Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139

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1 Supporting Information for Synthesis of 2,6-Hexatertiarybutylterphenyl Derivatives, 2,6- (2,4,6-t-Bu 3 C 6 H 2 ) 2 C 6 H 3 X, where X = I, Li, OH, SH, N 3, or NH 2. Konstantin V. Bukhryakov, Richard R. Schrock *, Amir Hoveyda, Peter Müller, and Jonathan Becker Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts Contents General experimental details... 1 Experimental procedures... 2 NMR spectra... 7 X-ray crystal structure data Crystal data and structure refinement for Li(Et2O)2HTBT Crystal data and structure refinement for W(OHTBT)2Cl General experimental details All air- and moisture-sensitive materials were manipulated under a nitrogen atmosphere in a Vacuum Atmospheres glovebox or on a dual-manifold Schlenk line. All glassware were either oven dried or flame dried prior to use. Benzene, THF, diethyl ether, n-hexane, and toluene were degassed, passed through activated alumina columns, and stored over 4 Å Linde-type molecular sieves prior to use. Pentane was washed with H2SO4, followed by water and saturated aqueous NaHCO3, and dried over CaCl2 pellets for at least 2 weeks prior to use in the solvent purification system. Deuterated solvents were dried over 4 Å Linde-type molecular sieves prior to use. 1 H NMR spectra were obtained on 400, 500, or 600 MHz spectrometers and 13 C NMR spectra on 101 or 151 MHz machines. Chemical shifts for 1 H and 13 C spectra are reported as parts per million relative to tetramethylsilane and 1

2 referenced to the residual 1 H or 13 C resonances of the deuterated solvent ( 1 H δ: benzene 7.16, chloroform 7.26, methylene chloride 5.32; 13 C δ: benzene , chloroform 77.16, methylene chloride 53.84). Experimental procedures Preparation of 2,2'',4,4'',6,6''-hexa-tert-butyl-2'-iodo-1,1':3',1''-terphenyl (HTBTI). Cl I Cl TMSCH 2 MgCl 0 ºC to RT THF, 10 min Cl MgCl Cl t-bu t-bu MgBr t-bu THF, reflux, 16 h t-bu t-bu t-bu t-bu MgX X = Cl, Br t-bu t-bu I I 2 TTBP TTBP hexane reflux, 1 h (TTBP = 2,4,6-t-Bu 3 C 6 H 2 ) A solution of TMSCH2MgCl (6.2 ml, 1.3 M in THF, 8.06 mmol, 1.1 eq.) was added to a solution of 1,3-dichloro-2-iodobenzene (2.0 g, 7.33 mmol, 1 eq.) in 20 ml of THF at 0 C. The reaction mixture was stirred at room temperature for 10 minutes and a solution of (2,4,6-tri-tert-butylphenyl)magnesium bromide 1 (56.8 ml, M in THF, mmol, 2 eq.) was added and the resulting mixture was refluxed under nitrogen overnight. THF was removed under reduced pressure and 100 ml of n-hexane was added. The reaction mixture was stirred for 10 minutes and hexane was removed in vacuo. The residue was suspended in 100 ml of n-hexane and iodine (3.72 g, mmol, 2 eq.) was added. The resulting mixture was refluxed under nitrogen for 1 hour and cooled to room temperature. A saturated aqueous solution of Na2S2O3 (20 ml) was added followed by 100 ml of water. The product was extracted into ether (3 x 100 ml). The ether extracts were combined and dried with Na2SO4. The mixture was filtered and the solvent removed from the filtrate in vacuo. The product was purified by column chromatography (hexane : ethyl acetate, 0- >2%). HTBTI (3.3 g, 65%) was obtained as white powder that could be recrystallized from n-hexane: 1 H NMR (600 MHz, CD2Cl2) δ 7.54 (d, J = 7.6 Hz, 2H), 7.49 (s, 4H), 7.22 (t, J = 7.6 Hz, 1H), 1.33 (s, 18H), 1.20 (s, 36H); 13 C NMR (151 MHz, CD2Cl2) δ , , 147.8, 141.3, 135.5, 124.7, 123.5, 117.0, 39.2, 35.37, 35.24, HRMS (m/z) calcd for C42H61I [M+]: , found: Salvi, L.; Davis, N. R.; Ali, S. Z.; Buchwald, S. Org. Lett., 2012, 14,

3 Preparation of (2,2'',4,4'',6,6''-hexa-tert-butyl-[1,1':3',1''-terphenyl]-2'-yl)lithium (Li(Et2O)2HTBT). I Li TTBP TTBP Li-t-Bu, ether TTBP TTBP A solution of HTBTI (200 mg, 0.30 mmol, 1 eq.) in 20 ml of diethyl ether was frozen by liquid nitrogen. A solution of Li-t-Bu (0.475 ml, 1.7 M in pentane, 0.81 mmol, 2.8 eq.) was added and the resulting mixture was placed into CO2/acetone bath and was stirred at 78 C for 2 hours. During this time reaction mixture melts and white precipitate forms. Ether was removed in vacuo. The residue was suspended in 30 ml of pentane and filtered off to remove LiI. Pentane was removed in vacuo and the Li(Et2O)2HTBT was dissolved in minimum amount of ether (~ 5 ml) at room temperature. The solution was kept in the freezer at 18 C overnight to get colorless crystals of Li(Et2O)2HTBT (140 mg, 67%) suitable for X-ray data collection. 1 H NMR (400 MHz; C6H6): δ 7.69 (s, 4H), 7.34 (d, J = 7.5 Hz, 2H), 7.10 (t, J = 7.5 Hz, 1H), 2.76 (q, J = 7.1 Hz, 4H), 1.52 (s, 36H), 1.40 (s, 18H), 0.56 (t, J = 7.1 Hz, 6H). 13 C NMR (151 MHz; C6D6): δ 151.4, 148.7, 148.3, 145.9, 130.4, 122.8, 119.9, 66.2, 39.1, 35.2, 34.9, 31.8, Anal. Calcd for C50H81LiO2: C, 83.28; H, Found: C, 83.69; H, Preparation of 2,2'',4,4'',6,6''-hexa-tert-butyl-[1,1':3',1''-terphenyl]-2'-ol (HTBTOH). 1. Li-t-Bu, ether I 2. B(OMe) 3, toluene OH TTBP TTBP reflux, 16 h TTBP TTBP 3. NaOH, H 2 O 2 EtOH, toluene reflux, 16 h A solution Li-t-Bu (10.15 ml, 1.7 M in pentane, mmol, 2.6 eq.) was added to a solution of HTBTI (4.6 g, 6.64 mmol, 1 eq.) in 400 ml of diethyl ether at 90 C. The reaction mixture was stirred at 78 C for 2 hours. During this time white precipitate formed. The cooling bath was removed and diethyl ether was removed in vacuo and 100 ml of toluene was added to the residue. B(OMe)3 (2.96 ml, mmol, 4.0 eq.) was added and the mixture was refluxed overnight under nitrogen. The reaction mixture was cooled to room temperature, 100 ml of HCl (1.0 M in water) was added, and the mixture stirred for 1 hour. The organic layer was removed and the aqueous solution was extracted with hexane (3 x 100 ml). All organic solutions were combined, dried under Na2SO4, and filtered through pad of silica gel. The solvent was removed in vacuo. The residue was 3

4 dissolved in the mixture of 100 ml of ethanol and 100 ml of toluene, NaOH (2.66 g, mmol, 10.0 eq.), 20 ml of water and H2O2 (10 ml, 35% wt. in water, mmol, 16 eq.) were added, and the resulting mixture was refluxed overnight. Solvents were removed in vacuo, aqueous HCl (1.0 M) was added to ph<2, and product was extracted by hexane (3 x 100 ml). Organic solutions were combined and dried with Na2SO4. The mixture was filtered and the solvent was removed from the filtrate in vacuo. The product was purified by column chromatography (hexane : ethyl acetate, 0->3%). HTBTOH (2.90 g, 75%) was obtained as white powder that could be recrystallized from methanol: 1 H NMR (500 MHz, CD2Cl2) δ 7.57 (s, 4H), 7.25 (d, J = 7.6 Hz, 2H), 6.82 (t, J = 7.6 Hz, 1H), 4.80 (s, 1H), 1.35 (s, 18H), 1.23 (s, 36H); 13 C NMR (101 MHz, CD2Cl2) δ 152.8, 150.0, 148.9, 137.6, 131.7, 129.3, 123.8, 116.3, 38.6, 34.9, 34.2, HRMS (m/z) calcd for C42H62O [M+NH4]: , found: Preparation of 2,2'',4,4'',6,6''-hexa-tert-butyl-[1,1':3',1''-terphenyl]-2'-thiol (HTBTSH). TTBP I TTBP 1. Li-t-Bu, ether 2. sulfur, RT, 16 h TTBP SH TTBP 3. LiAlH 4 RT, 24 h A solution of HTBTI (210 mg, 0.30 mmol, 1 eq.) in 20 ml of diethyl ether was frozen by liquid nitrogen. A solution of Li-t-Bu (0.5 ml, 1.7 M in pentane, mmol, 2.8 eq.) was added and the resulting mixture was placed into CO2/acetone bath and was stirred at 78 C for 2 hours. During this time reaction mixture melts and white precipitate forms. Elemental sulfur (39 mg, 1.21 mmol, 4 eq.) was added and the reaction mixture was stirred at room temperature overnight. LiAlH4 (115 mg, 3.0 mmol, 10 eq.) was added to the resulting suspension at 78 C and the reaction mixture stirred for additional 24 hours at room temperature. The resulting grey suspension was quenched with 3 ml of water at 78 C and stirred at room temperature for 10 minutes, aqueous HCl (1.0 M) was added to ph<2, and product was extracted by ether (3 x 10 ml). Organic solutions were combined and dried with Na2SO4. The mixture was filtered and the solvent was removed from the filtrate in vacuo. The product was purified by flesh chromatography (hexane). HTBTSH (160 mg, 88%) was obtained as white powder that could be recrystallized from ethanol. 1 H NMR (400 MHz; CD2Cl2): δ 7.55 (s, 4H), 7.43 (d, J = 7.7 Hz, 2H), 7.02 (t, J = 7.7 Hz, 1H), 2.70 (s, 1H), 1.35 (s, 18H), 1.23 (s, 36H). 13 C NMR (151 MHz; CD2Cl2): δ , , 140.8, 4

