Supporting Information for A Janus-type Bis(maloNHC) and its Zwitterionic Gold and Silver Metal Complexes

Supporting Information for A Janus-type Bis(maloNHC) and its Zwitterionic Gold and Silver Metal Complexes Ashley Carter, Alexander Mason, Michael A. Baker, Donald G. Bettler, Angelo Changas, Colin D. McMillen, and Daniela Tapu*, Department of Chemistry and Biochemistry, Kennesaw State University, 370 Paulding Avenue NW, Kennesaw, Georgia, 30144, United States Department of Chemistry, Clemson University, 379 Hunter Laboratories, Clemson, SC, 29634, United States dtapu@kennesaw.edu Contents NMR Spectra of 2, 3, 5-9 X-ray Crystallography of 6-9 Page S2 S11 S1

Figure S1. 1 H NMR spectrum of 2 (CDCl 3, 300 MHz) Figure S2. 13 C NMR spectrum of 2 (CDCl 3, 75.5 MHz) S2

Figure S3. 1 H NMR spectrum of 3 (DMSO-d 6, 300 MHz) Figure S4. 1 H NMR spectrum of 5 (CDCl 3, 300 MHz) S3

Figure S5. 13 C NMR spectrum of 5 (CDCl 3, 75.5 MHz) Figure S6. 1 H NMR spectrum of 6 (DMSO-d 6, 300 MHz) S4

Figure S7. 13 C NMR spectrum of 6 (CDCl 3, 75.5 MHz) Figure S8. 1 H NMR spectrum of 1 (DMSO-d 6, 300 MHz) S5

Figure S9. 13 C NMR spectrum of 1 (DMSO-d 6, 75.5 MHz) Figure S10. 1 H NMR spectrum of 7 (DMSO-d 6, 300 MHz) S6

Figure S11. 13 C NMR spectrum of 7 (DMSO-d 6, 75.5 MHz) Figure S12. 1 H NMR spectrum of 8 (CDCl 3, 300 MHz) S7

Figure S13. 13 C NMR spectrum of 8 (CD 2 Cl 2, 75.5 MHz) Figure S14. 31 P NMR spectrum of 8 (CDCl 3, 121.49 MHz) S8

Figure S15. 1 H NMR spectrum of 9 (CDCl 3, 300 MHz) Figure S16. 13 C NMR spectrum of 9 (CD 2 Cl 2, 75.5 MHz) S9

Figure S17. 31 P NMR spectrum of 9 (CDCl 3, 121.49 MHz) S10

Crystal Structure Report for 6 (C74H82N4O4 xc7h8 (x ~3-4.5)) A specimen of C 95 H 106 N 4 O 4, approximate dimensions 0.101 mm x 0.315 mm x 0.492 mm, was used for the X-ray crystallographic analysis. The X-ray intensity data were measured. The integration of the data using a monoclinic unit cell yielded a total of 175960 reflections to a maximum θ angle of 25.50 (0.83 Å resolution), of which 16123 were independent (average redundancy 10.914, completeness = 99.9%, R int = 7.01%, R sig = 2.97%) and 12902 (80.02%) were greater than 2σ(F 2 ). The final cell constants of a = 19.3986(12) Å, b = 20.1631(14) Å, c = 22.2441(14) Å, β = 94.617(2), volume = 8672.2(10) Å 3, are based upon the refinement of the XYZ-centroids of reflections above 20 σ(i). The calculated minimum and maximum transmission coefficients (based on crystal size) are 0.8658 and 1.0000. The structure was solved and refined using the Bruker SHELXTL Software Package, using the space group P 1 21/n 1, with Z = 4 for the formula unit, C 95 H 106 N 4 O 4. The final anisotropic full-matrix least-squares refinement on F 2 with 949 variables converged at R1 = 6.33%, for the observed data and wr2 = 19.07% for all data. The goodness-of-fit was 1.043. The largest peak in the final difference electron density synthesis was 1.872 e - /Å 3 and the largest hole was -0.660 e - /Å 3 with an RMS deviation of 0.080 e - /Å 3. On the basis of the final model, the calculated density was 1.048 g/cm 3 and F(000), 2944 e -. An additional 1.5 molecules of crystallized toluene solvent molecules per formula unit were modeled using the SQUEEZE algorithm of PLATON. Three crystallized solvent molecules per formula unit were modeled directly from the difference electron density map. Figure S18. Solid state molecular structure of 6 S11

Figure S19. Solid state packing diagram of 6 S12

Table S1. Sample and crystal data for 6 squeezed. Chemical formula C 95 H 106 N 4 O 4 Formula weight Temperature Wavelength Crystal size Crystal system 1367.83 g/mol 100(2) K 0.71073 Å 0.101 x 0.315 x 0.492 mm monoclinic Space group P 1 21/n 1 Unit cell dimensions a = 19.3986(12) Å α = 90 b = 20.1631(14) Å β = 94.617(2) c = 22.2441(14) Å γ = 90 Volume 8672.2(10) Å 3 Z 4 Density (calculated) 1.048 g/cm 3 Absorption coefficient 0.063 mm -1 F(000) 2944 Table S2. Data collection and structure refinement for 6 squeezed. Theta range for data collection 2.10 to 25.50 Index ranges -23 h 23, -24 k 24, -26 l 26 Reflections collected 175960 Independent reflections 16123 [R(int) = 0.0701] Max. and min. transmission 1.0000 and 0.8658 Structure solution technique direct methods Structure solution program SHELXT-2014 (Sheldrick 2014) Refinement method Full-matrix least-squares on F 2 Refinement program SHELXL-2014 (Sheldrick 2014) Function minimized 2 Σ w(f o - F c2 ) 2 S13

