(1) C(37) 48(1) 60(1) 47(1) -2(1) 12(1) -4(1) Table 5. Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for B1. x y z U(eq) H(2A) H(3A) H(4A) H(5A) H(8A) H(9A) H(11A) H(12A) H(13A) H(15A) H(16A) H(17A) H(18A) H(19A) H(22A) H(24A) H(26A) H(26B) H(26C) H(27A) H(27B) H(27C) H(28A) H(28B) H(28C) H(31A) S22

23 H(33A) H(35A) H(35B) H(35C) H(36A) H(36B) H(36C) H(37A) H(37B) H(37C) S23

24 S9.4. The crystal structural data of B1A. Table 1. Crystal data and structure refinement for B1A. Identification code B1A Empirical formula C40 H41 B Formula weight Temperature 180(2) K Wavelength Å Crystal system Monoclinic Space group P2(1)/n Unit cell dimensions a = (3) Å α= 90. b = (3) Å β= (2). c = (3) Å γ = 90. Volume (11) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1172 Crystal size 0.30 x 0.25 x 0.10 mm 3 Theta range for data collection 2.03 to Index ranges -17<=h<=15, -16<=k<=16, -16<=l<=18 Reflections collected Independent reflections 5826 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 5826 / 6 / 379 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 S24

25 Table 2. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for B1A. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) (1) 1327(1) 9791(1) 2308(1) 36(1) B(1) 1248(2) 9481(2) 3308(2) 36(1) C(1) 1310(2) 9209(2) 1624(2) 38(1) C(2) 1313(2) 9556(2) 786(2) 42(1) C(3) 1317(2) 10546(2) 670(2) 48(1) C(4) 1328(2) 11146(2) 1377(2) 46(1) C(5) 1331(2) 10757(2) 2197(2) 37(1) C(6) 1303(2) 11235(2) 3023(2) 40(1) C(7) 1363(2) 12219(2) 3166(2) 48(1) C(8) 1285(2) 12563(2) 3982(2) 53(1) C(9) 1147(2) 11925(2) 4623(2) 53(1) C(10) 1104(2) 10949(2) 4477(2) 45(1) C(11) 1173(2) 10571(2) 3659(2) 38(1) C(12) 1311(2) 8869(2) 100(2) 46(1) C(13) 1276(2) 8203(2) -393(2) 47(1) C(14) 1222(2) 7353(2) -917(2) 40(1) C(15) 810(2) 7362(2) -1810(2) 48(1) C(16) 737(2) 6531(2) -2289(2) 59(1) C(17) 1075(2) 5688(2) -1888(2) 62(1) C(18) 1492(2) 5674(2) -1011(2) 65(1) C(19) 1563(2) 6501(2) -516(2) 54(1) C(20) 368(2) 8731(2) 3128(2) 34(1) C(21) -555(2) 9054(2) 2992(2) 38(1) C(22) -1285(2) 8414(2) 2912(2) 43(1) C(23) -1161(2) 7435(2) 2940(2) 42(1) C(24) -266(2) 7114(2) 3019(2) 41(1) C(25) 488(2) 7730(2) 3096(2) 37(1) C(26) -811(2) 10105(2) 2876(2) 54(1) C(27) -1965(2) 6760(2) 2875(2) 59(1) C(28) 1404(2) 7231(2) 3120(2) 46(1) C(29) 2211(2) 9064(2) 3934(2) 35(1) S25

26 C(30) 2154(2) 8608(2) 4731(2) 38(1) C(31) 2938(2) 8228(2) 5288(2) 42(1) C(32) 3809(2) 8291(2) 5105(2) 45(1) C(33) 3873(2) 8784(2) 4352(2) 43(1) C(34) 3111(2) 9176(2) 3778(2) 37(1) C(35) 1263(2) 8486(2) 5054(2) 48(1) C(36) 4642(2) 7874(3) 5726(2) 69(1) C(37) 3321(2) 9744(2) 3016(2) 50(1) C(38A) 7911(9) 4387(8) 4145(8) 89(2) C(39A) 8652(6) 4965(7) 4757(7) 99(2) C(40A) 9640(8) 4652(9) 4712(10) 95(2) C(38B) 8039(9) 4190(9) 4123(8) 89(2) C(39B) 8744(6) 4556(7) 4859(7) 99(2) C(40B) 9621(7) 4886(10) 4683(10) 95(2) Table 3. Bond lengths [Å] and angles [ ] for B1A. (1)-C(1) 1.335(3) C(12)-C(13) 1.201(4) (1)-C(5) 1.361(3) C(13)-C(14) 1.433(4) (1)-B(1) 1.642(3) C(14)-C(19) 1.387(4) B(1)-C(11) 1.631(4) C(14)-C(15) 1.390(4) B(1)-C(20) 1.650(4) C(15)-C(16) 1.371(4) B(1)-C(29) 1.650(4) C(16)-C(17) 1.375(4) C(1)-C(2) 1.391(3) C(17)-C(18) 1.369(4) C(2)-C(3) 1.395(4) C(18)-C(19) 1.381(4) C(2)-C(12) 1.433(4) C(20)-C(25) 1.412(3) C(3)-C(4) 1.380(4) C(20)-C(21) 1.413(3) C(4)-C(5) 1.384(3) C(21)-C(22) 1.389(3) C(5)-C(6) 1.456(3) C(21)-C(26) 1.517(4) C(6)-C(7) 1.392(4) C(22)-C(23) 1.381(4) C(6)-C(11) 1.401(3) C(23)-C(24) 1.382(3) C(7)-C(8) 1.384(4) C(23)-C(27) 1.506(4) C(8)-C(9) 1.385(4) C(24)-C(25) 1.396(3) C(9)-C(10) 1.381(4) C(25)-C(28) 1.521(3) C(10)-C(11) 1.400(3) C(29)-C(30) 1.412(3) S26

