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
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 ): 10.21 (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, 121.9. HRMS calcd. for C 12 H 8 O: m/z 260.9789; found: 260.9787. 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
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, 85.0. HRMS calcd. for C 13 H 8 : m/z 256.9840; found: 256.9839. 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, 21.9. HRMS calcd. for C 17 H 18 O 2 : m/z 347.0519; found: 347.0521. 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, 21.7. S3
HRMS calcd. for C 35 H 40 BO 2 : m/z 517,3152; found: 517.3151. 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, 112.9. HRMS calcd. for C 27 H 18 3 3 : m/z 621.9123; found: 623.9136. 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 3 11 1,4-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
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 14 2 2 : m/z 442.9677; found: 442.9519. 1,4-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 22 2 2 : m/z 595.0205; found: 595.0149. S2. Reduction potentials of A1, B1A, B1-B3. Compound A1 B1A B1 B2 B3 Potential (V) vs FeCp 2 +/0 in DMF -2.36-2.11-2.09-1.94, -2.10-1.98, -2.13 S3. UV-Vis absorption (left) and Emission Spectral change (right) with 365 nm Irradiation. S1.1 Spectra of B1. S5
S1.2 Spectra of B1A. S1.3 Spectra of B2. S1.4 Spectra of B3. S6
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
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 1.0 0.8 0.6 0.4 0.2 2 UV 2 PL 11 UV 11 PL 9 UV 9 PL 2 11 9 0.0 300 350 400 450 500 550 600 Wavelength (nm) S8
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 2-5.62-2.15 358 410 trans-b1-5.56-2.31 381 428 cis-b1-5.57-2.27 376 428 All trans-b2-5.61-2.75 434 465 trans,cis-b2-5.63-2.68 420 ot Available All trans-b3-5.69-2.74 421 455 trans,trans,cis-b3-5.68-2.75 424 ot Available B1A -5.59-2.36 384 430 a 1.0 x 10-5 M in toluene. S9
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 1 435.88 0.0125 108 109 0.69957 2.8444 2 398.29 0.0085 106 109 107 109-0.35758 0.60211 3.1129 3 388.86 0.0056 106 109 107 109 0.60470 0.36019 3.1884 4 369.23 0.0010 105 109 0.70297 3.3579 5 363.56 0.0079 108 110 0.69859 3.4103 6 338.48 0.0019 106 110 107 110-0.38768 0.58348 3.6630 7 332.62 0.0159 104 109 106 110 107 110 8 329.18 0.0550 103 109 104 109 106 110 107 110 0.41549 0.46235 0.30571 0.11974 0.51844-0.35555-0.24441 3.7275 3.7664 9 317.31 0.0004 105 110 0.70390 3.9073 10 309.17 0.0911 103 109 104 110 0.64779-0.12189 4.0102 S10
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 1 455.74 0.0495 135 136 135 137 2 414.72 0.0086 133 136 134 136 3 407.85 0.0121 133 136 134 136 135 137 4 406.65 0.0216 132 136 133 136 134 136 135 137 5 386.24 0.0099 131 136 132 136 6 377.44 0.0070 133 137 134 137 7 369.57 0.4358 130 136 131 136 131 137 132 136 133 137 134 137 8 366.83 0.4436 131 136 132 136 132 137 133 136 133 137 134 137 9 350.23 0.0033 131 137 132 137 10 345.62 0.0959 131 136 131 137 132 137 0.68910-0.10667 0.44874 0.53227-0.34138 0.25522 0.54430 0.12762 0.38524-0.37135 0.42462-0.42122 0.55782 0.53279 0.44444 0.10872 0.40029-0.10649 0.25293 0.26422-0.37073 0.30815 0.24331-0.13155-0.10243-0.36091 0.37872-0.40860 0.56420 0.11194 0.53834 0.37525 2.7205 2.9896 3.0400 3.0490 3.2101 3.2849 3.3548 3.3798 3.5400 3.5873 S11