Data / restraints / parameters 16123 / 30 / 949 Goodness-of-fit on F 2 1.043 Δ/σmax 0.001 Final R indices 12902 data; I>2σ(I) R1 = 0.0633, wr2 = 0.1731 all data R1 = 0.0794, wr2 = 0.1907 Weighting scheme w=1/[σ 2 (F o2 )+(0.0962P) 2 +9.0880P] where P=(F o2 +2F c2 )/3 Largest diff. peak and hole 1.872 and -0.660 eå -3 R.M.S. deviation from mean 0.080 eå -3 Table S3. Atomic coordinates and equivalent isotropic atomic displacement parameters (Å 2 ) for 6 squeezed. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x/a y/b z/c U(eq) O1 0.08537(7) 0.25468(7) 0.74896(6) 0.0215(3) O2 0.26009(8) 0.42035(7) 0.75254(7) 0.0261(4) O3 0.59855(8) 0.21909(7) 0.77975(7) 0.0249(3) O4 0.72406(8) 0.41274(7) 0.73376(7) 0.0270(4) N1 0.26477(8) 0.32549(8) 0.69740(7) 0.0161(3) N2 0.18135(8) 0.24437(8) 0.69749(7) 0.0150(3) N3 0.73491(8) 0.31491(8) 0.68470(7) 0.0154(3) N4 0.67619(8) 0.22088(8) 0.70889(7) 0.0147(3) C1 0.23976(10) 0.26731(10) 0.67992(8) 0.0152(4) C2 0.14061(10) 0.28031(10) 0.73909(8) 0.0151(4) C3 0.17092(10) 0.34022(10) 0.76256(8) 0.0154(4) C4 0.23133(10) 0.36740(10) 0.74045(9) 0.0169(4) C5 0.13655(10) 0.37450(10) 0.81088(9) 0.0160(4) C6 0.10245(10) 0.33786(10) 0.85302(9) 0.0169(4) C7 0.06955(10) 0.36852(10) 0.89811(9) 0.0178(4) C8 0.06941(10) 0.43749(10) 0.90429(9) 0.0167(4) C9 0.10440(11) 0.47417(10) 0.86323(10) 0.0229(5) S14

C10 0.13716(11) 0.44354(10) 0.81745(10) 0.0220(5) C11 0.03403(10) 0.46933(10) 0.95330(9) 0.0159(4) C12 0.97139(10) 0.44475(10) 0.97089(9) 0.0170(4) C13 0.93788(10) 0.47462(10) 0.01656(9) 0.0170(4) C14 0.15997(10) 0.17757(10) 0.67975(9) 0.0163(4) C15 0.11144(11) 0.17052(11) 0.63032(9) 0.0206(4) C16 0.09234(12) 0.10608(12) 0.61403(10) 0.0260(5) C17 0.12021(12) 0.05238(11) 0.64618(10) 0.0279(5) C18 0.16785(12) 0.06130(11) 0.69542(10) 0.0247(5) C19 0.18880(11) 0.12474(10) 0.71374(9) 0.0190(4) C20 0.08349(12) 0.23088(12) 0.59546(10) 0.0258(5) C21 0.12977(13) 0.24885(13) 0.54538(11) 0.0349(6) C22 0.00857(13) 0.22286(14) 0.57039(12) 0.0369(6) C23 0.23824(11) 0.13559(11) 0.76974(10) 0.0231(5) C24 0.19905(15) 0.13175(15) 0.82644(11) 0.0407(7) C25 0.29920(12) 0.08722(12) 0.77349(11) 0.0305(5) C26 0.33280(10) 0.34385(10) 0.67923(10) 0.0199(4) C27 0.33731(12) 0.37434(11) 0.62322(10) 0.0262(5) C28 0.40398(14) 0.38767(13) 0.60697(12) 0.0374(6) C29 0.46185(13) 0.37155(14) 0.64480(14) 0.0416(7) C30 0.45543(12) 0.34269(13) 0.69994(13) 0.0352(6) C31 0.38993(11) 0.32868(11) 0.71887(10) 0.0245(5) C32 0.27412(13) 0.39554(12) 0.58312(10) 0.0311(5) C33 0.27647(17) 0.37332(17) 0.51761(12) 0.0486(7) C34 0.26559(18) 0.47084(14) 0.58701(14) 0.0498(7) C35 0.38345(11) 0.29995(12) 0.78134(10) 0.0277(5) C36 0.42359(13) 0.23512(14) 0.79133(14) 0.0424(7) C37 0.40631(16) 0.35234(16) 0.82880(13) 0.0469(7) C38 0.71990(10) 0.25186(10) 0.67655(8) 0.0153(4) S15

C39 0.63975(10) 0.25381(10) 0.75507(9) 0.0159(4) C40 0.65623(10) 0.32174(10) 0.76448(9) 0.0156(4) C41 0.70423(10) 0.35519(10) 0.73031(9) 0.0169(4) C42 0.62309(10) 0.35883(10) 0.81219(9) 0.0156(4) C43 0.60257(11) 0.32655(10) 0.86366(9) 0.0191(4) C44 0.57200(11) 0.36125(10) 0.90825(9) 0.0195(4) C45 0.56151(10) 0.42960(10) 0.90430(9) 0.0166(4) C46 0.58169(11) 0.46176(10) 0.85323(9) 0.0202(4) C47 0.61139(11) 0.42730(10) 0.80797(9) 0.0206(4) C48 0.52977(10) 0.46577(10) 0.95302(8) 0.0159(4) C49 0.55866(10) 0.52498(10) 0.97617(9) 0.0174(4) C50 0.52943(10) 0.55844(10) 0.02239(9) 0.0172(4) C51 0.65982(10) 0.15177(10) 0.69468(9) 0.0174(4) C52 0.69607(12) 0.10193(11) 0.72709(10) 0.0238(5) C53 0.68117(14) 0.03665(12) 0.70944(11) 0.0332(6) C54 0.63253(14) 0.02332(12) 0.66183(12) 0.0356(6) C55 0.59594(13) 0.07388(11) 0.63217(11) 0.0298(5) C56 0.60839(11) 0.13983(10) 0.64859(9) 0.0214(4) C57 0.74766(13) 0.11631(12) 0.78059(11) 0.0315(5) C58 0.81763(14) 0.08319(13) 0.77404(13) 0.0384(6) C59 0.71868(18) 0.0940(2) 0.83931(13) 0.0617(10) C60 0.56768(12) 0.19528(11) 0.61619(10) 0.0271(5) C61 0.58857(18) 0.20167(15) 0.55154(12) 0.0493(8) C62 0.49001(14) 0.18477(14) 0.61795(16) 0.0497(8) C63 0.78556(11) 0.34598(10) 0.64857(9) 0.0199(4) C64 0.85422(11) 0.34821(12) 0.67355(10) 0.0270(5) C65 0.90191(13) 0.37843(15) 0.63913(13) 0.0417(7) C66 0.88193(16) 0.40581(17) 0.58395(14) 0.0523(8) C67 0.81361(15) 0.40344(15) 0.56073(13) 0.0449(7) S16