27 C(29)-C(34) 1.417(3) C(30)-C(31) 1.395(3) C(30)-C(35) 1.522(3) C(31)-C(32) 1.385(4) C(32)-C(33) 1.381(4) C(32)-C(36) 1.509(4) C(33)-C(34) 1.391(3) C(34)-C(37) 1.512(3) C(38A)-C(39A) 1.520(10) C(39A)-C(40A) 1.546(11) C(40A)-C(40A)#1 1.57(3) C(38B)-C(39B) 1.464(10) C(39B)-C(40B) 1.460(11) C(40B)-C(40B)#1 1.36(3) C(1)-(1)-C(5) 120.1(2) C(1)-(1)-B(1) 126.9(2) C(5)-(1)-B(1) (19) C(11)-B(1)-(1) 95.44(18) C(11)-B(1)-C(20) 122.7(2) (1)-B(1)-C(20) (18) C(11)-B(1)-C(29) (19) (1)-B(1)-C(29) (19) C(20)-B(1)-C(29) 115.3(2) (1)-C(1)-C(2) 122.1(2) C(1)-C(2)-C(3) 117.9(2) C(1)-C(2)-C(12) 117.6(2) C(3)-C(2)-C(12) 124.6(2) C(4)-C(3)-C(2) 119.9(2) C(3)-C(4)-C(5) 119.5(2) (1)-C(5)-C(4) 120.5(2) (1)-C(5)-C(6) 109.9(2) C(4)-C(5)-C(6) 129.5(2) C(7)-C(6)-C(11) 123.7(2) C(7)-C(6)-C(5) 125.6(2) C(11)-C(6)-C(5) 110.7(2) C(8)-C(7)-C(6) 118.3(3) C(7)-C(8)-C(9) 119.4(3) C(10)-C(9)-C(8) 121.7(3) C(9)-C(10)-C(11) 120.8(3) C(10)-C(11)-C(6) 116.1(2) C(10)-C(11)-B(1) 132.9(2) C(6)-C(11)-B(1) 110.6(2) C(13)-C(12)-C(2) 170.8(3) C(12)-C(13)-C(14) 174.8(3) C(19)-C(14)-C(15) 119.7(3) C(19)-C(14)-C(13) 119.0(2) C(15)-C(14)-C(13) 121.2(2) C(16)-C(15)-C(14) 120.0(3) C(15)-C(16)-C(17) 120.1(3) C(18)-C(17)-C(16) 120.3(3) C(17)-C(18)-C(19) 120.4(3) C(18)-C(19)-C(14) 119.4(3) C(25)-C(20)-C(21) 115.9(2) C(25)-C(20)-B(1) 122.2(2) C(21)-C(20)-B(1) 121.8(2) C(22)-C(21)-C(20) 121.2(2) C(22)-C(21)-C(26) 116.2(2) C(20)-C(21)-C(26) 122.4(2) C(23)-C(22)-C(21) 122.7(2) C(22)-C(23)-C(24) 116.3(2) C(22)-C(23)-C(27) 121.4(2) C(24)-C(23)-C(27) 122.3(2) C(23)-C(24)-C(25) 122.9(2) C(24)-C(25)-C(20) 120.6(2) C(24)-C(25)-C(28) 114.4(2) C(20)-C(25)-C(28) 125.0(2) C(30)-C(29)-C(34) 116.0(2) C(30)-C(29)-B(1) 117.9(2) C(34)-C(29)-B(1) 126.0(2) C(31)-C(30)-C(29) 121.1(2) C(31)-C(30)-C(35) 114.8(2) S27

28 C(29)-C(30)-C(35) 124.2(2) C(33)-C(34)-C(37) 115.6(2) C(32)-C(31)-C(30) 122.5(2) C(29)-C(34)-C(37) 123.6(2) C(33)-C(32)-C(31) 116.4(2) C(38A)-C(39A)-C(40A) 112.6(10) C(33)-C(32)-C(36) 122.5(2) C(39A)-C(40A)-C(40A)# (11) C(31)-C(32)-C(36) 121.1(3) C(40B)-C(39B)-C(38B) 118.6(10) C(32)-C(33)-C(34) 123.0(2) C(40B)#1-C(40B)-C(39B) 124.6(16) C(33)-C(34)-C(29) 120.8(2) Symmetry transformations used to generate equivalent atoms: #1 -x+2,-y+1,-z+1 Table 4. Anisotropic displacement parameters (Å 2 x 10 3 )for B1A. The anisotropic displacement factor exponent takes the form: -2π 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 (1) 34(1) 35(1) 37(1) -3(1) 6(1) 0(1) B(1) 37(2) 35(2) 37(2) -1(1) 10(1) 1(1) C(1) 36(1) 36(1) 42(1) -6(1) 8(1) -2(1) C(2) 39(1) 49(2) 38(1) -6(1) 9(1) -4(1) C(3) 52(2) 49(2) 41(2) 9(1) 9(1) -2(1) C(4) 49(2) 39(2) 50(2) 4(1) 8(1) -1(1) C(5) 34(1) 33(1) 43(1) 0(1) 5(1) 0(1) C(6) 33(1) 37(1) 46(2) -5(1) 4(1) 4(1) C(7) 46(2) 34(1) 60(2) -3(1) 5(1) 1(1) C(8) 60(2) 35(2) 61(2) -11(1) 5(1) 4(1) C(9) 53(2) 51(2) 54(2) -16(2) 8(1) 6(1) C(10) 44(2) 44(2) 44(2) -7(1) 7(1) 4(1) C(11) 30(1) 40(1) 41(1) -4(1) 4(1) 2(1) C(12) 47(2) 52(2) 39(1) -5(1) 9(1) -8(1) C(13) 45(2) 54(2) 43(2) 2(1) 11(1) -4(1) C(14) 35(1) 43(2) 44(1) -2(1) 13(1) -3(1) C(15) 50(2) 46(2) 45(2) 0(1) 7(1) 2(1) C(16) 55(2) 65(2) 54(2) -14(2) 5(1) 3(2) C(17) 51(2) 49(2) 85(2) -19(2) 13(2) 1(1) C(18) 57(2) 46(2) 92(3) 11(2) 17(2) 11(2) C(19) 43(2) 54(2) 62(2) 7(2) 8(1) 6(1) S28