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 1 460.96 0.0389 134 135 0.69394 2.6897 2 419.50 0.0091 132 135 133 135 3 411.15 0.0205 132 135 133 135-0.34862 0.60364 0.60060 0.35342 2.9555 3.0156 4 391.01 0.0014 131 135 0.69930 3.1709 5 387.48 0.0019 134 136 0.69084 3.1997 6 363.78 0.4281 129 135 130 135 130 136 132 136 133 136 7 361.59 0.2240 129 135 130 135 132 136 133 136 8 352.60 0.0745 130 135 132 136 133 136-0.10692 0.52039 0.10122-0.32958 0.24543 0.10368-0.33453-0.28570 0.50318 0.11639 0.54378 0.40779 3.4082 3.4289 3.5163 9 338.26 0.0009 131 136 0.69403 3.6654 10 330.68 0.1602 129 135 130 135 0.66088 0.12397 3.7493 S12
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 1 499.86 0.3773 248 251 249 250 2 492.91 0.0000 248 250 249 251 3 448.87 0.6565 243 250 245 250 246 250 247 250 4 448.41 0.0283 244 250 245 250 245 251 246 250 5 448.08 0.3867 245 250 246 251 247 250 6 440.41 0.0017 243 251 244 250 246 250 7 431.95 0.9013 243 250 245 250 247 250 8 416.99 0.0024 241 250 242 250 9 416.58 0.0264 241 250 242 250 10 414.23 0.0008 248 250 248 252 249 251 249 253-0.13583 0.68284 0.68741-0.12535-0.18715 0.40059 0.17896 0.48655-0.28205-0.15357-0.11734 0.60226 0.52115-0.10387-0.43957-0.10483 0.62873 0.27529 0.65140 0.11641 0.10903-0.16632 0.66737 0.66766 0.16664 0.10740 0.40602 0.51908-0.18973 2.4804 2.5154 2.7621 2.7650 2.7670 2.8152 2.8703 2.9733 2.9762 2.9932 S13
References. 1. Wu, J.; Watson, M. D.; Zhang, L.; Wang, Z.; Mullen, K. J. Am. Chem. Soc. 2004, 126, 177-186. 2. Grave, C.; Lentz, D.; Schafer, A.; Samor, P.; Rabe, J. P.; Franke, P.; Schluter, A. D. J. Am. Chem. Soc. 2003, 125, 6907. 3. 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, 2004. S14
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 505.48 1102.70 1360.22 546.55 Crystal system Monoclinic Monoclinic Monoclinic Monoclinic Space Group P2 1 /n P2 1 /c P-1 P2 1 /n a, Å 14.9201(16) 18.4312(11) 16.582(4) 14.8343(3) b, Å 14.1025(15) 11.1173(8) 17.149(4) 13.9749(3) c, Å 15.2798(16) 15.6979(9) 19.939(6) 15.5452(3) α º 90 90 79.126(4) 90 βº 101.111(1) 112.74(4) 65.471(3) 102.543(2) γ,º 90 90 64.616(3) 90 V, Å 3 3154.8(6) 2966.5(3) 4660(2) 3145.73(11) Z 4 2 2 4 D calc, g cm -3 1.064 1.235 0.969 1.038 T, K 180 180 180 180 µ, mm -1 0.060 0.244 0.055 0.065 2θ max, º 54.24 52.00 53.00 51.00 Reflns measured 34525 13573 50862 13797 Reflns used 6950 5821 19197 5826 Parameters 358 366 964 379 R [I>2σ I)]: R 1 a wr 2 b 0.0552 0.1503 0.0604 0.1073 0.0672 0.1325 0.0608 0.1546 R (all data): a R 1 0.0848 0.1758 0.1993 0.0993 b wr 2 0.1640 0.1480 0.1619 0.1808 GOF on F 2 1.103 0.959 0.789 1.038 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
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) B1 1.646(2) 1.626(3) 1.648(2) 1.352(3) 1.653(2) B2 1.636(5) 1.624(5) 1.648(4) 1.326(4) 1.646(5) B3 1.638(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) B1 114.76(14) 123.22(14) 103.40(13) 95.68(13) 103.44(13) 115.32(13) B2 115.6(3) 123.2(3) 103.5(3) 95.4(3) 102.4(3) 115.4(3) B3 117.5(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) 104.21(19) 95.44(18) 102.97(18) 114.86(19) S16