C68 0.76326(12) 0.37280(12) 0.59257(10) 0.0279(5) C69 0.87538(12) 0.31842(14) 0.73456(11) 0.0337(6) C70 0.93409(14) 0.35701(17) 0.76946(14) 0.0493(8) C71 0.89565(16) 0.24652(15) 0.72914(14) 0.0494(7) C72 0.68773(13) 0.37272(13) 0.56785(10) 0.0313(5) C73 0.67865(16) 0.35289(16) 0.50120(12) 0.0438(7) C74 0.65481(16) 0.44015(16) 0.57769(14) 0.0503(8) C75 0.00504(13) 0.09751(17) 0.84580(12) 0.0445(7) C76 0.00526(14) 0.16551(16) 0.85561(13) 0.0445(7) C77 0.98859(15) 0.19141(14) 0.90944(14) 0.0445(7) C78 0.97171(15) 0.15051(14) 0.95554(13) 0.0410(6) C79 0.97250(16) 0.08295(14) 0.94703(13) 0.0427(7) C80 0.98912(15) 0.05684(15) 0.89286(14) 0.0457(7) C81 0.0203(2) 0.0689(3) 0.78573(16) 0.0832(14) C82 0.29400(13) 0.16017(16) 0.45392(13) 0.0423(7) C83 0.24729(13) 0.10928(15) 0.45946(12) 0.0409(6) C84 0.23462(13) 0.08396(14) 0.51495(13) 0.0380(6) C85 0.26981(13) 0.10922(15) 0.56658(12) 0.0386(6) C86 0.31715(13) 0.15920(15) 0.56159(13) 0.0415(7) C87 0.32920(13) 0.18454(14) 0.50587(14) 0.0414(7) C88 0.3062(2) 0.1877(3) 0.39235(17) 0.0845(14) C89 0.8116(3) 0.1989(2) 0.4930(3) 0.0864(13) C90 0.82333(16) 0.1871(2) 0.5489(2) 0.0736(11) C91 0.7982(2) 0.1323(2) 0.5791(2) 0.0803(10) C92 0.7490(2) 0.08780(19) 0.5385(2) 0.0761(12) C93 0.74165(16) 0.1104(2) 0.47998(19) 0.0701(11) C94 0.7736(2) 0.1639(3) 0.4618(3) 0.0879(14) C95 0.8421(4) 0.2594(3) 0.4591(3) 0.140(2) S17

Table S4. Bond lengths (Å) for 6 squeezed. O1-C2 1.225(2) O2-C4 1.224(2) O3-C39 1.225(2) O4-C41 1.223(3) N1-C1 1.316(3) N1-C26 1.459(2) N1-C4 1.467(2) N2-C1 1.312(3) N2-C14 1.454(3) N2-C2 1.457(2) N3-C38 1.314(3) N3-C63 1.460(3) N3-C41 1.463(2) N4-C38 1.313(3) N4-C39 1.454(2) N4-C51 1.458(3) C1-H1 0.95 C2-C3 1.424(3) C3-C4 1.417(3) C3-C5 1.481(3) C5-C10 1.400(3) C5-C6 1.401(3) C6-C7 1.378(3) C6-H6 0.95 C7-C8 1.398(3) C7-H7 0.95 C8-C9 1.393(3) C8-C11 1.481(3) C9-C10 1.388(3) C9-H9 0.95 C10-H10 0.95 C11-C12 1.397(3) C11-C13 1.402(3) C12-C13 1.387(3) C12-H12 0.95 C13-C11 1.402(3) C13-H13 0.95 C14-C15 1.396(3) C14-C19 1.397(3) C15-C16 1.391(3) C15-C20 1.520(3) C16-C17 1.384(3) C16-H16 0.95 C17-C18 1.387(3) C17-H17 0.95 C18-C19 1.393(3) C18-H18 0.95 C19-C23 1.525(3) C20-C22 1.523(3) C20-C21 1.529(3) C20-H20 1.0 C21-H21A 0.98 C21-H21B 0.98 C21-H21C 0.98 C22-H22A 0.98 C22-H22B 0.98 S18

C22-H22C 0.98 C23-C24 1.526(3) C23-C25 1.530(3) C23-H23 1.0 C24-H24A 0.98 C24-H24B 0.98 C24-H24C 0.98 C25-H25A 0.98 C25-H25B 0.98 C25-H25C 0.98 C26-C31 1.394(3) C26-C27 1.398(3) C27-C28 1.397(3) C27-C32 1.518(4) C28-C29 1.386(4) C28-H28 0.95 C29-C30 1.372(4) C29-H29 0.95 C30-C31 1.399(3) C30-H30 0.95 C31-C35 1.520(3) C32-C33 1.529(3) C32-C34 1.530(4) C32-H32 1.0 C33-H33A 0.98 C33-H33B 0.98 C33-H33C 0.98 C34-H34A 0.98 C34-H34B 0.98 C34-H34C 0.98 C35-C36 1.529(4) C35-C37 1.533(4) C35-H35 1.0 C36-H36A 0.98 C36-H36B 0.98 C36-H36C 0.98 C37-H37A 0.98 C37-H37B 0.98 C37-H37C 0.98 C38-H38 0.95 C39-C40 1.418(3) C40-C41 1.419(3) C40-C42 1.486(3) C42-C47 1.401(3) C42-C43 1.402(3) C43-C44 1.385(3) C43-H43 0.95 C44-C45 1.395(3) C44-H44 0.95 C45-C46 1.391(3) C45-C48 1.481(3) C46-C47 1.386(3) C46-H46 0.95 C47-H47 0.95 C48-C50 1.399(3) C48-C49 1.399(3) C49-C50 1.389(3) C49-H49 0.95 S19

C50-C48 1.399(3) C50-H50 0.95 C51-C56 1.393(3) C51-C52 1.394(3) C52-C53 1.397(3) C52-C57 1.520(3) C53-C54 1.387(4) C53-H53 0.95 C54-C55 1.380(4) C54-H54 0.95 C55-C56 1.395(3) C55-H55 0.95 C56-C60 1.517(3) C57-C58 1.530(3) C57-C59 1.531(4) C57-H57 1.0 C58-H58A 0.98 C58-H58B 0.98 C58-H58C 0.98 C59-H59A 0.98 C59-H59B 0.98 C59-H59C 0.98 C60-C62 1.525(4) C60-C61 1.530(4) C60-H60 1.0 C61-H61A 0.98 C61-H61B 0.98 C61-H61C 0.98 C62-H62A 0.98 C62-H62B 0.98 C62-H62C 0.98 C63-C68 1.395(3) C63-C64 1.402(3) C64-C65 1.388(3) C64-C69 1.510(3) C65-C66 1.373(4) C65-H65 0.95 C66-C67 1.384(4) C66-H66 0.95 C67-C68 1.396(3) C67-H67 0.95 C68-C72 1.523(3) C69-C71 1.510(4) C69-C70 1.537(3) C69-H69 1.0 C70-H70A 0.98 C70-H70B 0.98 C70-H70C 0.98 C71-H71A 0.98 C71-H71B 0.98 C71-H71C 0.98 C72-C74 1.525(4) C72-C73 1.532(4) C72-H72 1.0 C73-H73A 0.98 C73-H73B 0.98 C73-H73C 0.98 C74-H74A 0.98 S20