29 C(20) 35(1) 36(1) 32(1) -2(1) 6(1) 1(1) C(21) 35(1) 37(1) 39(1) -2(1) 5(1) 3(1) C(22) 34(1) 48(2) 45(2) -2(1) 6(1) 3(1) C(23) 40(2) 47(2) 39(1) -1(1) 9(1) -6(1) C(24) 47(2) 34(1) 43(1) -3(1) 11(1) -2(1) C(25) 34(1) 37(1) 39(1) -3(1) 6(1) 3(1) C(26) 37(2) 44(2) 76(2) -4(2) 1(1) 7(1) C(27) 47(2) 57(2) 74(2) -4(2) 18(1) -13(1) C(28) 40(2) 38(2) 59(2) -10(1) 8(1) 4(1) C(29) 34(1) 30(1) 40(1) -6(1) 7(1) 0(1) C(30) 38(1) 37(1) 39(1) -6(1) 9(1) -2(1) C(31) 46(2) 46(2) 34(1) -3(1) 5(1) 4(1) C(32) 39(2) 52(2) 40(1) -4(1) 2(1) 9(1) C(33) 32(1) 51(2) 46(2) -4(1) 7(1) 1(1) C(34) 36(1) 33(1) 42(1) -2(1) 8(1) -1(1) C(35) 46(2) 58(2) 41(1) 1(1) 14(1) 0(1) C(36) 50(2) 103(3) 50(2) 8(2) 3(1) 22(2) C(37) 35(1) 56(2) 60(2) 12(1) 12(1) -2(1) Table 5. Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for B1A. x y z U(eq) H(1A) H(3A) H(4A) H(7A) H(8A) H(9A) H(10A) H(15A) H(16A) H(17A) H(18A) S29

30 H(19A) H(22A) H(24A) H(26A) H(26B) H(26C) H(27A) H(27B) H(27C) H(28A) H(28B) H(28C) H(31A) H(33A) H(35A) H(35B) H(35C) H(36A) H(36B) H(36C) H(37A) H(37B) H(37C) H(38A) H(38B) H(38C) H(39A) H(39B) H(40A) H(40B) H(38D) H(38E) H(38F) H(39C) H(39D) H(40C) S30

31 H(40D) S31

32 S9.5. The crystal structural data of B2. Table 1. Crystal data and structure refinement for B2. Identification code baik4 Empirical formula C35 H35 B Cl2 Formula weight Temperature 180(2) K Wavelength Å Crystal system Monoclinic Space group P2(1)/c Unit cell dimensions a = (11) Å α= 90. b = (8) Å β= (4). c = (9) Å γ = 90. Volume (3) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1164 Crystal size 0.20 x 0.20 x 0.05 mm 3 Theta range for data collection 2.84 to Index ranges -22<=h<=11, -12<=k<=13, -18<=l<=19 Reflections collected Independent reflections 5821 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 5821 / 0 / 366 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 S32

33 Table 2. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for B2. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) B(1) 7620(2) 5535(4) 1078(3) 36(1) (1) 6776(2) 5601(3) 180(2) 32(1) C(1) 7286(2) 6102(3) 1808(2) 35(1) Cl(1) 2321(1) 8796(1) 454(1) 79(1) Cl(2) 3493(1) 7483(1) 1956(1) 74(1) C(2) 7631(2) 6337(3) 2762(2) 44(1) C(3) 7180(2) 6678(3) 3247(2) 47(1) C(4) 6373(2) 6762(3) 2821(2) 40(1) C(5) 6004(2) 6554(3) 1884(2) 42(1) C(6) 6465(2) 6239(3) 1395(2) 33(1) C(7) 6188(2) 6018(3) 410(2) 33(1) C(8) 5449(2) 6216(3) -263(2) 39(1) C(9) 5312(2) 5987(3) -1174(2) 38(1) C(10) 5926(2) 5560(3) -1417(2) 33(1) C(11) 6653(2) 5411(3) -708(2) 35(1) C(12) 5837(2) 5350(3) -2371(2) 36(1) C(13) 5171(2) 5311(3) -3112(2) 36(1) C(14) 5094(2) 5158(3) -4072(2) 37(1) C(15) 4371(2) 4865(4) -4752(2) 44(1) C(16) 5723(2) 5297(4) -4342(3) 44(1) C(17) 7907(2) 4177(3) 1486(2) 33(1) C(18) 7434(2) 3138(4) 1289(2) 34(1) C(19) 7739(2) 2028(4) 1694(2) 40(1) C(20) 8506(2) 1891(4) 2321(2) 42(1) C(21) 8964(2) 2923(4) 2545(2) 44(1) C(22) 8679(2) 4045(4) 2161(2) 39(1) C(23) 6572(2) 3122(3) 665(2) 44(1) C(24) 8833(2) 702(4) 2739(3) 60(1) C(25) 9266(2) 5067(4) 2473(2) 54(1) C(26) 9857(2) 8185(4) -201(3) 59(1) C(27) 8214(2) 6259(4) 707(2) 35(1) S33