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 505.48 Temperature 180(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group P2(1)/n Unit cell dimensions a = 14.9202(16) Å α= 90. b = 14.1025(15) Å β= 101.1110(10). c = 15.2798(16) Å γ = 90. Volume 3154.8(6) Å 3 Z 4 Density (calculated) 1.064 Mg/m 3 Absorption coefficient 0.060 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 27.12. Index ranges -19<=h<=19, -18<=k<=17, -19<=l<=19 Reflections collected 34525 Independent reflections 6950 [R(int) = 0.0441] Completeness to theta = 27.12 99.7 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9970 and 0.9881 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 6950 / 0 / 358 Goodness-of-fit on F 2 1.103 Final R indices [I>2sigma(I)] R1 = 0.0552, wr2 = 0.1503 R indices (all data) R1 = 0.0848, wr2 = 0.1640 Largest diff. peak and hole 0.377 and -0.208 e.å -3 S17
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
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) 123.22(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) 103.44(13) C(14)-C(15) 1.408(3) C(1)-B(1)-C(29) 103.40(13) C(15)-C(16) 1.371(3) C(20)-B(1)-C(29) 114.76(14) C(16)-C(17) 1.411(3) (1)-B(1)-C(29) 115.32(13) C(17)-C(18) 1.329(3) C(11)-(1)-C(7) 120.25(15) C(18)-C(19) 1.400(3) C(11)-(1)-B(1) 126.97(14) C(20)-C(21) 1.415(2) C(7)-(1)-B(1) 112.54(14) S19
C(2)-C(1)-C(6) 116.37(16) C(21)-C(20)-C(25) 115.73(14) C(2)-C(1)-B(1) 132.92(16) C(21)-C(20)-B(1) 122.20(14) C(6)-C(1)-B(1) 110.17(15) C(25)-C(20)-B(1) 122.07(14) C(3)-C(2)-C(1) 120.73(18) C(22)-C(21)-C(20) 121.21(15) C(4)-C(3)-C(2) 121.1(2) C(22)-C(21)-C(26) 116.38(15) C(5)-C(4)-C(3) 120.05(18) C(20)-C(21)-C(26) 122.40(15) C(4)-C(5)-C(6) 118.78(19) C(23)-C(22)-C(21) 122.32(15) C(5)-C(6)-C(1) 122.95(18) C(24)-C(23)-C(22) 116.49(15) C(5)-C(6)-C(7) 126.13(18) C(24)-C(23)-C(27) 122.15(16) C(1)-C(6)-C(7) 110.89(15) C(22)-C(23)-C(27) 121.33(16) (1)-C(7)-C(8) 119.85(17) C(23)-C(24)-C(25) 123.21(16) (1)-C(7)-C(6) 110.18(15) C(24)-C(25)-C(20) 120.70(14) C(8)-C(7)-C(6) 129.93(17) C(24)-C(25)-C(28) 115.16(15) C(9)-C(8)-C(7) 119.41(18) C(20)-C(25)-C(28) 124.14(14) C(8)-C(9)-C(10) 121.07(18) C(34)-C(29)-C(30) 116.11(15) C(11)-C(10)-C(9) 116.42(18) C(34)-C(29)-B(1) 117.59(14) C(11)-C(10)-C(12) 121.15(18) C(30)-C(29)-B(1) 126.08(15) C(9)-C(10)-C(12) 122.40(18) C(31)-C(30)-C(29) 120.57(17) (1)-C(11)-C(10) 122.94(17) C(31)-C(30)-C(35) 115.98(15) C(13)-C(12)-C(10) 125.73(18) C(29)-C(30)-C(35) 123.43(15) C(12)-C(13)-C(14) 129.16(18) C(32)-C(31)-C(30) 122.76(17) C(19)-C(14)-C(15) 118.34(18) C(33)-C(32)-C(31) 116.99(17) C(19)-C(14)-C(13) 119.92(18) C(33)-C(32)-C(36) 120.9(2) C(15)-C(14)-C(13) 121.61(17) C(31)-C(32)-C(36) 122.09(19) C(16)-C(15)-C(14) 120.57(19) C(32)-C(33)-C(34) 122.46(19) C(15)-C(16)-C(17) 119.4(2) C(33)-C(34)-C(29) 120.98(16) C(18)-C(17)-C(16) 120.0(2) C(33)-C(34)-C(37) 114.83(16) C(17)-C(18)-C(19) 120.9(2) C(29)-C(34)-C(37) 124.19(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 11 +... + 2 h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 S20
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
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) 1013 4512 4871 59 H(3A) 1082 2885 5117 70 H(4A) 1314 1842 4002 73 H(5A) 1425 2418 2599 65 H(8A) 1329 3238 1152 67 H(9A) 1287 4247-57 69 H(11A) 1186 6479 1563 54 H(12A) 1037 5889-708 65 H(13A) 1678 7292 527 60 H(15A) 671 6974-1797 64 H(16A) 490 8151-2878 76 H(17A) 980 9713-2476 80 H(18A) 1674 10042-1050 89 H(19A) 1877 8860 43 74 H(22A) -1909 6388 2875 55 H(24A) -175 8559 2935 52 H(26A) -1516 4882 2748 89 H(26B) -627 4634 3481 89 H(26C) -574 4635 2445 89 H(27A) -2527 7954 2654 95 H(27B) -1871 8815 2512 95 H(27C) -1963 8507 3498 95 H(28A) 1257 8305 2569 74 H(28B) 1760 7301 2745 74 H(28C) 1644 7961 3568 74 H(31A) 4376 6124 4095 59 S22