C74-H74B 0.98 C74-H74C 0.98 C75-C80 1.384(4) C75-C76 1.388(5) C75-C81 1.507(4) C76-C77 1.369(4) C76-H76 0.95 C77-C78 1.376(4) C77-H77 0.95 C78-C79 1.375(4) C78-H78 0.95 C79-C80 1.377(4) C79-H79 0.95 C80-H80 0.95 C81-H81A 0.98 C81-H81B 0.98 C81-H81C 0.98 C82-C83 1.381(4) C82-C87 1.384(4) C82-C88 1.514(4) C83-C84 1.376(4) C83-H83 0.95 C84-C85 1.385(4) C84-H84 0.95 C85-C86 1.374(4) C85-H85 0.95 C86-C87 1.378(4) C86-H86 0.95 C87-H87 0.95 C88-H88A 0.98 C88-H88B 0.98 C88-H88C 0.98 C89-C94 1.200(7) C89-C90 1.267(7) C89-C95 1.575(8) C90-C91 1.402(6) C90-H90 0.95 C91-C92 1.547(7) C91-H91 0.95 C92-C93 1.375(6) C92-H92 0.95 C93-C94 1.324(6) C93-H93 0.95 C94-H94 0.95 C95-H95A 0.98 C95-H95B 0.98 C95-H95C 0.98 Table S5. Bond angles ( ) for 6 squeezed. C1-N1-C26 117.68(16) C1-N1-C4 122.31(16) C26-N1-C4 119.47(16) C1-N2-C14 118.68(16) C1-N2-C2 122.63(16) C14-N2-C2 118.37(15) S21

C38-N3-C63 119.40(16) C38-N3-C41 122.34(16) C63-N3-C41 118.23(16) C38-N4-C39 122.82(17) C38-N4-C51 118.34(16) C39-N4-C51 118.68(16) N2-C1-N1 122.19(18) N2-C1-H1 118.9 N1-C1-H1 118.9 O1-C2-C3 129.29(18) O1-C2-N2 115.53(17) C3-C2-N2 115.19(16) C4-C3-C2 121.96(17) C4-C3-C5 120.30(17) C2-C3-C5 117.73(17) O2-C4-C3 129.47(18) O2-C4-N1 115.36(17) C3-C4-N1 115.16(17) C10-C5-C6 117.07(18) C10-C5-C3 122.66(18) C6-C5-C3 120.26(18) C7-C6-C5 121.47(19) C7-C6-H6 119.3 C5-C6-H6 119.3 C6-C7-C8 121.51(18) C6-C7-H7 119.2 C8-C7-H7 119.2 C9-C8-C7 117.31(18) C9-C8-C11 122.12(18) C7-C8-C11 120.57(18) C10-C9-C8 121.38(19) C10-C9-H9 119.3 C8-C9-H9 119.3 C9-C10-C5 121.24(19) C9-C10-H10 119.4 C5-C10-H10 119.4 C12-C11-C13 117.74(18) C12-C11-C8 121.17(18) C13-C11-C8 121.09(18) C13-C12-C11 121.37(19) C13-C12-H12 119.3 C11-C12-H12 119.3 C12-C13-C11 120.89(18) C12-C13-H13 119.6 C11-C13-H13 119.6 C15-C14-C19 124.33(19) C15-C14-N2 117.87(18) C19-C14-N2 117.80(17) C16-C15-C14 116.7(2) C16-C15-C20 122.58(19) C14-C15-C20 120.71(19) C17-C16-C15 120.8(2) C17-C16-H16 119.6 C15-C16-H16 119.6 C16-C17-C18 121.0(2) C16-C17-H17 119.5 C18-C17-H17 119.5 C17-C18-C19 120.7(2) S22

C17-C18-H18 119.7 C19-C18-H18 119.7 C18-C19-C14 116.57(19) C18-C19-C23 121.34(19) C14-C19-C23 122.04(18) C15-C20-C22 113.1(2) C15-C20-C21 110.81(19) C22-C20-C21 110.93(19) C15-C20-H20 107.2 C22-C20-H20 107.2 C21-C20-H20 107.2 C20-C21-H21A 109.5 C20-C21-H21B 109.5 H21A-C21-H21B 109.5 C20-C21-H21C 109.5 H21A-C21-H21C 109.5 H21B-C21-H21C 109.5 C20-C22-H22A 109.5 C20-C22-H22B 109.5 H22A-C22-H22B 109.5 C20-C22-H22C 109.5 H22A-C22-H22C 109.5 H22B-C22-H22C 109.5 C19-C23-C24 110.20(19) C19-C23-C25 112.67(18) C24-C23-C25 110.90(19) C19-C23-H23 107.6 C24-C23-H23 107.6 C25-C23-H23 107.6 C23-C24-H24A 109.5 C23-C24-H24B 109.5 H24A-C24-H24B 109.5 C23-C24-H24C 109.5 H24A-C24-H24C 109.5 H24B-C24-H24C 109.5 C23-C25-H25A 109.5 C23-C25-H25B 109.5 H25A-C25-H25B 109.5 C23-C25-H25C 109.5 H25A-C25-H25C 109.5 H25B-C25-H25C 109.5 C31-C26-C27 123.82(19) C31-C26-N1 117.39(19) C27-C26-N1 118.78(19) C28-C27-C26 116.2(2) C28-C27-C32 121.0(2) C26-C27-C32 122.80(19) C29-C28-C27 121.3(2) C29-C28-H28 119.4 C27-C28-H28 119.4 C30-C29-C28 121.0(2) C30-C29-H29 119.5 C28-C29-H29 119.5 C29-C30-C31 120.3(2) C29-C30-H30 119.8 C31-C30-H30 119.8 C26-C31-C30 117.4(2) C26-C31-C35 122.83(19) S23