5 139.0, 136.2, 135.6, 124.7, 120.0, 39.1, 35.08, 34.91, HRMS (m/z) calcd for C42H62S [M+Na]: , found: Preparation of 2'-azido-2,2'',4,4'',6,6''-hexa-tert-butyl-1,1':3',1''-terphenyl (HTBTN3). I TTBP TTBP 1. Li-t-Bu, ether TTBP 2. TsN 3, RT, 16 h N 3 TTBP A solution of HTBTI (300 mg, 0.43 mmol, 1 eq.) in 30 ml of diethyl ether was frozen by liquid nitrogen. A solution of Li-t-Bu (0.715 ml, 1.7 M in pentane, 1.21 mmol, 2.8 eq.) was added and the resulting mixture was placed into CO2/acetone bath and was stirred at 78 C for 2 hours. During this time reaction mixture melts and white precipitate forms. Tosyl azide (0.2 ml, 256 mg, 1.30 mmol, 3 eq.) was added and the reaction mixture was stirred at room temperature overnight. The resulting solution was quenched with 3 ml of water and product was extracted by hexane (3 x 20 ml). Organic solutions were combined and dried with Na2SO4. The mixture was filtered and the solvent was removed from the filtrate in vacuo. The product was purified by flesh chromatography (hexane). HTBTN3 (240 mg, 91%) was obtained as white powder that could be recrystallized from mixture of ethanol and ethyl acetate (1:1 by volume). 1 H NMR (400 MHz; CD2Cl2): δ 7.56 (s, 4H), 7.40 (d, J = 7.7 Hz, 2H), 7.02 (t, J = 7.7 Hz, 1H), 1.38 (s, 18H), 1.29 (s, 36H). 13 C NMR (101 MHz; CD2Cl2): δ , , 140.2, 138.2, 135.9, 133.7, 123.7, 120.0, 39.0, 35.2, 34.7, HRMS (m/z) calcd for C42H61N3 [M+Na]: , found: Preparation of 2,2'',4,4'',6,6''-hexa-tert-butyl-[1,1':3',1''-terphenyl]-2'-amine (HTBTNH2). TTBP N 3 NH 2 TTBP LiAlH 4 TTBP TTBP ether, RT, 16h A solution of HTBTN3 (200 mg, 0.33 mmol, 1 eq.) in 5 ml of ether was added to a suspension of LiAlH4 (62 mg, 1.64 mmol, 5 eq.) in 5 ml of ether. The resulting suspension was stirred at room temperature overnight. The resulting grey suspension was quenched with 3 ml of water at 78 C and stirred at room temperature for 10 minutes, aqueous 5

6 NaOH (1.0 M) was added to ph>12, and product was extracted by ether (3 x 10 ml). Organic solutions were combined and dried with Na2SO4. The mixture was filtered and the solvent was removed from the filtrate in vacuo. The product was purified by flesh chromatography (hexane). HTBTNH2 (180 mg, 94%) was obtained as white powder that could be recrystallized from ethanol. 1 H NMR (600 MHz; CD2Cl2): δ 7.55 (s, 4H), 7.15 (d, J = 7.6 Hz, 2H), 6.64 (t, J = 7.6 Hz, 1H), 3.21 (s, 2H), 1.33 (s, 18H), 1.24 (s, 36H). 13 C NMR (151 MHz; CD2Cl2): δ 149.9, 148.6, 145.5, 136.8, 133.8, 128.0, 124.3, 113.6, 39.0, 35.1, 34.7, HRMS (m/z) calcd for C42H63N [M+H]: , found: Preparation of W(OHTBT)2Cl4 WCl TTBP OLi TTBP toluene RT, 16 h TTBP Cl Cl TTBP O W O Cl Cl TTBP TTBP HTBTOH (500 mg, 0.86 mmol, 1.00 eq.) was dissolved in 10 ml of pentane. Li-n-Bu (0.36 ml, 2.5 M in hexane, 1.05 eq.) was added and the resulting suspension was stirred for 30 minutes at room temperature. The product was filtered off, washed with pentane, and dried in vacuo. HTBTOLi (410 mg, 81%) was obtained as white powder. HTBTOLi is not soluble in pentane, ether, benzene and toluene, and was used without further purification. WCl6 (135 mg, 0.34 mmol, 1.00 eq.) and HTBTOLi (410 mg, 0.70, 2.05 eq.) were mixed as a solids and 10 ml of toluene was added. The resulting black mixture was stirred at room temperature overnight. Reaction mixture was filtered through celite and toluene was removed in vacuo. The residue was dissolved in minimum amount of pentane (~ 15 ml) at room temperature. The solution was kept in the freezer at 18 C overnight to get black crystals of W(OHTBT)2Cl4 (216 mg, 43%). Crystals suitable for X-ray data collection was obtained by slow evaporation of benzene of saturated solution of W(OHTBT)2Cl4 in benzene at room temperature: 1 H NMR (600 MHz; CDCl3): δ 7.53 (d, J = 7.6 Hz, 4H), 7.37 (s, 8H), 6.71 (t, J = 7.7 Hz, 2H), 1.25 (s, 36H), 1.15 (s, 72H); 13 C NMR (151 MHz; CDCl3): δ 163.1, 149.9, 148.5, 140.4, 136.8, 131.5, 124.1, 122.8, 38.9, 35.7, 34.7, Anal. Calcd for C84H122Cl4O2W: C, 67.73; H, Found: C, 67.32; H,

7 NMR spectra Figure 1. 1 H NMR of HTBTI in CD 2Cl 2. Figure C NMR of HTBTI in CD 2Cl 2. 7

8 Figure 3. 1 H NMR of HTBTLi in C 6D 6. Figure C NMR of HTBTLi in C 6D 6. 8

9 Figure 5. 1 H NMR of HTBTOH in CD 2Cl 2. Figure C NMR of HTBTOH in CD 2Cl 2. 9

10 Figure 7. 1 H NMR of HTBTSH in CD 2Cl 2. Figure C NMR of HTBTSH in CD 2Cl 2. 10

11 Figure 9. 1 H NMR of HTBTN 3 in CD 2Cl 2. Figure C NMR of HTBTN 3 in CD 2Cl 2. 11

12 Figure H NMR of HTBTNH 2 in CD 2Cl 2. Figure C NMR of HTBTNH 2 in CD 2Cl 2. 12

13 Figure H NMR of W(OHTBT) 2Cl 4 in CDCl 3. Figure C NMR of W(OHTBT) 2Cl 4 in CDCl 3. 13

14 X-ray crystal structure data Crystal data and structure refinement for Li(Et 2 O) 2 HTBT Low-temperature diffraction data (100K) for Li(Et2O)2HTBT were Bruker-AXS X8 Kappa Duo diffractometer coupled to a Smart APEX2 CCD detector with Mo Kα radiation (λ = Å) from an IμS micro-source, performing φ- and ω-scans. Absorption correction and scaling was performed with the program SADABS. 2 The structure was solved by direct methods using SHELXT 3 and refined against F 2 on all data by full-matrix least squares with SHELXL(2015). 4,5 All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were included into the model at geometrically calculated positions and refined using a riding model. The isotropic displacement parameters of all hydrogen atoms were fixed to 1.2 times the U value of the atoms they are linked to (1.5 times for methyl groups). 2 Krause, L.; Herbst-Irmer, R.; Sheldrick, G. M.; Stalke, D. J. Appl. Cryst., 2015, 48, Sheldrick, G. M. Acta Crystallogr. A, 2015, 71, Sheldrick, G. M. Acta Crystallogr. C, 2015, 71, Müller, P. Crystallography Reviews, 2009, 15,