34 C(28) 8654(2) 5658(3) 270(2) 36(1) C(29) 9166(2) 6300(4) -28(2) 41(1) C(30) 9278(2) 7520(4) 91(2) 43(1) C(31) 8821(2) 8118(4) 478(2) 44(1) C(32) 8290(2) 7521(4) 767(2) 39(1) C(33) 8620(2) 4318(3) 90(2) 47(1) C(34) 7779(2) 8304(4) 1093(3) 55(1) C(35) 2690(3) 8456(4) 1622(3) 73(2) Table 3. Bond lengths [Å] and angles [ ] for B2. B(1)-C(1) 1.624(5) C(15)-C(16)# (5) B(1)-C(27) 1.636(5) C(16)-C(15)# (5) B(1)-C(17) 1.646(5) C(17)-C(18) 1.407(5) B(1)-(1) 1.648(4) C(17)-C(22) 1.415(5) (1)-C(11) 1.341(4) C(18)-C(19) 1.403(5) (1)-C(7) 1.348(4) C(18)-C(23) 1.509(4) C(1)-C(6) 1.405(4) C(19)-C(20) 1.384(5) C(1)-C(2) 1.407(4) C(20)-C(21) 1.386(5) Cl(1)-C(35) 1.733(4) C(20)-C(24) 1.495(5) Cl(2)-C(35) 1.742(4) C(21)-C(22) 1.397(5) C(2)-C(3) 1.379(5) C(22)-C(25) 1.514(5) C(3)-C(4) 1.378(5) C(26)-C(30) 1.507(5) C(4)-C(5) 1.380(4) C(27)-C(32) 1.409(5) C(5)-C(6) 1.393(4) C(27)-C(28) 1.416(4) C(6)-C(7) 1.449(4) C(28)-C(29) 1.398(5) C(7)-C(8) 1.382(4) C(28)-C(33) 1.514(5) C(8)-C(9) 1.377(4) C(29)-C(30) 1.375(5) C(9)-C(10) 1.408(4) C(30)-C(31) 1.384(5) C(10)-C(11) 1.382(4) C(31)-C(32) 1.397(5) C(10)-C(12) 1.461(4) C(32)-C(34) 1.509(5) C(12)-C(13) 1.326(4) C(13)-C(14) 1.468(4) C(1)-B(1)-C(27) 123.2(3) C(14)-C(15) 1.387(5) C(1)-B(1)-C(17) 103.5(3) C(14)-C(16) 1.390(5) C(27)-B(1)-C(17) 115.6(3) S34

35 C(1)-B(1)-(1) 95.4(3) C(15)#1-C(16)-C(14) 121.0(4) C(27)-B(1)-(1) 102.4(3) C(18)-C(17)-C(22) 116.0(3) C(17)-B(1)-(1) 115.4(3) C(18)-C(17)-B(1) 126.0(3) C(11)-(1)-C(7) 120.2(3) C(22)-C(17)-B(1) 117.7(3) C(11)-(1)-B(1) 127.2(3) C(19)-C(18)-C(17) 121.1(3) C(7)-(1)-B(1) 112.2(3) C(19)-C(18)-C(23) 114.9(3) C(6)-C(1)-C(2) 115.7(3) C(17)-C(18)-C(23) 124.0(3) C(6)-C(1)-B(1) 110.6(3) C(20)-C(19)-C(18) 122.6(4) C(2)-C(1)-B(1) 133.3(3) C(19)-C(20)-C(21) 116.3(4) C(3)-C(2)-C(1) 121.2(3) C(19)-C(20)-C(24) 122.5(4) C(4)-C(3)-C(2) 121.2(3) C(21)-C(20)-C(24) 121.2(4) C(3)-C(4)-C(5) 120.0(3) C(20)-C(21)-C(22) 122.7(4) C(4)-C(5)-C(6) 118.4(3) C(21)-C(22)-C(17) 121.1(4) C(5)-C(6)-C(1) 123.5(3) C(21)-C(22)-C(25) 115.3(3) C(5)-C(6)-C(7) 126.3(3) C(17)-C(22)-C(25) 123.5(4) C(1)-C(6)-C(7) 110.2(3) C(32)-C(27)-C(28) 116.2(3) (1)-C(7)-C(8) 120.4(3) C(32)-C(27)-B(1) 121.9(3) (1)-C(7)-C(6) 110.8(3) C(28)-C(27)-B(1) 121.8(3) C(8)-C(7)-C(6) 128.7(3) C(29)-C(28)-C(27) 120.5(4) C(9)-C(8)-C(7) 119.7(3) C(29)-C(28)-C(33) 115.2(3) C(8)-C(9)-C(10) 120.0(3) C(27)-C(28)-C(33) 124.3(3) C(11)-C(10)-C(9) 116.9(3) C(30)-C(29)-C(28) 123.0(4) C(11)-C(10)-C(12) 119.6(3) C(29)-C(30)-C(31) 116.6(4) C(9)-C(10)-C(12) 123.3(3) C(29)-C(30)-C(26) 122.1(4) (1)-C(11)-C(10) 122.6(3) C(31)-C(30)-C(26) 121.4(4) C(13)-C(12)-C(10) 127.0(3) C(30)-C(31)-C(32) 122.5(4) C(12)-C(13)-C(14) 126.4(3) C(31)-C(32)-C(27) 121.0(4) C(15)-C(14)-C(16) 117.2(3) C(31)-C(32)-C(34) 116.4(4) C(15)-C(14)-C(13) 120.1(3) C(27)-C(32)-C(34) 122.6(3) C(16)-C(14)-C(13) 122.7(3) Cl(1)-C(35)-Cl(2) 113.2(2) C(16)#1-C(15)-C(14) 121.8(4) Symmetry transformations used to generate equivalent atoms: #1 -x+1,-y+1,-z-1 S35