C30-C31-C35 119.7(2) C27-C32-C33 113.1(2) C27-C32-C34 109.4(2) C33-C32-C34 110.9(2) C27-C32-H32 107.7 C33-C32-H32 107.7 C34-C32-H32 107.7 C32-C33-H33A 109.5 C32-C33-H33B 109.5 H33A-C33-H33B 109.5 C32-C33-H33C 109.5 H33A-C33-H33C 109.5 H33B-C33-H33C 109.5 C32-C34-H34A 109.5 C32-C34-H34B 109.5 H34A-C34-H34B 109.5 C32-C34-H34C 109.5 H34A-C34-H34C 109.5 H34B-C34-H34C 109.5 C31-C35-C36 112.3(2) C31-C35-C37 109.0(2) C36-C35-C37 111.9(2) C31-C35-H35 107.8 C36-C35-H35 107.8 C37-C35-H35 107.8 C35-C36-H36A 109.5 C35-C36-H36B 109.5 H36A-C36-H36B 109.5 C35-C36-H36C 109.5 H36A-C36-H36C 109.5 H36B-C36-H36C 109.5 C35-C37-H37A 109.5 C35-C37-H37B 109.5 H37A-C37-H37B 109.5 C35-C37-H37C 109.5 H37A-C37-H37C 109.5 H37B-C37-H37C 109.5 N4-C38-N3 122.03(17) N4-C38-H38 119.0 N3-C38-H38 119.0 O3-C39-C40 129.29(18) O3-C39-N4 115.32(17) C40-C39-N4 115.39(17) C39-C40-C41 122.00(17) C39-C40-C42 119.07(17) C41-C40-C42 118.92(17) O4-C41-C40 129.35(18) O4-C41-N3 115.26(17) C40-C41-N3 115.38(17) C47-C42-C43 117.19(18) C47-C42-C40 121.67(18) C43-C42-C40 121.14(18) C44-C43-C42 121.07(19) C44-C43-H43 119.5 C42-C43-H43 119.5 C43-C44-C45 121.50(19) C43-C44-H44 119.3 C45-C44-H44 119.3 S24

C46-C45-C44 117.56(18) C46-C45-C48 121.94(18) C44-C45-C48 120.49(18) C47-C46-C45 121.34(19) C47-C46-H46 119.3 C45-C46-H46 119.3 C46-C47-C42 121.32(19) C46-C47-H47 119.3 C42-C47-H47 119.3 C50-C48-C49 118.10(18) C50-C48-C45 121.13(18) C49-C48-C45 120.77(18) C50-C49-C48 120.78(19) C50-C49-H49 119.6 C48-C49-H49 119.6 C49-C50-C48 121.13(19) C49-C50-H50 119.4 C48-C50-H50 119.4 C56-C51-C52 123.90(19) C56-C51-N4 117.09(18) C52-C51-N4 119.01(18) C51-C52-C53 116.7(2) C51-C52-C57 122.7(2) C53-C52-C57 120.5(2) C54-C53-C52 120.6(2) C54-C53-H53 119.7 C52-C53-H53 119.7 C55-C54-C53 121.0(2) C55-C54-H54 119.5 C53-C54-H54 119.5 C54-C55-C56 120.5(2) C54-C55-H55 119.7 C56-C55-H55 119.7 C51-C56-C55 117.1(2) C51-C56-C60 122.47(19) C55-C56-C60 120.37(19) C52-C57-C58 112.1(2) C52-C57-C59 110.4(2) C58-C57-C59 110.0(2) C52-C57-H57 108.1 C58-C57-H57 108.1 C59-C57-H57 108.1 C57-C58-H58A 109.5 C57-C58-H58B 109.5 H58A-C58-H58B 109.5 C57-C58-H58C 109.5 H58A-C58-H58C 109.5 H58B-C58-H58C 109.5 C57-C59-H59A 109.5 C57-C59-H59B 109.5 H59A-C59-H59B 109.5 C57-C59-H59C 109.5 H59A-C59-H59C 109.5 H59B-C59-H59C 109.5 C56-C60-C62 111.3(2) C56-C60-C61 110.0(2) C62-C60-C61 111.9(2) C56-C60-H60 107.9 S25

C62-C60-H60 107.9 C61-C60-H60 107.9 C60-C61-H61A 109.5 C60-C61-H61B 109.5 H61A-C61-H61B 109.5 C60-C61-H61C 109.5 H61A-C61-H61C 109.5 H61B-C61-H61C 109.5 C60-C62-H62A 109.5 C60-C62-H62B 109.5 H62A-C62-H62B 109.5 C60-C62-H62C 109.5 H62A-C62-H62C 109.5 H62B-C62-H62C 109.5 C68-C63-C64 123.9(2) C68-C63-N3 118.95(19) C64-C63-N3 117.11(19) C65-C64-C63 116.7(2) C65-C64-C69 121.7(2) C63-C64-C69 121.6(2) C66-C65-C64 121.1(2) C66-C65-H65 119.4 C64-C65-H65 119.4 C65-C66-C67 120.9(2) C65-C66-H66 119.6 C67-C66-H66 119.6 C66-C67-C68 120.9(3) C66-C67-H67 119.5 C68-C67-H67 119.5 C63-C68-C67 116.4(2) C63-C68-C72 122.8(2) C67-C68-C72 120.6(2) C71-C69-C64 111.3(2) C71-C69-C70 109.8(2) C64-C69-C70 112.9(2) C71-C69-H69 107.5 C64-C69-H69 107.5 C70-C69-H69 107.5 C69-C70-H70A 109.5 C69-C70-H70B 109.5 H70A-C70-H70B 109.5 C69-C70-H70C 109.5 H70A-C70-H70C 109.5 H70B-C70-H70C 109.5 C69-C71-H71A 109.5 C69-C71-H71B 109.5 H71A-C71-H71B 109.5 C69-C71-H71C 109.5 H71A-C71-H71C 109.5 H71B-C71-H71C 109.5 C68-C72-C74 110.4(2) C68-C72-C73 112.5(2) C74-C72-C73 110.8(2) C68-C72-H72 107.7 C74-C72-H72 107.7 C73-C72-H72 107.7 C72-C73-H73A 109.5 C72-C73-H73B 109.5 S26