15 Identification code X17076 Empirical formula C50 H81 Li O2 Formula weight Temperature 100(2) K Wavelength Å Crystal system Monoclinic Space group P2 1 /n Unit cell dimensions a = (16) Å a= 90 b = (4) Å b= (3) c = (3) Å g = 90 Volume (13) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1600 Crystal size x x mm 3 Theta range for data collection to Index ranges -13<=h<=13, -35<=k<=35, -25<=l<=25 Reflections collected Independent reflections [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / 0 / 500 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 15

16 Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for X U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) C(1) 4027(2) 7169(1) 6643(1) 18(1) C(2) 3873(2) 7713(1) 6746(1) 18(1) C(3) 2708(2) 7930(1) 7031(1) 22(1) C(4) 1597(2) 7625(1) 7177(1) 22(1) C(5) 1673(2) 7094(1) 7065(1) 22(1) C(6) 2873(2) 6870(1) 6830(1) 19(1) C(11) 4902(2) 8119(1) 6531(1) 19(1) C(12) 6098(2) 8253(1) 6986(1) 21(1) C(13) 6891(2) 8674(1) 6798(1) 23(1) C(14) 6562(2) 8990(1) 6200(1) 23(1) C(15) 5424(2) 8854(1) 5764(1) 22(1) C(16) 4594(2) 8424(1) 5897(1) 20(1) C(17) 6590(2) 7960(1) 7692(1) 24(1) C(18) 5490(2) 7971(1) 8249(1) 28(1) C(19) 7873(2) 8203(1) 8079(1) 32(1) C(20) 6999(2) 7402(1) 7516(1) 27(1) C(21) 7463(2) 9460(1) 6057(1) 27(1) C(22) 8900(2) 9276(1) 5889(1) 34(1) C(23) 6882(2) 9787(1) 5417(1) 41(1) C(24) 7573(3) 9806(1) 6735(1) 44(1) C(25) 3367(2) 8356(1) 5324(1) 22(1) C(26) 3787(2) 8497(1) 4556(1) 34(1) C(27) 2761(2) 7813(1) 5248(1) 31(1) C(28) 2221(2) 8733(1) 5512(1) 35(1) C(31) 2842(2) 6280(1) 6834(1) 18(1) C(32) 3026(2) 6014(1) 7513(1) 20(1) C(33) 2807(2) 5479(1) 7529(1) 24(1) C(34) 2469(2) 5180(1) 6919(1) 23(1) C(35) 2343(2) 5442(1) 6262(1) 22(1) C(36) 2505(2) 5977(1) 6196(1) 19(1) C(37) 3392(2) 6247(1) 8281(1) 24(1) 16

17 C(38) 4421(3) 5894(1) 8706(1) 41(1) C(39) 4034(3) 6785(1) 8314(1) 36(1) C(40) 2070(2) 6269(1) 8692(1) 38(1) C(41) 2262(2) 4595(1) 6989(1) 29(1) C(42) 3605(2) 4347(1) 7300(1) 40(1) C(43) 1882(3) 4336(1) 6257(1) 44(1) C(44) 1126(3) 4491(1) 7495(2) 45(1) C(45) 2314(2) 6200(1) 5416(1) 22(1) C(46) 3676(2) 6417(1) 5187(1) 25(1) C(47) 1880(2) 5783(1) 4847(1) 34(1) C(48) 1193(2) 6613(1) 5352(1) 26(1) Li(1) 5846(3) 6864(1) 6227(2) 26(1) O(1) 6921(1) 7139(1) 5444(1) 25(1) C(51) 7416(2) 7663(1) 5398(1) 26(1) C(52) 8948(2) 7700(1) 5434(1) 36(1) C(53) 7159(2) 6822(1) 4824(1) 27(1) C(54) 6435(2) 7016(1) 4127(1) 38(1) O(2) 6826(1) 6214(1) 6481(1) 26(1) C(55) 8295(2) 6184(1) 6511(1) 32(1) C(56) 8947(3) 6007(1) 7229(2) 50(1) C(57) 6150(2) 5737(1) 6634(1) 30(1) C(58) 6429(3) 5308(1) 6107(2) 47(1) 17

18 Bond lengths [Å] and angles [ ] for X C(1)-C(2) 1.430(2) C(1)-C(6) 1.431(2) C(1)-Li(1) 2.137(4) C(2)-C(3) 1.406(2) C(2)-C(11) 1.525(2) C(3)-C(4) 1.385(3) C(3)-H(3) C(4)-C(5) 1.392(2) C(4)-H(4) C(5)-C(6) 1.405(2) C(5)-H(5) C(6)-C(31) 1.526(2) C(11)-C(16) 1.429(2) C(11)-C(12) 1.439(2) C(12)-C(13) 1.396(2) C(12)-C(17) 1.558(2) C(13)-C(14) 1.395(2) C(13)-H(13) C(14)-C(15) 1.377(2) C(14)-C(21) 1.536(2) C(15)-C(16) 1.409(2) C(15)-H(15) C(16)-C(25) 1.559(2) C(17)-C(18) 1.538(3) C(17)-C(20) 1.539(2) C(17)-C(19) 1.540(3) C(18)-H(18A) C(18)-H(18B) C(18)-H(18C) C(19)-H(19A) C(19)-H(19B) C(19)-H(19C) C(20)-H(20A) C(20)-H(20B)

19 C(20)-H(20C) C(21)-C(23) 1.533(3) C(21)-C(24) 1.537(3) C(21)-C(22) 1.538(3) C(22)-H(22A) C(22)-H(22B) C(22)-H(22C) C(23)-H(23A) C(23)-H(23B) C(23)-H(23C) C(24)-H(24A) C(24)-H(24B) C(24)-H(24C) C(25)-C(27) 1.530(2) C(25)-C(28) 1.544(3) C(25)-C(26) 1.546(3) C(26)-H(26A) C(26)-H(26B) C(26)-H(26C) C(27)-H(27A) C(27)-H(27B) C(27)-H(27C) C(28)-H(28A) C(28)-H(28B) C(28)-H(28C) C(31)-C(32) 1.432(2) C(31)-C(36) 1.435(2) C(32)-C(33) 1.402(2) C(32)-C(37) 1.561(2) C(33)-C(34) 1.389(2) C(33)-H(33) C(34)-C(35) 1.388(2) C(34)-C(41) 1.536(2) C(35)-C(36) 1.401(2) C(35)-H(35) C(36)-C(45) 1.554(2) 19

20 C(37)-C(39) 1.527(3) C(37)-C(38) 1.537(3) C(37)-C(40) 1.545(3) C(38)-H(38A) C(38)-H(38B) C(38)-H(38C) C(39)-H(39A) C(39)-H(39B) C(39)-H(39C) C(40)-H(40A) C(40)-H(40B) C(40)-H(40C) C(41)-C(44) 1.524(3) C(41)-C(43) 1.533(3) C(41)-C(42) 1.541(3) C(42)-H(42A) C(42)-H(42B) C(42)-H(42C) C(43)-H(43A) C(43)-H(43B) C(43)-H(43C) C(44)-H(44A) C(44)-H(44B) C(44)-H(44C) C(45)-C(48) 1.531(3) C(45)-C(46) 1.532(3) C(45)-C(47) 1.546(2) C(46)-H(46A) C(46)-H(46B) C(46)-H(46C) C(47)-H(47A) C(47)-H(47B) C(47)-H(47C) C(48)-H(48A) C(48)-H(48B) C(48)-H(48C)

21 Li(1)-O(1) 1.977(3) Li(1)-O(2) 1.978(3) O(1)-C(53) 1.441(2) O(1)-C(51) 1.445(2) C(51)-C(52) 1.502(3) C(51)-H(51A) C(51)-H(51B) C(52)-H(52A) C(52)-H(52B) C(52)-H(52C) C(53)-C(54) 1.515(3) C(53)-H(53A) C(53)-H(53B) C(54)-H(54A) C(54)-H(54B) C(54)-H(54C) O(2)-C(57) 1.438(2) O(2)-C(55) 1.439(2) C(55)-C(56) 1.506(3) C(55)-H(55A) C(55)-H(55B) C(56)-H(56A) C(56)-H(56B) C(56)-H(56C) C(57)-C(58) 1.512(3) C(57)-H(57A) C(57)-H(57B) C(58)-H(58A) C(58)-H(58B) C(58)-H(58C) C(2)-C(1)-C(6) (15) C(2)-C(1)-Li(1) (15) C(6)-C(1)-Li(1) (14) C(3)-C(2)-C(1) (15) C(3)-C(2)-C(11) (14) 21