36 Table 4. Anisotropic displacement parameters (Å 2 x 10 3 )for B2. The anisotropic displacement factor exponent takes the form: -2π 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 B(1) 27(3) 53(3) 25(2) -7(2) 6(2) -4(2) (1) 30(2) 42(2) 22(2) -2(1) 7(1) 2(2) C(1) 37(2) 40(2) 25(2) -3(2) 6(2) -1(2) Cl(1) 113(1) 78(1) 50(1) 5(1) 36(1) 4(1) Cl(2) 70(1) 80(1) 70(1) -12(1) 25(1) 3(1) C(2) 39(2) 60(3) 28(2) -3(2) 7(2) 1(2) C(3) 58(3) 55(3) 24(2) -9(2) 11(2) 3(2) C(4) 54(3) 43(3) 29(2) -5(2) 23(2) 0(2) C(5) 40(2) 53(3) 35(2) -4(2) 17(2) 3(2) C(6) 35(2) 39(2) 23(2) -1(2) 9(2) 1(2) C(7) 31(2) 43(3) 25(2) 0(2) 10(2) 1(2) C(8) 32(2) 50(3) 34(2) -4(2) 13(2) 7(2) C(9) 31(2) 52(3) 26(2) 1(2) 5(2) 0(2) C(10) 32(2) 40(2) 25(2) 1(2) 11(2) -5(2) C(11) 36(2) 43(2) 24(2) 0(2) 10(2) 0(2) C(12) 33(2) 47(3) 25(2) -1(2) 7(2) -2(2) C(13) 38(2) 45(3) 26(2) 1(2) 12(2) -5(2) C(14) 37(2) 46(3) 25(2) 0(2) 9(2) 1(2) C(15) 34(3) 71(3) 23(2) 0(2) 9(2) -6(2) C(16) 33(3) 67(3) 25(2) -5(2) 4(2) -9(2) C(17) 29(2) 50(3) 21(2) 0(2) 10(2) 5(2) C(18) 30(2) 52(3) 20(2) -2(2) 9(2) 3(2) C(19) 38(3) 48(3) 33(2) -6(2) 13(2) 4(2) C(20) 44(3) 59(3) 26(2) 2(2) 16(2) 12(2) C(21) 30(2) 70(3) 29(2) 5(2) 8(2) 14(2) C(22) 31(2) 59(3) 27(2) -1(2) 11(2) 0(2) C(23) 34(2) 48(3) 44(2) 6(2) 9(2) 0(2) C(24) 57(3) 71(3) 45(2) 4(2) 13(2) 25(2) C(25) 35(3) 82(3) 37(2) 1(2) 5(2) -2(2) C(26) 54(3) 64(3) 55(3) 17(2) 19(2) -4(2) C(27) 29(2) 48(3) 22(2) -5(2) 3(2) 2(2) S36

37 C(28) 33(2) 49(3) 24(2) 3(2) 10(2) -1(2) C(29) 36(2) 56(3) 29(2) 1(2) 9(2) 5(2) C(30) 37(3) 58(3) 26(2) 8(2) 4(2) -1(2) C(31) 40(3) 47(3) 34(2) 3(2) 1(2) -2(2) C(32) 36(2) 51(3) 24(2) -2(2) 4(2) 1(2) C(33) 52(3) 53(3) 42(2) -3(2) 27(2) 4(2) C(34) 53(3) 52(3) 61(3) -2(2) 23(2) -1(2) C(35) 110(4) 66(3) 59(3) 16(3) 50(3) 25(3) Table 5. Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for B2. x y z U(eq) H(2A) H(3A) H(4A) H(5A) H(8A) H(9A) H(11A) H(12A) H(13A) H(19A) H(21A) H(23A) H(23B) H(23C) H(24A) H(24B) H(24C) H(25A) H(25B) H(25C) H(26A) S37

38 H(26B) H(26C) H(29A) H(31A) H(33A) H(33B) H(33C) H(34A) H(34B) H(34C) H(35A) H(35B) H(15) 3939(18) 4780(30) -4590(20) 36(10) H(16) 6228(19) 5510(30) -3880(20) 44(10) S38

39 S9.6. The crystal structural data of B3. Table 1. Crystal data and structure refinement for B3. Identification code baik1 Empirical formula C99 H96 B3 3 Formula weight Temperature 180(2) K Wavelength Å Crystal system Triclinic Space group P-1 Unit cell dimensions a = (4) Å α= (4). b = (4) Å β= (3). c = (6) Å γ = (3). Volume 4660(2) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1452 Crystal size 0.20 x 0.10 x 0.10 mm 3 Theta range for data collection 1.12 to Index ranges -20<=h<=20, -21<=k<=21, -25<=l<=24 Reflections collected Independent reflections [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / 0 / 964 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 S39