H73A-C73-H73B 109.5 C72-C73-H73C 109.5 H73A-C73-H73C 109.5 H73B-C73-H73C 109.5 C72-C74-H74A 109.5 C72-C74-H74B 109.5 H74A-C74-H74B 109.5 C72-C74-H74C 109.5 H74A-C74-H74C 109.5 H74B-C74-H74C 109.5 C80-C75-C76 117.7(3) C80-C75-C81 121.0(3) C76-C75-C81 121.3(3) C77-C76-C75 121.1(3) C77-C76-H76 119.4 C75-C76-H76 119.4 C76-C77-C78 120.7(3) C76-C77-H77 119.7 C78-C77-H77 119.7 C79-C78-C77 119.0(3) C79-C78-H78 120.5 C77-C78-H78 120.5 C78-C79-C80 120.3(3) C78-C79-H79 119.8 C80-C79-H79 119.8 C79-C80-C75 121.2(3) C79-C80-H80 119.4 C75-C80-H80 119.4 C75-C81-H81A 109.5 C75-C81-H81B 109.5 H81A-C81-H81B 109.5 C75-C81-H81C 109.5 H81A-C81-H81C 109.5 H81B-C81-H81C 109.5 C83-C82-C87 118.2(3) C83-C82-C88 120.3(3) C87-C82-C88 121.5(3) C84-C83-C82 121.4(3) C84-C83-H83 119.3 C82-C83-H83 119.3 C83-C84-C85 119.7(3) C83-C84-H84 120.1 C85-C84-H84 120.1 C86-C85-C84 119.4(3) C86-C85-H85 120.3 C84-C85-H85 120.3 C85-C86-C87 120.5(3) C85-C86-H86 119.7 C87-C86-H86 119.7 C86-C87-C82 120.7(3) C86-C87-H87 119.6 C82-C87-H87 119.6 C82-C88-H88A 109.5 C82-C88-H88B 109.5 H88A-C88-H88B 109.5 C82-C88-H88C 109.5 H88A-C88-H88C 109.5 H88B-C88-H88C 109.5 S27

C94-C89-C90 120.7(6) C94-C89-C95 114.5(6) C90-C89-C95 124.7(6) C89-C90-C91 125.2(4) C89-C90-H90 117.4 C91-C90-H90 117.4 C90-C91-C92 113.5(4) C90-C91-H91 123.3 C92-C91-H91 123.3 C93-C92-C91 111.9(4) C93-C92-H92 124.0 C91-C92-H92 124.0 C94-C93-C92 122.9(4) C94-C93-H93 118.5 C92-C93-H93 118.5 C89-C94-C93 125.7(6) C89-C94-H94 117.2 C93-C94-H94 117.2 C89-C95-H95A 109.5 C89-C95-H95B 109.5 H95A-C95-H95B 109.5 C89-C95-H95C 109.5 H95A-C95-H95C 109.5 H95B-C95-H95C 109.5 Table S6. Anisotropic atomic displacement parameters (Å 2 ) for 6 squeezed. The anisotropic atomic displacement factor exponent takes the form: -2π 2 [ h 2 a *2 U 11 +... + 2 h k a * b * U 12 ] U11 U22 U33 U23 U13 U12 O1 0.0181(7) 0.0239(8) 0.0234(8) -0.0069(6) 0.0084(6) -0.0051(6) O2 0.0265(8) 0.0196(8) 0.0343(9) -0.0095(7) 0.0150(7) -0.0077(6) O3 0.0279(8) 0.0196(8) 0.0293(8) -0.0047(6) 0.0148(7) -0.0054(6) O4 0.0314(8) 0.0170(8) 0.0349(9) -0.0085(6) 0.0172(7) -0.0075(6) N1 0.0169(8) 0.0165(9) 0.0157(8) -0.0023(7) 0.0064(6) -0.0011(7) N2 0.0173(8) 0.0140(8) 0.0140(8) -0.0022(6) 0.0035(6) -0.0002(6) N3 0.0147(8) 0.0174(9) 0.0147(8) -0.0026(7) 0.0046(6) -0.0004(6) N4 0.0165(8) 0.0137(8) 0.0140(8) -0.0020(6) 0.0014(6) 0.0015(6) C1 0.0168(9) 0.0168(10) 0.0122(9) -0.0003(7) 0.0030(7) 0.0023(8) C2 0.0173(10) 0.0159(10) 0.0123(9) -0.0004(7) 0.0025(7) 0.0019(8) C3 0.0175(9) 0.0143(10) 0.0146(9) 0.0003(7) 0.0031(7) 0.0021(8) C4 0.0199(10) 0.0149(10) 0.0165(10) -0.0028(8) 0.0057(8) 0.0020(8) C5 0.0166(9) 0.0167(10) 0.0147(9) -0.0010(8) 0.0018(7) 0.0019(8) S28

C6 0.0214(10) 0.0132(10) 0.0163(9) -0.0022(8) 0.0033(8) -0.0005(8) C7 0.0198(10) 0.0185(10) 0.0157(9) 0.0014(8) 0.0046(8) -0.0006(8) C8 0.0188(10) 0.0163(10) 0.0154(9) -0.0003(8) 0.0036(8) 0.0020(8) C9 0.0322(12) 0.0121(10) 0.0263(11) -0.0013(8) 0.0131(9) 0.0008(8) C10 0.0286(11) 0.0163(11) 0.0231(11) 0.0017(8) 0.0135(9) -0.0007(9) C11 0.0198(10) 0.0145(10) 0.0141(9) 0.0024(7) 0.0050(7) 0.0040(8) C12 0.0210(10) 0.0136(10) 0.0165(9) -0.0005(8) 0.0031(8) 0.0005(8) C13 0.0172(9) 0.0160(10) 0.0185(10) 0.0019(8) 0.0063(8) -0.0002(8) C14 0.0164(9) 0.0160(10) 0.0174(9) -0.0057(8) 0.0066(8) -0.0019(8) C15 0.0207(10) 0.0233(11) 0.0182(10) -0.0052(8) 0.0046(8) -0.0006(8) C16 0.0266(11) 0.0281(12) 0.0229(11) -0.0086(9) -0.0009(9) -0.0059(9) C17 0.0364(13) 0.0193(11) 0.0285(12) -0.0079(9) 0.0057(10) -0.0059(9) C18 0.0328(12) 0.0168(11) 0.0251(11) -0.0029(9) 0.0061(9) 0.0012(9) C19 0.0218(10) 0.0185(11) 0.0174(10) -0.0031(8) 0.0061(8) 0.0007(8) C20 0.0289(12) 0.0251(12) 0.0223(11) -0.0042(9) -0.0042(9) 0.0023(9) C21 0.0386(14) 0.0369(14) 0.0282(12) 0.0068(10) -0.0047(10) -0.0035(11) C22 0.0303(13) 0.0471(16) 0.0322(13) -0.0055(11) -0.0035(10) 0.0078(11) C23 0.0297(11) 0.0176(11) 0.0214(11) -0.0014(8) -0.0017(9) 0.0020(9) C24 0.0448(15) 0.0562(18) 0.0208(12) -0.0033(11) 0.0012(11) 0.0150(13) C25 0.0298(12) 0.0271(13) 0.0339(13) -0.0017(10) -0.0011(10) 0.0041(10) C26 0.0187(10) 0.0166(10) 0.0259(11) -0.0067(8) 0.0117(8) -0.0034(8) C27 0.0328(12) 0.0198(11) 0.0283(12) -0.0025(9) 0.0173(10) -0.0019(9) C28 0.0436(15) 0.0328(14) 0.0394(14) 0.0012(11) 0.0256(12) -0.0056(11) C29 0.0269(13) 0.0409(16) 0.0605(18) -0.0046(13) 0.0245(12) -0.0098(11) C30 0.0206(11) 0.0357(14) 0.0509(16) -0.0069(12) 0.0118(11) -0.0054(10) C31 0.0197(10) 0.0223(11) 0.0324(12) -0.0084(9) 0.0080(9) -0.0033(9) C32 0.0414(14) 0.0282(13) 0.0253(12) 0.0047(10) 0.0130(10) -0.0012(10) C33 0.0596(19) 0.0584(19) 0.0288(14) -0.0009(13) 0.0106(13) -0.0009(15) C34 0.065(2) 0.0331(16) 0.0520(18) 0.0074(13) 0.0106(15) 0.0091(14) S29