22 C(1)-C(2)-C(11) (15) C(4)-C(3)-C(2) (15) C(4)-C(3)-H(3) C(2)-C(3)-H(3) C(3)-C(4)-C(5) (16) C(3)-C(4)-H(4) C(5)-C(4)-H(4) C(4)-C(5)-C(6) (16) C(4)-C(5)-H(5) C(6)-C(5)-H(5) C(5)-C(6)-C(1) (15) C(5)-C(6)-C(31) (15) C(1)-C(6)-C(31) (15) C(16)-C(11)-C(12) (15) C(16)-C(11)-C(2) (15) C(12)-C(11)-C(2) (14) C(13)-C(12)-C(11) (15) C(13)-C(12)-C(17) (15) C(11)-C(12)-C(17) (15) C(14)-C(13)-C(12) (16) C(14)-C(13)-H(13) C(12)-C(13)-H(13) C(15)-C(14)-C(13) (16) C(15)-C(14)-C(21) (16) C(13)-C(14)-C(21) (16) C(14)-C(15)-C(16) (16) C(14)-C(15)-H(15) C(16)-C(15)-H(15) C(15)-C(16)-C(11) (16) C(15)-C(16)-C(25) (14) C(11)-C(16)-C(25) (15) C(18)-C(17)-C(20) (15) C(18)-C(17)-C(19) (15) C(20)-C(17)-C(19) (15) C(18)-C(17)-C(12) (15) C(20)-C(17)-C(12) (13) 22

23 C(19)-C(17)-C(12) (15) C(17)-C(18)-H(18A) C(17)-C(18)-H(18B) H(18A)-C(18)-H(18B) C(17)-C(18)-H(18C) H(18A)-C(18)-H(18C) H(18B)-C(18)-H(18C) C(17)-C(19)-H(19A) C(17)-C(19)-H(19B) H(19A)-C(19)-H(19B) C(17)-C(19)-H(19C) H(19A)-C(19)-H(19C) H(19B)-C(19)-H(19C) C(17)-C(20)-H(20A) C(17)-C(20)-H(20B) H(20A)-C(20)-H(20B) C(17)-C(20)-H(20C) H(20A)-C(20)-H(20C) H(20B)-C(20)-H(20C) C(23)-C(21)-C(14) (16) C(23)-C(21)-C(24) (18) C(14)-C(21)-C(24) (16) C(23)-C(21)-C(22) (18) C(14)-C(21)-C(22) (15) C(24)-C(21)-C(22) (18) C(21)-C(22)-H(22A) C(21)-C(22)-H(22B) H(22A)-C(22)-H(22B) C(21)-C(22)-H(22C) H(22A)-C(22)-H(22C) H(22B)-C(22)-H(22C) C(21)-C(23)-H(23A) C(21)-C(23)-H(23B) H(23A)-C(23)-H(23B) C(21)-C(23)-H(23C) H(23A)-C(23)-H(23C)

24 H(23B)-C(23)-H(23C) C(21)-C(24)-H(24A) C(21)-C(24)-H(24B) H(24A)-C(24)-H(24B) C(21)-C(24)-H(24C) H(24A)-C(24)-H(24C) H(24B)-C(24)-H(24C) C(27)-C(25)-C(28) (16) C(27)-C(25)-C(26) (15) C(28)-C(25)-C(26) (16) C(27)-C(25)-C(16) (14) C(28)-C(25)-C(16) (15) C(26)-C(25)-C(16) (15) C(25)-C(26)-H(26A) C(25)-C(26)-H(26B) H(26A)-C(26)-H(26B) C(25)-C(26)-H(26C) H(26A)-C(26)-H(26C) H(26B)-C(26)-H(26C) C(25)-C(27)-H(27A) C(25)-C(27)-H(27B) H(27A)-C(27)-H(27B) C(25)-C(27)-H(27C) H(27A)-C(27)-H(27C) H(27B)-C(27)-H(27C) C(25)-C(28)-H(28A) C(25)-C(28)-H(28B) H(28A)-C(28)-H(28B) C(25)-C(28)-H(28C) H(28A)-C(28)-H(28C) H(28B)-C(28)-H(28C) C(32)-C(31)-C(36) (14) C(32)-C(31)-C(6) (14) C(36)-C(31)-C(6) (14) C(33)-C(32)-C(31) (15) C(33)-C(32)-C(37) (14) 24

25 C(31)-C(32)-C(37) (14) C(34)-C(33)-C(32) (15) C(34)-C(33)-H(33) C(32)-C(33)-H(33) C(35)-C(34)-C(33) (15) C(35)-C(34)-C(41) (16) C(33)-C(34)-C(41) (15) C(34)-C(35)-C(36) (16) C(34)-C(35)-H(35) C(36)-C(35)-H(35) C(35)-C(36)-C(31) (14) C(35)-C(36)-C(45) (14) C(31)-C(36)-C(45) (14) C(39)-C(37)-C(38) (17) C(39)-C(37)-C(40) (17) C(38)-C(37)-C(40) (17) C(39)-C(37)-C(32) (14) C(38)-C(37)-C(32) (15) C(40)-C(37)-C(32) (16) C(37)-C(38)-H(38A) C(37)-C(38)-H(38B) H(38A)-C(38)-H(38B) C(37)-C(38)-H(38C) H(38A)-C(38)-H(38C) H(38B)-C(38)-H(38C) C(37)-C(39)-H(39A) C(37)-C(39)-H(39B) H(39A)-C(39)-H(39B) C(37)-C(39)-H(39C) H(39A)-C(39)-H(39C) H(39B)-C(39)-H(39C) C(37)-C(40)-H(40A) C(37)-C(40)-H(40B) H(40A)-C(40)-H(40B) C(37)-C(40)-H(40C) H(40A)-C(40)-H(40C)

26 H(40B)-C(40)-H(40C) C(44)-C(41)-C(43) (19) C(44)-C(41)-C(34) (16) C(43)-C(41)-C(34) (16) C(44)-C(41)-C(42) (18) C(43)-C(41)-C(42) (18) C(34)-C(41)-C(42) (16) C(41)-C(42)-H(42A) C(41)-C(42)-H(42B) H(42A)-C(42)-H(42B) C(41)-C(42)-H(42C) H(42A)-C(42)-H(42C) H(42B)-C(42)-H(42C) C(41)-C(43)-H(43A) C(41)-C(43)-H(43B) H(43A)-C(43)-H(43B) C(41)-C(43)-H(43C) H(43A)-C(43)-H(43C) H(43B)-C(43)-H(43C) C(41)-C(44)-H(44A) C(41)-C(44)-H(44B) H(44A)-C(44)-H(44B) C(41)-C(44)-H(44C) H(44A)-C(44)-H(44C) H(44B)-C(44)-H(44C) C(48)-C(45)-C(46) (14) C(48)-C(45)-C(47) (15) C(46)-C(45)-C(47) (15) C(48)-C(45)-C(36) (14) C(46)-C(45)-C(36) (14) C(47)-C(45)-C(36) (14) C(45)-C(46)-H(46A) C(45)-C(46)-H(46B) H(46A)-C(46)-H(46B) C(45)-C(46)-H(46C) H(46A)-C(46)-H(46C)

27 H(46B)-C(46)-H(46C) C(45)-C(47)-H(47A) C(45)-C(47)-H(47B) H(47A)-C(47)-H(47B) C(45)-C(47)-H(47C) H(47A)-C(47)-H(47C) H(47B)-C(47)-H(47C) C(45)-C(48)-H(48A) C(45)-C(48)-H(48B) H(48A)-C(48)-H(48B) C(45)-C(48)-H(48C) H(48A)-C(48)-H(48C) H(48B)-C(48)-H(48C) O(1)-Li(1)-O(2) (15) O(1)-Li(1)-C(1) (16) O(2)-Li(1)-C(1) (17) C(53)-O(1)-C(51) (14) C(53)-O(1)-Li(1) (14) C(51)-O(1)-Li(1) (14) O(1)-C(51)-C(52) (15) O(1)-C(51)-H(51A) C(52)-C(51)-H(51A) O(1)-C(51)-H(51B) C(52)-C(51)-H(51B) H(51A)-C(51)-H(51B) C(51)-C(52)-H(52A) C(51)-C(52)-H(52B) H(52A)-C(52)-H(52B) C(51)-C(52)-H(52C) H(52A)-C(52)-H(52C) H(52B)-C(52)-H(52C) O(1)-C(53)-C(54) (16) O(1)-C(53)-H(53A) C(54)-C(53)-H(53A) O(1)-C(53)-H(53B) C(54)-C(53)-H(53B)