40 Table 2. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for B3. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) (1) 8977(2) 8135(2) -1398(1) 37(1) (2) 1022(2) 7091(2) 1616(1) 39(1) (3) 4166(2) 7209(2) 5944(2) 39(1) C(1) 5941(2) 7647(2) 1569(2) 41(1) C(2) 5358(2) 7522(2) 1303(2) 44(1) C(3) 4524(2) 7392(2) 1779(2) 43(1) C(4) 4295(2) 7382(2) 2536(2) 44(1) C(5) 4857(2) 7510(2) 2817(2) 47(1) C(6) 5678(2) 7643(2) 2325(2) 49(1) C(7) 6807(2) 7812(2) 1086(2) 41(1) C(8) 7201(2) 7728(2) 350(2) 46(1) C(9) 8264(2) 7911(2) -895(2) 41(1) C(10) 8025(2) 7934(2) -145(2) 39(1) C(11) 8558(2) 8200(2) 82(2) 43(1) C(12) 9256(2) 8454(2) -427(2) 42(1) C(13) 9451(2) 8448(2) -1173(2) 37(1) C(14) 10095(2) 8742(2) -1794(2) 40(1) C(15) 10691(2) 9097(2) -1759(2) 43(1) C(16) 11243(2) 9374(2) -2417(2) 47(1) C(17) 11210(3) 9280(2) -3078(2) 53(1) C(18) 10608(2) 8933(2) -3095(2) 48(1) C(19) 10010(2) 8666(2) -2452(2) 40(1) C(20) 3950(2) 7236(2) 1457(2) 48(1) C(21) 3044(2) 7311(2) 1801(2) 48(1) C(22) 1543(2) 7300(2) 1863(2) 40(1) C(23) 2523(3) 7093(2) 1481(2) 46(1) C(24) 2941(3) 6664(2) 813(2) 54(1) C(25) 2431(2) 6423(2) 570(2) 50(1) C(26) 1453(3) 6638(2) 989(2) 41(1) C(27) 760(2) 6429(2) 867(2) 40(1) C(28) 945(3) 6006(2) 257(2) 56(1) S40

41 C(29) 224(3) 5834(2) 236(2) 56(1) C(30) -670(3) 6080(2) 818(2) 56(1) C(31) -848(2) 6505(2) 1425(2) 47(1) C(32) -126(2) 6695(2) 1465(2) 39(1) C(33) 4662(3) 7469(2) 3607(2) 56(1) C(34) 3903(2) 7385(2) 4142(2) 45(1) C(35) 4346(2) 7301(2) 5221(2) 40(1) C(36) 3709(3) 7307(2) 4934(2) 45(1) C(37) 2868(2) 7219(2) 5435(2) 47(1) C(38) 2658(2) 7165(2) 6179(2) 46(1) C(39) 3320(2) 7163(2) 6432(2) 39(1) C(40) 3269(3) 7149(2) 7176(2) 43(1) C(41) 2508(2) 7096(2) 7810(2) 51(1) C(42) 2525(3) 7132(2) 8501(2) 58(1) C(43) 3312(3) 7214(2) 8517(2) 56(1) C(44) 4086(3) 7242(2) 7879(2) 48(1) C(45) 4070(2) 7221(2) 7185(2) 41(1) C(46) 10016(2) 7269(2) -2727(2) 40(1) C(47) 10244(3) 7271(3) -3502(2) 44(1) C(51) 10523(2) 6491(2) -2434(2) 41(1) C(48) 10915(3) 6548(3) -3927(2) 53(1) C(49) 11403(3) 5804(3) -3631(2) 58(1) C(50) 11203(3) 5783(2) -2881(2) 53(1) C(52) 10377(2) 6342(2) -1623(2) 56(1) C(53) 12154(3) 5003(3) -4088(2) 95(2) C(54) 9759(3) 8038(2) -3920(2) 60(1) C(55) 8250(2) 8696(2) -2384(2) 44(1) C(56) 7747(3) 9598(3) -2321(2) 51(1) C(57) 6851(3) 10017(3) -2382(2) 65(1) C(58) 6421(3) 9557(3) -2505(2) 71(1) C(59) 6871(3) 8679(3) -2538(2) 64(1) C(60) 7756(3) 8242(3) -2470(2) 49(1) C(61) 8127(3) 10177(2) -2149(2) 74(1) C(62) 5418(3) 10042(3) -2568(3) 105(2) C(63) 8138(2) 7262(2) -2480(2) 56(1) C(64) -273(2) 7013(2) 2883(2) 37(1) S41