C35 0.0179(10) 0.0344(13) 0.0307(12) -0.0030(10) 0.0009(9) -0.0024(9) C36 0.0295(13) 0.0448(16) 0.0534(17) 0.0075(13) 0.0073(12) 0.0042(12) C37 0.0483(16) 0.0543(18) 0.0365(15) -0.0084(13) -0.0058(12) -0.0101(14) C38 0.0144(9) 0.0179(10) 0.0135(9) -0.0027(7) 0.0010(7) 0.0033(8) C39 0.0158(9) 0.0176(10) 0.0146(9) -0.0029(8) 0.0021(7) 0.0015(8) C40 0.0167(9) 0.0160(10) 0.0143(9) -0.0020(8) 0.0019(7) 0.0022(8) C41 0.0167(9) 0.0177(11) 0.0164(10) -0.0042(8) 0.0031(8) 0.0011(8) C42 0.0148(9) 0.0177(10) 0.0145(9) -0.0034(8) 0.0017(7) 0.0004(8) C43 0.0224(10) 0.0161(10) 0.0191(10) -0.0006(8) 0.0034(8) 0.0034(8) C44 0.0236(10) 0.0214(11) 0.0142(9) 0.0016(8) 0.0053(8) 0.0039(8) C45 0.0156(9) 0.0200(10) 0.0144(9) -0.0024(8) 0.0025(7) 0.0029(8) C46 0.0266(11) 0.0141(10) 0.0207(10) -0.0009(8) 0.0068(8) 0.0020(8) C47 0.0268(11) 0.0183(11) 0.0177(10) 0.0002(8) 0.0083(8) 0.0002(9) C48 0.0176(9) 0.0186(10) 0.0113(9) 0.0006(7) 0.0009(7) 0.0063(8) C49 0.0160(9) 0.0204(11) 0.0163(9) -0.0001(8) 0.0049(7) 0.0015(8) C50 0.0191(10) 0.0172(10) 0.0151(9) -0.0019(8) 0.0002(8) 0.0010(8) C51 0.0209(10) 0.0137(10) 0.0183(10) -0.0034(8) 0.0049(8) -0.0002(8) C52 0.0298(11) 0.0196(11) 0.0220(11) -0.0019(9) 0.0020(9) 0.0045(9) C53 0.0453(14) 0.0175(12) 0.0361(13) 0.0026(10) -0.0022(11) 0.0072(10) C54 0.0469(15) 0.0147(11) 0.0441(15) -0.0055(10) -0.0025(12) -0.0042(10) C55 0.0334(12) 0.0196(12) 0.0352(13) -0.0068(10) -0.0048(10) -0.0032(10) C56 0.0244(11) 0.0174(11) 0.0223(11) -0.0031(8) 0.0013(8) -0.0010(8) C57 0.0414(14) 0.0237(12) 0.0276(12) -0.0023(10) -0.0082(10) 0.0108(10) C58 0.0373(14) 0.0317(14) 0.0444(15) -0.0004(11) -0.0069(12) 0.0067(11) C59 0.059(2) 0.098(3) 0.0269(14) 0.0024(16) -0.0023(13) 0.0223(19) C60 0.0300(12) 0.0190(11) 0.0302(12) -0.0058(9) -0.0109(9) 0.0018(9) C61 0.079(2) 0.0354(15) 0.0312(14) 0.0027(12) -0.0108(14) 0.0123(15) C62 0.0307(14) 0.0330(15) 0.082(2) -0.0120(15) -0.0173(14) 0.0045(11) C63 0.0213(10) 0.0185(11) 0.0217(10) -0.0034(8) 0.0119(8) -0.0015(8) S30