H(33A) 2782 7049 5742 60 H(35A) 3901 5317 2867 86 H(35B) 2949 5673 2292 86 H(35C) 3000 4690 2822 86 H(36A) 4870 7485 5330 128 H(36B) 4934 6520 5890 128 H(36C) 4336 7385 6139 128 H(37A) 762 6025 4728 77 H(37B) 931 7145 4780 77 H(37C) 1315 6492 5626 77 S23
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 546.55 Temperature 180(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group P2(1)/n Unit cell dimensions a = 14.8343(3) Å α= 90. b = 13.9749(3) Å β= 102.543(2). c = 15.5452(3) Å γ = 90. Volume 3145.73(11) Å 3 Z 4 Density (calculated) 1.154 Mg/m 3 Absorption coefficient 0.065 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 25.50. Index ranges -17<=h<=15, -16<=k<=16, -16<=l<=18 Reflections collected 13797 Independent reflections 5826 [R(int) = 0.0471] Completeness to theta = 25.50 99.6 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9935 and 0.9807 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 5826 / 6 / 379 Goodness-of-fit on F 2 1.038 Final R indices [I>2sigma(I)] R1 = 0.0608, wr2 = 0.1546 R indices (all data) R1 = 0.0993, wr2 = 0.1808 Largest diff. peak and hole 0.413 and -0.348 e.å -3 S24
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
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
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) 112.70(19) C(11)-B(1)-(1) 95.44(18) C(11)-B(1)-C(20) 122.7(2) (1)-B(1)-C(20) 102.97(18) C(11)-B(1)-C(29) 104.21(19) (1)-B(1)-C(29) 114.86(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
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)#1 109.4(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 11 +... + 2 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
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) 1296 8537 1712 46 H(3A) 1311 10807 105 57 H(4A) 1333 11820 1302 56 H(7A) 1456 12643 2716 57 H(8A) 1325 13230 4101 64 H(9A) 1079 12165 5177 64 H(10A) 1027 10530 4937 53 H(15A) 579 7944-2089 57 H(16A) 452 6537-2898 71 H(17A) 1018 5113-2221 74 H(18A) 1735 5091-742 78 S29
H(19A) 1843 6488 95 64 H(22A) -1894 8661 2835 51 H(24A) -158 6444 3021 49 H(26A) -1485 10168 2716 81 H(26B) -542 10377 2407 81 H(26C) -572 10446 3429 81 H(27A) -1792 6125 2698 88 H(27B) -2493 7000 2435 88 H(27C) -2134 6716 3449 88 H(28A) 1297 6649 2761 69 H(28B) 1691 7062 3730 69 H(28C) 1814 7661 2885 69 H(31A) 2871 7914 5812 51 H(33A) 4464 8860 4219 52 H(35A) 1397 8532 5699 71 H(35B) 994 7859 4872 71 H(35C) 826 8990 4800 71 H(36A) 4995 7485 5391 103 H(36B) 4439 7474 6165 103 H(36C) 5032 8394 6023 103 H(37A) 3991 9799 3085 75 H(37B) 3049 10384 3010 75 H(37C) 3057 9416 2461 75 H(38A) 7300 4620 4190 134 H(38B) 7972 3711 4314 134 H(38C) 7985 4458 3537 134 H(39A) 8572 4893 5369 119 H(39B) 8571 5651 4597 119 H(40A) 9711 4667 4093 114 H(40B) 9752 3989 4934 114 H(38D) 7488 4009 4336 134 H(38E) 8280 3629 3869 134 H(38F) 7878 4688 3672 134 H(39C) 8469 5095 5126 119 H(39D) 8882 4045 5309 119 H(40C) 9822 4385 4315 114 S30
H(40D) 9476 5459 4305 114 S31