42 C(65) -560(2) 7619(2) 3406(2) 38(1) C(66) -735(2) 7401(3) 4146(2) 49(1) C(67) -640(3) 6589(3) 4406(2) 54(1) C(68) -305(3) 5966(3) 3893(2) 54(1) C(69) -109(2) 6158(2) 3154(2) 45(1) C(70) -718(2) 8563(2) 3220(2) 53(1) C(71) -847(3) 6347(3) 5221(2) 76(1) C(72) 319(3) 5407(2) 2644(2) 65(1) C(73) -853(3) 8241(2) 1847(2) 40(1) C(74) -589(3) 8830(2) 1282(2) 45(1) C(75) -1294(3) 9538(2) 1105(2) 56(1) C(76) -2255(3) 9726(3) 1446(3) 60(1) C(77) -2522(3) 9165(3) 2004(2) 58(1) C(78) -1856(3) 8439(2) 2214(2) 47(1) C(79) 446(3) 8732(2) 842(2) 66(1) C(80) -2985(3) 10495(3) 1210(3) 105(2) C(81) -2282(2) 7932(2) 2862(2) 56(1) C(82) 5724(2) 6183(2) 6334(2) 43(1) C(83) 5812(2) 5417(2) 6108(2) 44(1) C(84) 6578(3) 4637(2) 6133(2) 50(1) C(85) 7266(3) 4585(3) 6377(2) 54(1) C(86) 7153(3) 5336(3) 6613(2) 57(1) C(87) 6414(3) 6119(3) 6600(2) 47(1) C(88) 8091(3) 3751(3) 6367(2) 73(1) C(89) 6430(3) 6887(3) 6869(2) 69(1) C(90) 5123(3) 5330(2) 5830(2) 66(1) C(91) 5241(3) 7933(2) 5954(2) 43(1) C(92) 4692(3) 8788(3) 6204(2) 50(1) C(96) 6130(3) 7790(2) 5367(2) 46(1) C(93) 5060(3) 9427(3) 5935(2) 58(1) C(95) 6480(3) 8448(3) 5110(2) 58(1) C(94) 5978(3) 9263(3) 5401(2) 62(1) C(97) 3650(3) 9072(2) 6735(2) 68(1) C(98) 6379(3) 9960(3) 5164(2) 89(2) C(99) 6776(2) 6947(2) 4960(2) 60(1) B(1) 9296(3) 8186(3) -2298(2) 38(1) S42

43 B(2) -121(3) 7278(3) 2024(2) 41(1) B(3) 4865(3) 7159(3) 6337(2) 45(1) Table 3. Bond lengths [Å] and angles [ ] for B3. (1)-C(9) 1.347(4) C(18)-C(19) 1.396(4) (1)-C(13) 1.361(4) C(19)-B(1) 1.616(5) (1)-B(1) 1.642(4) C(20)-C(21) 1.326(4) (2)-C(22) 1.342(4) C(21)-C(23) 1.454(4) (2)-C(26) 1.351(4) C(22)-C(23) 1.389(4) (2)-B(2) 1.629(4) C(23)-C(24) 1.401(4) (3)-C(35) 1.338(4) C(24)-C(25) 1.355(4) (3)-C(39) 1.362(4) C(25)-C(26) 1.393(4) (3)-B(3) 1.615(4) C(26)-C(27) 1.457(4) C(1)-C(2) 1.382(4) C(27)-C(28) 1.388(4) C(1)-C(6) 1.383(4) C(27)-C(32) 1.403(4) C(1)-C(7) 1.472(4) C(28)-C(29) 1.366(4) C(2)-C(3) 1.399(4) C(29)-C(30) 1.394(5) C(3)-C(4) 1.394(4) C(30)-C(31) 1.391(4) C(3)-C(20) 1.477(4) C(31)-C(32) 1.403(4) C(4)-C(5) 1.374(4) C(32)-B(2) 1.635(5) C(5)-C(6) 1.393(4) C(33)-C(34) 1.313(4) C(5)-C(33) 1.465(4) C(34)-C(36) 1.466(4) C(7)-C(8) 1.343(4) C(35)-C(36) 1.391(4) C(8)-C(10) 1.459(4) C(36)-C(37) 1.389(4) C(9)-C(10) 1.382(4) C(37)-C(38) 1.371(4) C(10)-C(11) 1.398(4) C(38)-C(39) 1.384(4) C(11)-C(12) 1.359(4) C(39)-C(40) 1.446(4) C(12)-C(13) 1.386(4) C(40)-C(41) 1.390(4) C(13)-C(14) 1.433(4) C(40)-C(45) 1.394(4) C(14)-C(15) 1.393(4) C(41)-C(42) 1.402(5) C(14)-C(19) 1.412(4) C(42)-C(43) 1.386(5) C(15)-C(16) 1.388(4) C(43)-C(44) 1.393(4) C(16)-C(17) 1.383(4) C(44)-C(45) 1.402(4) C(17)-C(18) 1.378(4) C(45)-B(3) 1.645(5) S43