28 H(53A)-C(53)-H(53B) C(53)-C(54)-H(54A) C(53)-C(54)-H(54B) H(54A)-C(54)-H(54B) C(53)-C(54)-H(54C) H(54A)-C(54)-H(54C) H(54B)-C(54)-H(54C) C(57)-O(2)-C(55) (14) C(57)-O(2)-Li(1) (15) C(55)-O(2)-Li(1) (15) O(2)-C(55)-C(56) (18) O(2)-C(55)-H(55A) C(56)-C(55)-H(55A) O(2)-C(55)-H(55B) C(56)-C(55)-H(55B) H(55A)-C(55)-H(55B) C(55)-C(56)-H(56A) C(55)-C(56)-H(56B) H(56A)-C(56)-H(56B) C(55)-C(56)-H(56C) H(56A)-C(56)-H(56C) H(56B)-C(56)-H(56C) O(2)-C(57)-C(58) (17) O(2)-C(57)-H(57A) C(58)-C(57)-H(57A) O(2)-C(57)-H(57B) C(58)-C(57)-H(57B) H(57A)-C(57)-H(57B) C(57)-C(58)-H(58A) C(57)-C(58)-H(58B) H(58A)-C(58)-H(58B) C(57)-C(58)-H(58C) H(58A)-C(58)-H(58C) H(58B)-C(58)-H(58C) Symmetry transformations used to generate equivalent atom. 28

29 Anisotropic displacement parameters (Å 2 x 10 3 ) for X The anisotropic displacement factor exponent takes the form: -2p 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 C(1) 24(1) 20(1) 8(1) 0(1) -1(1) 0(1) C(2) 24(1) 21(1) 10(1) -1(1) -1(1) 1(1) C(3) 31(1) 20(1) 15(1) -3(1) 1(1) 2(1) C(4) 26(1) 24(1) 18(1) -1(1) 3(1) 4(1) C(5) 27(1) 22(1) 17(1) 0(1) 3(1) 0(1) C(6) 27(1) 20(1) 9(1) 0(1) 0(1) 2(1) C(11) 25(1) 18(1) 14(1) -3(1) 1(1) 2(1) C(12) 28(1) 22(1) 13(1) -4(1) 1(1) 2(1) C(13) 25(1) 26(1) 18(1) -5(1) 0(1) -2(1) C(14) 27(1) 22(1) 21(1) -4(1) 4(1) -1(1) C(15) 28(1) 21(1) 18(1) 0(1) 1(1) 1(1) C(16) 25(1) 20(1) 16(1) -1(1) 2(1) 0(1) C(17) 29(1) 27(1) 14(1) -3(1) -4(1) 1(1) C(18) 39(1) 31(1) 13(1) -2(1) 1(1) 2(1) C(19) 37(1) 37(1) 21(1) -4(1) -10(1) -2(1) C(20) 35(1) 28(1) 18(1) -2(1) -4(1) 5(1) C(21) 30(1) 24(1) 27(1) -4(1) 3(1) -6(1) C(22) 32(1) 38(1) 34(1) -3(1) 7(1) -6(1) C(23) 44(1) 29(1) 49(1) 9(1) -2(1) -11(1) C(24) 57(2) 32(1) 43(1) -16(1) 16(1) -20(1) C(25) 27(1) 22(1) 17(1) 3(1) -3(1) -2(1) C(26) 39(1) 46(1) 18(1) 4(1) -3(1) -13(1) C(27) 42(1) 27(1) 24(1) 3(1) -10(1) -7(1) C(28) 35(1) 37(1) 34(1) 1(1) -4(1) 8(1) C(31) 22(1) 20(1) 12(1) 1(1) 2(1) 1(1) C(32) 25(1) 22(1) 13(1) 1(1) 2(1) 0(1) C(33) 32(1) 24(1) 15(1) 5(1) 0(1) 0(1) C(34) 28(1) 21(1) 20(1) 2(1) -1(1) -2(1) C(35) 30(1) 21(1) 16(1) -1(1) -2(1) -2(1) C(36) 24(1) 20(1) 13(1) 1(1) 0(1) -1(1) C(37) 36(1) 25(1) 12(1) 1(1) 1(1) 1(1) 29

30 C(38) 58(2) 41(1) 21(1) -4(1) -12(1) 13(1) C(39) 59(1) 35(1) 15(1) -1(1) -4(1) -9(1) C(40) 45(1) 49(1) 21(1) -4(1) 10(1) 2(1) C(41) 40(1) 22(1) 26(1) 3(1) -1(1) -3(1) C(42) 43(1) 26(1) 50(1) 7(1) -4(1) 0(1) C(43) 66(2) 24(1) 40(1) -1(1) -5(1) -9(1) C(44) 51(1) 29(1) 57(2) 7(1) 19(1) -4(1) C(45) 30(1) 23(1) 11(1) 1(1) -2(1) -3(1) C(46) 31(1) 29(1) 14(1) 1(1) 4(1) 0(1) C(47) 56(1) 29(1) 14(1) 0(1) -5(1) -8(1) C(48) 29(1) 31(1) 18(1) 6(1) -2(1) 0(1) Li(1) 34(2) 27(2) 18(1) 2(1) 5(1) 4(1) O(1) 34(1) 25(1) 17(1) -1(1) 6(1) 0(1) C(51) 34(1) 22(1) 22(1) 1(1) 4(1) 3(1) C(52) 34(1) 30(1) 43(1) 2(1) 2(1) -1(1) C(53) 36(1) 30(1) 16(1) -3(1) 3(1) -1(1) C(54) 48(1) 45(1) 19(1) 1(1) -2(1) -1(1) O(2) 28(1) 24(1) 26(1) 4(1) 3(1) 3(1) C(55) 28(1) 27(1) 41(1) 8(1) 6(1) 2(1) C(56) 38(1) 45(1) 65(2) 27(1) -11(1) -7(1) C(57) 31(1) 29(1) 29(1) 6(1) 4(1) 1(1) C(58) 52(2) 30(1) 60(2) -8(1) 9(1) -2(1) 30

31 Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for X x y z U(eq) H(3) H(4) H(5) H(13) H(15) H(18A) H(18B) H(18C) H(19A) H(19B) H(19C) H(20A) H(20B) H(20C) H(22A) H(22B) H(22C) H(23A) H(23B) H(23C) H(24A) H(24B) H(24C) H(26A) H(26B) H(26C) H(27A) H(27B) H(27C) H(28A)

32 H(28B) H(28C) H(33) H(35) H(38A) H(38B) H(38C) H(39A) H(39B) H(39C) H(40A) H(40B) H(40C) H(42A) H(42B) H(42C) H(43A) H(43B) H(43C) H(44A) H(44B) H(44C) H(46A) H(46B) H(46C) H(47A) H(47B) H(47C) H(48A) H(48B) H(48C) H(51A) H(51B) H(52A) H(52B) H(52C)

33 H(53A) H(53B) H(54A) H(54B) H(54C) H(55A) H(55B) H(56A) H(56B) H(56C) H(57A) H(57B) H(58A) H(58B) H(58C)

34 Crystal data and structure refinement for W(OHTBT) 2 Cl 4 Diffraction data for W(OHTBT)2Cl4 were collected using φ- and ω-scans on a Bruker- AXS X8 Kappa Duo diffractometer coupled to a Smart APEX2 CCD detector with Mo Kα radiation (λ= Å) from an IμS micro-source at low temperature (100 K). The data were corrected for absorption with SADABS. [1] The structure was solved in the monoclinic space group C2/c by direct methods using SHELXT [2] and refined against F 2 on all data by full-matrix least squares with SHELXL(2015). [3,4] Considering the systematic absences, several space groups, including orthorhombic space groups, could be possible. However, refinement was only possible in the space group C2/c because the compound showed a whole molecule disorder with very badly defined atom positions, which could not be refined further in the other space groups. In C2/c the asymmetric unit contains 1.5 target molecules. The structure was refined as pseudo-merohedral twin with the twin law [ ]. The twin ratio converged to 0.484(1). Hydrogen atoms in the model were positioned at geometrically calculated positions and refined using a riding model. The isotropic displacement parameters of all hydrogen atoms were fixed to 1.2x (CH and CH2- groups) or 1.5x (CH3-groups) the Ueq value of the atoms they are linked to. The structure was refined with the help of similarity restraints on 1,2- and 1,3 distances, advanced rigid 34

35 bond (doubled strength), similar ADP (four times strength) restraints, restraints on their Uij components to approximate to isotropic behavior (double strength), and restraints for atoms on a common plane to this plane (normal or double strength). 6 Additional exact constraints on the ADP were used to constrain several atoms to the same displacement parameters. The first target molecule in the asymmetric unit was found to be disordered over two positions. The disorder ratio was refined freely and converged at (7). The position of the central tungsten atom (and to some extend that of the four coordinating chloride ions as well) is rather well-defined; however, the OHTBT ligands essentially form a sphere around the WCl4 core. The two refined positions of the ligand seem to be the most prominent ones but there is apparently a lot of movement in the ligand positions rotating around the tungsten-oxygen axis. A stable refinement model was only possible with the use of strong restraints. The second, half target molecule suffers from very similar problems. The whole molecule disorder was also modeled over two positions with a disorder ratio refining to (8). This molecule was refined as half occupied molecule in a negative part because of its proximity to a symmetry center to avoid unreasonable bond distances and angles to symmetry equivalents. Space fill plot of part 1 of one molecule. The sphere formed by the ligand around the central core is clearly visible. This makes a well ordered crystal packing difficult. 6 Thorn, A.; Dittrich, B.; Sheldrick, G. M. Acta Crystallogr. A, 2012, 68,