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 551.35 Temperature 180(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group P2(1)/c Unit cell dimensions a = 18.4312(11) Å α= 90. b = 11.1173(8) Å β= 112.743(4). c = 15.6979(9) Å γ = 90. Volume 2966.5(3) Å 3 Z 4 Density (calculated) 1.235 Mg/m 3 Absorption coefficient 0.244 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 26.00. Index ranges -22<=h<=11, -12<=k<=13, -18<=l<=19 Reflections collected 13573 Independent reflections 5821 [R(int) = 0.0815] Completeness to theta = 26.00 99.7 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9879 and 0.9529 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 5821 / 0 / 366 Goodness-of-fit on F 2 0.959 Final R indices [I>2sigma(I)] R1 = 0.0604, wr2 = 0.1073 R indices (all data) R1 = 0.1758, wr2 = 0.1480 Largest diff. peak and hole 0.223 and -0.267 e.å -3 S32
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
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)#1 1.375(5) B(1)-C(27) 1.636(5) C(16)-C(15)#1 1.375(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
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
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 11 +... + 2 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
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) 8184 6260 3077 53 H(3A) 7431 6859 3886 56 H(4A) 6071 6964 3172 48 H(5A) 5449 6624 1581 50 H(8A) 5037 6510-98 46 H(9A) 4804 6117-1639 46 H(11A) 7084 5164-856 42 H(12A) 6308 5228-2471 43 H(13A) 4697 5389-3011 44 H(19A) 7406 1342 1530 48 H(21A) 9492 2864 2977 53 H(23A) 6352 2327 691 66 H(23B) 6514 3292 29 66 H(23C) 6293 3735 869 66 H(24A) 9301 831 3305 89 H(24B) 8978 235 2299 89 H(24C) 8436 262 2886 89 H(25A) 9635 4920 3109 81 H(25B) 8987 5825 2446 81 H(25C) 9557 5116 2068 81 H(26A) 9874 7810-758 88 S37
H(26B) 10380 8152 297 88 H(26C) 9692 9026-332 88 H(29A) 9448 5873-326 49 H(31A) 8871 8966 550 53 H(33A) 8749 4157-449 70 H(33B) 8088 4021-29 70 H(33C) 8999 3906 631 70 H(34A) 7228 8061 781 83 H(34B) 7837 9147 947 83 H(34C) 7940 8213 1762 83 H(35A) 2267 8085 1775 88 H(35B) 2849 9212 1980 88 H(15) 3939(18) 4780(30) -4590(20) 36(10) H(16) 6228(19) 5510(30) -3880(20) 44(10) S38
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 1360.22 Temperature 180(2) K Wavelength 0.71073 Å Crystal system Triclinic Space group P-1 Unit cell dimensions a = 16.582(4) Å α= 79.126(4). b = 17.149(4) Å β= 65.471(3). c = 19.939(6) Å γ = 64.616(3). Volume 4660(2) Å 3 Z 2 Density (calculated) 0.969 Mg/m 3 Absorption coefficient 0.055 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 26.50. Index ranges -20<=h<=20, -21<=k<=21, -25<=l<=24 Reflections collected 50862 Independent reflections 19197 [R(int) = 0.1126] Completeness to theta = 26.50 99.4 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9945 and 0.9891 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 19197 / 0 / 964 Goodness-of-fit on F 2 0.786 Final R indices [I>2sigma(I)] R1 = 0.0672, wr2 = 0.1325 R indices (all data) R1 = 0.1993, wr2 = 0.1619 Largest diff. peak and hole 0.207 and -0.180 e.å -3 S39
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
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
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
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
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
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