44 C(46)-C(51) 1.407(4) C(46)-C(47) 1.430(4) C(46)-B(1) 1.638(5) C(47)-C(48) 1.387(4) C(47)-C(54) 1.519(5) C(51)-C(50) 1.393(4) C(51)-C(52) 1.520(4) C(48)-C(49) 1.362(5) C(49)-C(50) 1.388(5) C(49)-C(53) 1.527(5) C(55)-C(56) 1.409(5) C(55)-C(60) 1.423(4) C(55)-B(1) 1.641(5) C(56)-C(57) 1.394(5) C(56)-C(61) 1.530(4) C(57)-C(58) 1.375(5) C(58)-C(59) 1.364(5) C(58)-C(62) 1.555(5) C(59)-C(60) 1.385(5) C(60)-C(63) 1.521(5) C(64)-C(65) 1.403(4) C(64)-C(69) 1.413(4) C(64)-B(2) 1.628(5) C(65)-C(66) 1.391(4) C(65)-C(70) 1.522(4) C(66)-C(67) 1.357(5) C(67)-C(68) 1.388(5) C(67)-C(71) 1.528(5) C(68)-C(69) 1.376(4) C(69)-C(72) 1.520(4) C(73)-C(74) 1.421(4) C(73)-C(78) 1.421(4) C(73)-B(2) 1.656(5) C(74)-C(75) 1.388(5) C(74)-C(79) 1.518(5) C(75)-C(76) 1.360(5) C(76)-C(77) 1.382(5) C(76)-C(80) 1.515(5) C(77)-C(78) 1.397(5) C(78)-C(81) 1.506(4) C(82)-C(83) 1.399(4) C(82)-C(87) 1.405(4) C(82)-B(3) 1.668(5) C(83)-C(84) 1.405(4) C(83)-C(90) 1.527(4) C(84)-C(85) 1.380(4) C(85)-C(86) 1.365(5) C(85)-C(88) 1.493(5) C(86)-C(87) 1.381(5) C(87)-C(89) 1.527(4) C(91)-C(96) 1.404(4) C(91)-C(92) 1.408(4) C(91)-B(3) 1.633(5) C(92)-C(93) 1.393(5) C(92)-C(97) 1.515(4) C(96)-C(95) 1.403(5) C(96)-C(99) 1.512(4) C(93)-C(94) 1.389(5) C(95)-C(94) 1.375(5) C(94)-C(98) 1.517(5) C(9)-(1)-C(13) 119.8(3) C(9)-(1)-B(1) 127.4(3) C(13)-(1)-B(1) 112.4(3) C(22)-(2)-C(26) 120.2(3) C(22)-(2)-B(2) 126.6(3) C(26)-(2)-B(2) 113.0(3) C(35)-(3)-C(39) 120.6(3) C(35)-(3)-B(3) 126.4(3) C(39)-(3)-B(3) 113.0(3) C(2)-C(1)-C(6) 118.2(3) C(2)-C(1)-C(7) 123.0(3) C(6)-C(1)-C(7) 118.8(3) S44

45 C(1)-C(2)-C(3) 121.4(3) C(4)-C(3)-C(2) 118.3(3) C(4)-C(3)-C(20) 123.0(3) C(2)-C(3)-C(20) 118.6(3) C(5)-C(4)-C(3) 121.6(3) C(4)-C(5)-C(6) 118.3(3) C(4)-C(5)-C(33) 123.1(3) C(6)-C(5)-C(33) 118.5(3) C(1)-C(6)-C(5) 122.2(3) C(8)-C(7)-C(1) 124.2(3) C(7)-C(8)-C(10) 125.4(3) (1)-C(9)-C(10) 122.5(3) C(9)-C(10)-C(11) 117.4(3) C(9)-C(10)-C(8) 117.8(3) C(11)-C(10)-C(8) 124.8(3) C(12)-C(11)-C(10) 120.0(3) C(11)-C(12)-C(13) 120.7(3) (1)-C(13)-C(12) 119.4(3) (1)-C(13)-C(14) 110.4(3) C(12)-C(13)-C(14) 130.2(3) C(15)-C(14)-C(19) 123.8(3) C(15)-C(14)-C(13) 125.4(3) C(19)-C(14)-C(13) 110.7(3) C(16)-C(15)-C(14) 117.4(3) C(17)-C(16)-C(15) 120.6(3) C(18)-C(17)-C(16) 120.8(3) C(17)-C(18)-C(19) 121.6(3) C(18)-C(19)-C(14) 115.7(3) C(18)-C(19)-B(1) 133.2(3) C(14)-C(19)-B(1) 110.7(3) C(21)-C(20)-C(3) 126.1(3) C(20)-C(21)-C(23) 124.5(3) (2)-C(22)-C(23) 122.3(3) C(22)-C(23)-C(24) 116.2(3) C(22)-C(23)-C(21) 118.9(3) C(24)-C(23)-C(21) 124.8(3) C(25)-C(24)-C(23) 122.0(3) C(24)-C(25)-C(26) 118.6(3) (2)-C(26)-C(25) 120.5(3) (2)-C(26)-C(27) 110.1(3) C(25)-C(26)-C(27) 129.4(3) C(28)-C(27)-C(32) 124.0(3) C(28)-C(27)-C(26) 125.6(3) C(32)-C(27)-C(26) 110.4(3) C(29)-C(28)-C(27) 118.4(3) C(28)-C(29)-C(30) 119.9(3) C(31)-C(30)-C(29) 121.1(3) C(30)-C(31)-C(32) 120.5(3) C(27)-C(32)-C(31) 115.9(3) C(27)-C(32)-B(2) 110.2(3) C(31)-C(32)-B(2) 133.4(3) C(34)-C(33)-C(5) 126.0(3) C(33)-C(34)-C(36) 127.2(3) (3)-C(35)-C(36) 121.8(3) C(37)-C(36)-C(35) 116.9(3) C(37)-C(36)-C(34) 120.4(3) C(35)-C(36)-C(34) 122.7(3) C(38)-C(37)-C(36) 121.6(3) C(37)-C(38)-C(39) 118.8(3) (3)-C(39)-C(38) 120.1(3) (3)-C(39)-C(40) 109.5(3) C(38)-C(39)-C(40) 130.4(3) C(41)-C(40)-C(45) 123.3(3) C(41)-C(40)-C(39) 124.9(3) C(45)-C(40)-C(39) 111.7(3) C(40)-C(41)-C(42) 119.3(4) C(43)-C(42)-C(41) 117.9(3) C(42)-C(43)-C(44) 122.5(4) C(43)-C(44)-C(45) 120.0(3) C(40)-C(45)-C(44) 116.9(3) C(40)-C(45)-B(3) 109.2(3) C(44)-C(45)-B(3) 133.6(3) S45