36 In order to achieve convergence of the refinement the DAMP instruction was used for multiplying the diagonal elements of the least-squares matrix with 11 (DAMP 10000) before inversion. In the final model there is a minor collision between two ligand models. This collision is caused by the poorly defined positions of the ligands and could not be avoided to obtain a stable refinement model. The ligand positions are not completely defined anyway owing to the movement of the ligand itself. An additional issue of the structure is the challenging absorption correction. This challenge is caused by the high absorption of the compound as well as the unfortunate crystal shape (plate). The problems are reflected in the final R1 (I > 2sigma(I) ) of 17.07% and a high remaining difference electron density. Thus the meaning of bond lengths and angles remain limited. Identification code X17061 Empirical formula C 126 H 183 Cl 6 O 3 W 1.50 Formula weight Temperature 100(2) K Wavelength Å Crystal system Monoclinic Space group C2/c Unit cell dimensions a = (4) Å α = 90 b = (14) Å β = 90 c = (4) Å γ = 90 Volume 24584(9) Å 3 Z 8 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 9408 Crystal size x x mm 3 Theta range for data collection to Index ranges -26<=h<=26, -87<=k<=87, -25<=l<=25 Reflections collected Independent reflections [R(int) = ] Completeness to theta = % 36

37 Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / / 2242 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 37

38 Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for X U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) W(1) 2494(1) 5766(1) 146(1) 43(1) Cl(1) 3614(1) 5721(1) 33(1) 49(1) Cl(2) 2335(1) 5422(1) -15(1) 49(1) Cl(3) 1341(1) 5752(1) 150(1) 49(1) Cl(4) 2408(1) 6115(1) 268(1) 49(1) W(1A) 2522(1) 5772(1) 135(1) 43(1) Cl(1A) 3688(1) 5773(1) 260(1) 49(1) Cl(2A) 2617(1) 5427(1) 114(1) 49(1) Cl(3A) 1366(1) 5809(1) 303(1) 49(1) Cl(4A) 2618(1) 6128(1) 70(1) 49(1) O(1) 2421(3) 5782(1) -854(2) 43(1) C(1) 2326(2) 5779(1) -1593(2) 47(1) C(2) 1816(2) 5721(1) -1957(2) 50(1) C(3) 1743(2) 5697(1) -2559(2) 51(1) C(4) 2327(2) 5738(1) -3046(2) 51(1) C(5) 2945(2) 5815(1) -2742(2) 50(1) C(6) 2970(2) 5830(1) -1992(2) 49(1) C(11) 1115(2) 5676(1) -1570(2) 52(1) C(12) 647(1) 5816(1) -1344(1) 52(1) C(13) 106(2) 5781(1) -949(2) 52(1) C(14) -28(2) 5568(1) -727(2) 52(1) C(15) 428(2) 5426(1) -923(3) 52(1) C(16) 1009(2) 5460(1) -1328(2) 52(1) C(31) 3669(1) 5893(1) -1636(1) 54(1) C(32) 4192(1) 5766(1) -1445(1) 54(1) C(33) 4727(1) 5804(1) -1068(1) 56(1) C(34) 4740(2) 6038(1) -810(2) 54(1) C(35) 4287(2) 6151(1) -965(3) 54(1) C(36) 3684(2) 6102(1) -1365(2) 54(1) C(17) 581(2) 6045(1) -1506(2) 52(1) C(18) 995(3) 6179(1) -1000(3) 58(1) 38

39 C(19) -131(2) 6127(1) -1344(4) 63(1) C(20) 699(4) 6099(1) -2289(2) 62(1) C(21) -602(2) 5530(1) -194(2) 58(1) C(22) -621(4) 5301(1) 29(4) 59(1) C(23) -1305(2) 5577(1) -460(4) 70(1) C(24) -489(4) 5650(1) 511(2) 63(1) C(25) 1318(2) 5256(1) -1595(2) 54(1) C(26) 1230(4) 5076(1) -1078(3) 56(1) C(27) 2065(2) 5257(1) -1735(4) 56(1) C(28) 912(3) 5192(1) -2270(2) 56(1) C(37) 4215(2) 5539(1) -1686(2) 51(1) C(38) 4731(2) 5408(1) -1286(3) 52(1) C(39) 3562(2) 5422(1) -1624(4) 52(1) C(40) 4434(3) 5536(1) -2480(2) 52(1) C(41) 5310(2) 6114(1) -342(2) 68(1) C(42) 5175(4) 6334(1) -85(4) 75(1) C(43) 5970(2) 6128(1) -750(3) 82(2) C(44) 5392(4) 5973(1) 314(2) 65(1) C(45) 3241(2) 6289(1) -1577(2) 67(1) C(46) 3461(4) 6344(1) -2351(2) 74(1) C(47) 2496(2) 6258(1) -1634(4) 73(1) C(48) 3380(4) 6485(1) -1136(3) 72(1) O(1A) 2619(3) 5807(1) -777(2) 43(1) C(1A) 2556(2) 5799(1) -1525(2) 46(1) C(2A) 2077(1) 5840(1) -1959(2) 50(1) C(3A) 1994(2) 5846(1) -2564(2) 50(1) C(4A) 2595(2) 5797(1) -3016(2) 52(1) C(5A) 3207(2) 5747(1) -2656(2) 50(1) C(6A) 3212(2) 5748(1) -1898(2) 50(1) C(11A) 1358(2) 5900(1) -1634(2) 53(1) C(12A) 1177(2) 6098(1) -1488(2) 56(1) C(13A) 650(2) 6160(1) -1117(2) 55(1) C(14A) 202(2) 6000(1) -822(2) 53(1) C(15A) 305(2) 5808(1) -1072(3) 53(1) C(16A) 884(2) 5739(1) -1402(3) 53(1) C(31A) 3881(2) 5661(1) -1540(2) 54(1) 39

40 C(32A) 4026(2) 5459(1) -1408(1) 54(1) C(33A) 4517(2) 5387(1) -1021(2) 54(1) C(34A) 4967(2) 5562(1) -654(2) 58(1) C(35A) 4870(2) 5737(1) -837(3) 56(1) C(36A) 4309(2) 5821(1) -1251(3) 56(1) C(17A) 1575(2) 6280(1) -1780(2) 62(1) C(18A) 1908(3) 6409(1) -1190(2) 62(1) C(19A) 1167(3) 6429(1) -2224(3) 68(1) C(20A) 2167(2) 6213(1) -2275(3) 69(1) C(21A) -397(2) 6037(1) -325(2) 51(1) C(22A) -428(4) 5877(1) 283(2) 54(1) C(23A) -1072(2) 6011(1) -692(3) 49(1) C(24A) -385(4) 6250(1) 43(3) 53(1) C(25A) 855(2) 5512(1) -1643(2) 54(1) C(26A) 1465(2) 5390(1) -1386(4) 56(1) C(27A) 837(5) 5492(1) -2445(2) 56(1) C(28A) 238(2) 5404(1) -1313(3) 56(1) C(37A) 3687(2) 5266(1) -1730(2) 51(1) C(38A) 3805(4) 5070(1) -1290(3) 52(1) C(39A) 4015(3) 5210(1) -2437(2) 52(1) C(40A) 2923(2) 5283(1) -1846(4) 52(1) C(41A) 5572(2) 5489(1) -221(2) 63(1) C(42A) 6232(2) 5569(1) -547(4) 65(1) C(43A) 5653(5) 5257(1) -193(5) 63(2) C(44A) 5541(5) 5564(1) 558(2) 65(2) C(45A) 4266(2) 6057(1) -1286(2) 59(1) C(46A) 4763(3) 6155(1) -753(3) 65(1) C(47A) 4476(4) 6137(1) -2011(2) 67(1) C(48A) 3579(2) 6153(1) -1099(4) 62(1) O(2) 2515(3) 5748(1) 1105(2) 43(1) C(51) 2644(1) 5715(1) 1828(2) 52(1) C(52) 2832(1) 5553(1) 2171(2) 57(1) C(53) 2938(1) 5510(1) 2751(2) 59(1) C(54) 2840(4) 5679(1) 3286(2) 62(1) C(55) 2647(4) 5878(1) 3037(2) 61(1) C(56) 2541(3) 5902(1) 2291(2) 59(1) 40

41 C(61) 2974(2) 5350(1) 1714(2) 58(1) C(62) 3585(1) 5313(1) 1396(1) 58(1) C(63) 3709(2) 5159(1) 956(2) 56(1) C(64) 3172(2) 5012(1) 794(2) 54(1) C(65) 2566(2) 5039(1) 1131(2) 56(1) C(66) 2424(2) 5201(1) 1585(2) 58(1) C(81) 2287(2) 6124(1) 2064(1) 63(1) C(82) 2653(2) 6283(1) 1797(1) 62(1) C(83) 2438(2) 6448(1) 1485(2) 65(1) C(84) 1629(2) 6454(1) 1422(3) 67(1) C(85) 1305(2) 6311(1) 1651(3) 67(1) C(86) 1555(2) 6126(1) 1997(3) 67(1) C(67) 4270(2) 5407(1) 1591(2) 61(1) C(68) 4235(4) 5635(1) 1799(4) 53(1) C(69) 4583(3) 5303(1) 2239(2) 63(1) C(70) 4789(2) 5396(1) 973(2) 65(1) C(71) 3280(2) 4836(1) 267(2) 58(1) C(72) 2755(2) 4838(1) -333(2) 63(1) C(73) 3203(4) 4625(1) 608(3) 59(1) C(74) 3986(2) 4840(1) -84(3) 63(1) C(75) 1691(2) 5213(1) 1871(2) 62(1) C(76) 1570(4) 5359(1) 2500(2) 63(1) C(77) 1431(3) 5006(1) 2112(4) 63(1) C(78) 1230(3) 5301(1) 1273(2) 63(1) C(87) 3428(2) 6301(1) 1862(2) 62(1) C(88) 3627(4) 6379(1) 2606(2) 62(1) C(89) 3812(3) 6102(1) 1775(4) 62(1) C(90) 3740(3) 6456(1) 1327(2) 62(1) C(91) 1342(2) 6647(1) 1083(2) 75(1) C(92) 1502(4) 6646(1) 282(2) 76(2) C(93) 1627(3) 6849(1) 1355(4) 84(1) C(94) 567(2) 6659(1) 1154(5) 82(2) C(95) 1053(2) 5975(1) 2351(2) 72(1) C(96) 1388(3) 5781(1) 2658(4) 80(1) C(97) 775(3) 6077(1) 3017(2) 76(1) C(98) 489(2) 5901(1) 1860(3) 75(1) 41

42 O(2A) 2536(4) 5750(1) 1083(2) 43(1) C(51A) 2513(1) 5749(1) 1824(2) 52(1) C(52A) 2385(1) 5616(1) 2294(2) 58(1) C(53A) 2303(1) 5580(1) 2876(2) 60(1) C(54A) 2411(5) 5774(1) 3313(2) 60(1) C(55A) 2535(5) 5962(1) 2938(2) 60(1) C(56A) 2586(3) 5960(1) 2181(2) 58(1) C(61A) 2183(2) 5395(1) 1935(1) 60(1) C(62A) 2597(1) 5243(1) 1692(1) 59(1) C(63A) 2482(2) 5085(1) 1280(1) 59(1) C(64A) 1779(2) 5064(1) 1031(2) 59(1) C(65A) 1342(2) 5212(1) 1222(3) 60(1) C(66A) 1483(2) 5382(1) 1643(2) 60(1) C(81A) 2879(2) 6166(1) 1852(2) 60(1) C(82A) 3530(2) 6208(1) 1660(1) 60(1) C(83A) 3771(2) 6359(1) 1284(2) 60(1) C(84A) 3196(2) 6519(1) 1062(2) 64(1) C(85A) 2619(2) 6479(1) 1221(3) 64(1) C(86A) 2368(2) 6316(1) 1682(3) 64(1) C(67A) 3338(2) 5226(1) 1920(2) 61(1) C(68A) 3755(3) 5375(1) 1467(3) 62(1) C(69A) 3404(5) 5280(1) 2700(2) 62(1) C(70A) 3643(3) 5010(1) 1819(5) 62(1) C(71A) 1625(2) 4886(1) 529(2) 59(1) C(72A) 2069(3) 4905(1) -141(2) 56(1) C(73A) 1813(4) 4679(1) 844(4) 63(1) C(74A) 886(2) 4881(1) 280(4) 59(2) C(75A) 858(2) 5499(1) 1915(2) 62(1) C(76A) 951(5) 5732(1) 1998(5) 63(1) C(77A) 664(4) 5428(1) 2659(2) 63(1) C(78A) 237(2) 5464(1) 1432(3) 63(1) C(87A) 4152(2) 6090(1) 1943(2) 62(1) C(88A) 4023(4) 5862(1) 2067(5) 62(1) C(89A) 4758(2) 6107(2) 1452(3) 62(1) C(90A) 4362(4) 6177(1) 2680(2) 62(1) C(91A) 3336(2) 6696(1) 558(2) 65(1) 42

43 C(92A) 4048(2) 6704(2) 245(4) 67(2) C(93A) 3222(5) 6904(1) 900(3) 68(1) C(94A) 2850(3) 6681(1) -92(2) 60(1) C(95A) 1592(2) 6292(1) 1767(2) 68(1) C(96A) 1392(4) 6204(1) 2495(2) 68(1) C(97A) 1324(4) 6147(1) 1206(3) 68(1) C(98A) 1230(3) 6500(1) 1692(5) 68(1) W(2) 2544(1) 7335(1) -4866(1) 58(1) Cl(5) 3714(1) 7356(1) -4666(2) 47(1) Cl(6) 2624(2) 7687(1) -4748(1) 47(1) Cl(7) 1424(1) 7311(1) -4957(2) 47(1) Cl(8) 2659(2) 6989(1) -5020(1) 47(1) O(11) 2581(5) 7308(1) -3850(2) 55(1) C(101) 2453(2) 7310(1) -3117(2) 54(1) C(102) 2561(1) 7453(1) -2649(2) 54(1) C(103) 2503(2) 7458(1) -2045(2) 54(1) C(104) 2223(4) 7270(1) -1680(3) 54(1) C(105) 2076(5) 7093(1) -2103(2) 54(1) C(106) 2241(3) 7103(1) -2834(2) 54(1) C(111) 2837(2) 7666(1) -2941(2) 54(1) C(112) 3496(2) 7714(1) -3048(1) 54(1) C(113) 3739(2) 7885(1) -3328(2) 54(1) C(114) 3262(2) 8042(1) -3576(3) 54(1) C(115) 2604(2) 8011(1) -3409(4) 54(1) C(116) 2348(2) 7820(1) -3223(3) 54(1) C(131) 2044(2) 6905(1) -3283(2) 50(1) C(132) 1421(2) 6873(1) -3570(2) 50(1) C(133) 1251(2) 6726(1) -4005(2) 50(1) C(134) 1871(2) 6583(1) -4221(2) 50(1) C(135) 2398(2) 6602(1) -3909(2) 49(1) C(136) 2598(2) 6766(1) -3425(2) 50(1) C(117) 4078(2) 7589(1) -2734(2) 54(1) C(118) 3945(5) 7356(1) -2680(5) 54(1) C(119) 4725(2) 7607(1) -3154(3) 54(1) C(120) 4216(5) 7666(1) -1965(2) 54(1) C(121) 3476(2) 8244(1) -3924(2) 57(1) 43

44 C(122) 3121(3) 8429(1) -3576(4) 58(1) C(123) 4221(2) 8293(1) -3891(5) 58(1) C(124) 3268(4) 8250(1) -4722(2) 58(1) C(125) 1593(2) 7831(1) -3020(2) 55(1) C(126) 1121(3) 7781(1) -3637(2) 55(1) C(127) 1403(4) 8042(1) -2744(4) 55(1) C(128) 1473(5) 7672(1) -2422(2) 55(1) C(137) 761(2) 6988(1) -3393(2) 51(1) C(138) 816(5) 7220(1) -3291(5) 50(1) C(139) 236(2) 6970(1) -3985(2) 50(1) C(140) 426(3) 6902(1) -2710(2) 50(1) C(141) 1761(2) 6414(1) -4763(2) 51(1) C(142) 2315(2) 6416(1) -5341(2) 51(1) C(143) 1830(5) 6203(1) -4428(3) 51(1) C(144) 1079(2) 6432(1) -5154(3) 51(1) C(145) 3331(2) 6748(1) -3149(2) 51(1) C(146) 3429(5) 6782(1) -2347(2) 50(1) C(147) 3632(3) 6536(1) -3261(5) 50(1) C(148) 3795(3) 6902(1) -3539(3) 50(1) W(2A) 2611(1) 7406(1) -4881(1) 66(1) Cl(5A) 3779(2) 7369(1) -4891(4) 47(1) Cl(6A) 2700(4) 7727(1) -5330(3) 47(1) Cl(7A) 1438(2) 7419(1) -4900(4) 47(1) Cl(8A) 2327(3) 7065(1) -4700(3) 47(1) O(11A) 2538(8) 7358(2) -3944(2) 57(1) C(01A) 2652(2) 7342(1) -3209(2) 54(1) C(02A) 2625(1) 7482(1) -2723(2) 54(1) C(03A) 2742(2) 7492(1) -2134(2) 54(1) C(04A) 3002(5) 7298(1) -1793(3) 54(1) C(05A) 3062(6) 7118(1) -2222(2) 54(1) C(06A) 2893(4) 7134(1) -2953(2) 54(1) C(11B) 2293(2) 7690(1) -3011(1) 54(1) C(12B) 2634(2) 7853(1) -3285(1) 54(1) C(13B) 2381(2) 8022(1) -3565(1) 54(1) C(14B) 1640(2) 8039(1) -3593(3) 55(1) C(15B) 1280(3) 7881(1) -3331(3) 54(1) 44

45 C(16B) 1548(2) 7702(1) -3045(3) 54(1) C(31B) 2953(2) 6932(1) -3424(2) 50(1) C(32B) 2451(2) 6796(1) -3580(2) 50(1) C(33B) 2468(2) 6630(1) -3955(2) 50(1) C(34B) 3201(2) 6592(1) -4302(2) 50(1) C(35B) 3651(2) 6705(1) -4120(3) 50(1) C(36B) 3633(2) 6890(1) -3678(2) 50(1) C(17B) 3402(2) 7878(1) -3292(2) 54(1) C(18B) 3767(3) 7678(1) -3493(5) 54(1) C(19B) 3641(4) 8036(1) -3826(3) 54(1) C(20B) 3667(4) 7940(1) -2546(2) 54(1) C(21B) 1306(2) 8229(1) -3917(2) 58(1) C(22B) 1011(4) 8188(2) -4659(2) 58(1) C(23B) 1806(3) 8403(1) -4022(6) 58(1) C(24B) 727(2) 8312(1) -3448(3) 58(1) C(25B) 988(2) 7563(1) -2744(2) 54(1) C(26B) 1258(4) 7380(1) -2319(3) 55(1) C(27B) 524(3) 7477(1) -3307(3) 55(1) C(28B) 550(3) 7689(1) -2214(3) 55(1) C(37B) 1749(2) 6811(1) -3222(2) 51(1) C(38B) 1809(6) 6814(2) -2406(2) 50(1) C(39B) 1286(3) 6634(1) -3394(5) 50(1) C(40B) 1374(3) 7010(1) -3435(5) 50(1) C(41B) 3223(2) 6422(1) -4859(2) 51(1) C(42B) 2690(3) 6454(2) -5447(3) 51(1) C(43B) 3042(5) 6213(1) -4552(4) 51(1) C(44B) 3899(2) 6400(2) -5258(4) 52(2) C(45B) 4276(2) 6967(1) -3293(2) 51(1) C(46B) 4424(5) 6842(1) -2619(2) 50(1) C(47B) 4202(6) 7186(1) -3022(4) 50(1) C(48B) 4911(2) 6954(2) -3763(3) 50(1) O(12) 2563(4) 7355(1) -5738(2) 60(1) C(151) 2752(2) 7361(1) -6465(2) 60(1) C(152) 3274(2) 7305(1) -6829(2) 60(1) C(153) 3387(2) 7286(1) -7424(2) 59(1) C(154) 2838(2) 7325(1) -7954(2) 58(1) 45

46 C(155) 2213(2) 7400(1) -7683(2) 58(1) C(156) 2153(2) 7414(1) -6933(2) 59(1) C(161) 3952(2) 7244(1) -6424(2) 61(1) C(162) 4101(2) 7048(1) -6204(1) 61(1) C(163) 4605(2) 6986(1) -5800(2) 61(1) C(164) 5091(2) 7141(1) -5573(2) 61(1) C(165) 4963(2) 7338(1) -5771(3) 61(1) C(166) 4432(2) 7404(1) -6192(3) 61(1) C(181) 1424(1) 7485(1) -6682(1) 58(1) C(182) 908(1) 7356(1) -6528(1) 57(1) C(183) 360(1) 7389(1) -6185(1) 58(1) C(184) 312(2) 7623(1) -5919(2) 60(1) C(185) 769(2) 7740(1) -6049(2) 60(1) C(186) 1394(2) 7696(1) -6430(2) 61(1) C(167) 3767(2) 6856(1) -6518(2) 62(1) C(168) 4146(3) 6799(1) -7213(2) 63(1) C(169) 3787(5) 6663(1) -6072(3) 63(1) C(170) 3025(2) 6890(2) -6743(5) 63(1) C(171) 5665(2) 7110(1) -5035(2) 66(1) C(172) 6347(2) 7178(1) -5346(4) 67(1) C(173) 5570(5) 7246(1) -4384(2) 67(1) C(174) 5738(5) 6887(1) -4777(4) 67(1) C(175) 4488(2) 7635(1) -6366(2) 62(1) C(176) 4282(4) 7771(1) -5736(2) 63(1) C(177) 5202(2) 7696(1) -6565(5) 63(1) C(178) 4035(3) 7703(1) -6995(2) 63(1) C(187) 881(2) 7131(1) -6808(2) 58(1) C(188) 282(2) 7013(1) -6504(4) 58(1) C(189) 793(5) 7119(2) -7612(2) 58(1) C(190) 1526(2) 7011(1) -6620(5) 58(1) C(191) -316(2) 7677(1) -5494(2) 61(1) C(192) -134(4) 7794(1) -4808(2) 62(1) C(193) -814(3) 7813(1) -5883(3) 62(1) C(194) -702(3) 7482(1) -5245(4) 62(1) C(195) 1854(2) 7880(1) -6621(2) 66(1) C(196) 2586(2) 7822(1) -6778(5) 68(1) 46

47 C(197) 1595(4) 7976(1) -7315(2) 68(1) C(198) 1856(5) 8049(1) -6049(3) 68(1) O(12A) 2284(6) 7409(2) -5945(2) 60(1) C(51B) 2306(2) 7365(1) -6676(2) 59(1) C(52B) 2762(1) 7406(1) -7146(2) 60(1) C(53B) 2790(2) 7405(1) -7750(2) 58(1) C(54B) 2158(2) 7346(2) -8145(3) 57(1) C(55B) 1579(2) 7287(2) -7739(2) 57(1) C(56B) 1623(2) 7307(1) -6994(2) 58(1) C(61B) 3476(2) 7481(1) -6844(2) 61(1) C(62B) 3990(2) 7355(1) -6628(1) 61(1) C(63B) 4540(2) 7406(1) -6276(2) 61(1) C(64B) 4659(2) 7626(1) -6131(2) 61(1) C(65B) 4165(2) 7755(1) -6342(4) 61(1) C(66B) 3556(2) 7700(1) -6644(3) 61(1) C(81B) 996(1) 7233(1) -6532(1) 58(1) C(82B) 857(1) 7038(1) -6321(1) 58(1) C(83B) 409(1) 6965(1) -5897(1) 58(1) C(84B) -58(2) 7146(1) -5585(2) 59(1) C(85B) 62(3) 7320(1) -5773(3) 58(1) C(86B) 571(2) 7398(1) -6263(3) 58(1) C(67B) 4035(2) 7124(1) -6778(2) 62(1) C(68B) 3439(2) 7044(1) -7220(3) 63(1) C(69B) 4659(2) 7059(1) -7187(3) 63(1) C(70B) 4030(6) 6998(1) -6077(2) 63(1) C(71B) 5159(2) 7705(1) -5574(2) 66(1) C(72B) 4781(3) 7835(1) -5012(3) 67(1) C(73B) 5690(3) 7850(1) -5858(4) 67(1) C(74B) 5504(4) 7530(1) -5157(3) 67(1) C(75B) 3144(2) 7896(1) -6798(2) 62(1) C(76B) 2587(2) 7932(2) -6245(3) 63(1) C(77B) 3581(3) 8088(1) -6734(6) 63(1) C(78B) 2822(4) 7895(2) -7543(2) 63(1) C(87B) 1246(2) 6854(1) -6646(2) 58(1) C(88B) 1954(2) 6917(1) -6892(5) 58(1) C(89B) 1335(6) 6673(1) -6154(3) 58(1) 47

48 C(90B) 884(3) 6778(1) -7331(2) 58(1) C(91B) -574(2) 7074(1) -5038(2) 61(1) C(92B) -443(5) 7168(1) -4298(2) 62(1) C(93B) -1296(2) 7127(2) -5215(5) 62(1) C(94B) -537(6) 6839(1) -4923(6) 62(1) C(95B) 638(2) 7628(1) -6449(2) 59(1) C(96B) 1279(2) 7722(1) -6129(4) 59(1) C(97B) 61(2) 7759(1) -6188(4) 59(1) C(98B) 701(6) 7662(2) -7264(2) 59(1) 48