C64 0.0225(11) 0.0301(13) 0.0295(12) -0.0080(10) 0.0089(9) -0.0030(9) C65 0.0251(12) 0.0551(18) 0.0466(16) -0.0058(13) 0.0144(11) -0.0139(12) C66 0.0423(16) 0.066(2) 0.0517(18) 0.0128(15) 0.0255(14) -0.0164(15) C67 0.0456(16) 0.0540(18) 0.0375(15) 0.0164(13) 0.0187(12) -0.0032(13) C68 0.0300(12) 0.0278(12) 0.0273(12) 0.0025(9) 0.0108(9) 0.0004(10) C69 0.0185(11) 0.0531(16) 0.0294(12) -0.0071(11) 0.0024(9) -0.0031(11) C70 0.0286(13) 0.070(2) 0.0481(17) -0.0229(15) -0.0054(12) -0.0001(13) C71 0.0462(16) 0.0492(18) 0.0500(17) 0.0055(14) -0.0132(13) -0.0040(14) C72 0.0324(13) 0.0370(14) 0.0249(12) 0.0087(10) 0.0055(10) 0.0044(10) C73 0.0511(17) 0.0512(18) 0.0292(13) 0.0043(12) 0.0037(12) 0.0049(14) C74 0.0485(17) 0.0566(19) 0.0459(17) 0.0000(14) 0.0046(13) 0.0182(15) C75 0.0267(13) 0.074(2) 0.0340(14) -0.0053(14) 0.0084(11) -0.0144(13) C76 0.0310(13) 0.060(2) 0.0411(15) 0.0215(14) -0.0031(11) -0.0158(13) C77 0.0419(15) 0.0301(14) 0.0610(19) 0.0080(13) 0.0012(13) -0.0107(12) C78 0.0456(15) 0.0379(15) 0.0409(15) -0.0051(12) 0.0113(12) -0.0086(12) C79 0.0569(17) 0.0322(15) 0.0417(15) 0.0083(12) 0.0206(13) -0.0033(13) C80 0.0494(17) 0.0336(15) 0.0571(18) -0.0045(13) 0.0227(14) -0.0037(12) C81 0.059(2) 0.147(4) 0.047(2) -0.032(2) 0.0235(17) -0.036(2) C82 0.0271(13) 0.0593(19) 0.0403(15) 0.0117(13) 0.0023(11) 0.0093(12) C83 0.0260(12) 0.0585(18) 0.0374(14) -0.0072(13) -0.0017(11) 0.0055(12) C84 0.0271(12) 0.0398(15) 0.0483(16) -0.0043(12) 0.0102(11) 0.0038(11) C85 0.0303(13) 0.0517(17) 0.0351(14) -0.0009(12) 0.0113(11) 0.0150(12) C86 0.0242(12) 0.0569(18) 0.0433(15) -0.0219(13) 0.0022(11) 0.0132(12) C87 0.0223(12) 0.0402(16) 0.0622(18) -0.0027(13) 0.0057(12) 0.0036(11) C88 0.055(2) 0.137(4) 0.063(2) 0.050(3) 0.0104(18) 0.006(2) C89 0.069(2) 0.082(3) 0.112(3) -0.016(2) 0.030(2) 0.018(2) C90 0.0329(15) 0.076(2) 0.112(3) -0.059(2) 0.0070(17) 0.0062(15) C91 0.0809(13) 0.0868(13) 0.0743(13) -0.0041(9) 0.0121(9) 0.0551(9) C92 0.062(2) 0.057(2) 0.116(3) 0.0034(19) 0.051(2) 0.0220(16) S31

C93 0.0299(16) 0.097(3) 0.081(3) -0.037(2) -0.0068(16) 0.0016(18) C94 0.039(2) 0.104(4) 0.121(4) 0.014(3) 0.008(2) 0.018(2) C95 0.151(5) 0.135(5) 0.140(5) 0.010(4) 0.056(4) 0.028(4) Table S7. Hydrogen atomic coordinates and isotropic atomic displacement parameters (Å 2 ) for 6 squeezed. x/a y/b z/c U(eq) H1 0.2648 0.2411 0.6537 0.018 H6 0.1020 0.2908 0.8505 0.02 H7 0.0464 0.3422 0.9256 0.021 H9 0.1059 0.5211 0.8666 0.028 H10 0.1604 0.4699 0.7901 0.026 H12-0.0487 0.4068 0.9512 0.02 H13-0.1047 0.4569 1.0276 0.02 H16 0.0598 0.0989 0.5804 0.031 H17 0.1065 0.0087 0.6344 0.033 H18 0.1864 0.0238 0.7169 0.03 H20 0.0851 0.2690 0.6243 0.031 H21A 0.1762 0.2600 0.5632 0.052 H21B 0.1102 0.2871 0.5228 0.052 H21C 0.1326 0.2110 0.5180 0.052 H22A 0.0055 0.1878 0.5398 0.055 H22B -0.0081 0.2647 0.5521 0.055 H22C -0.0200 0.2109 0.6031 0.055 H23 0.2575 0.1815 0.7674 0.028 H24A 0.1630 0.1659 0.8247 0.061 H24B 0.2313 0.1390 0.8621 0.061 H24C 0.1777 0.0879 0.8289 0.061 H25A 0.2819 0.0417 0.7764 0.046 H25B 0.3303 0.0974 0.8093 0.046 S32

H25C 0.3245 0.0916 0.7373 0.046 H28 0.4098 0.4082 0.5693 0.045 H29 0.5066 0.3806 0.6324 0.05 H30 0.4956 0.3322 0.7254 0.042 H32 0.2327 0.3746 0.5993 0.037 H33A 0.3151 0.3953 0.4999 0.073 H33B 0.2330 0.3853 0.4947 0.073 H33C 0.2828 0.3251 0.5163 0.073 H34A 0.2617 0.4837 0.6291 0.075 H34B 0.2237 0.4844 0.5625 0.075 H34C 0.3059 0.4927 0.5719 0.075 H35 0.3335 0.2902 0.7852 0.033 H36A 0.4074 0.2030 0.7603 0.064 H36B 0.4160 0.2173 0.8313 0.064 H36C 0.4730 0.2435 0.7888 0.064 H37A 0.4547 0.3643 0.8248 0.07 H37B 0.4016 0.3344 0.8692 0.07 H37C 0.3772 0.3919 0.8227 0.07 H38 0.7413 0.2279 0.6463 0.018 H43 0.6097 0.2801 0.8680 0.023 H44 0.5579 0.3380 0.9423 0.023 H46 0.5750 0.5083 0.8493 0.024 H47 0.6241 0.4506 0.7734 0.025 H49 0.5988 0.5425 0.9601 0.021 H50 0.5500 0.5985 1.0376 0.021 H53 0.7046 0.0010 0.7303 0.04 H54 0.6243-0.0213 0.6495 0.043 H55 0.5620 0.0637 0.6003 0.036 H57 0.7551 0.1654 0.7828 0.038 S33

H58A 0.8122 0.0349 0.7750 0.058 H58B 0.8506 0.0971 0.8074 0.058 H58C 0.8349 0.0964 0.7356 0.058 H59A 0.6741 0.1158 0.8433 0.093 H59B 0.7511 0.1062 0.8736 0.093 H59C 0.7123 0.0458 0.8386 0.093 H60 0.5801 0.2377 0.6377 0.033 H61A 0.6383 0.2105 0.5523 0.074 H61B 0.5630 0.2383 0.5313 0.074 H61C 0.5778 0.1603 0.5296 0.074 H62A 0.4759 0.1453 0.5943 0.074 H62B 0.4652 0.2236 0.6008 0.074 H62C 0.4790 0.1786 0.6598 0.074 H65 0.9492 0.3802 0.6540 0.05 H66 0.9154 0.4266 0.5614 0.063 H67 0.8008 0.4229 0.5226 0.054 H69 0.8342 0.3201 0.7589 0.04 H70A 0.9400 0.3408 0.8111 0.074 H70B 0.9226 0.4043 0.7695 0.074 H70C 0.9772 0.3505 0.7500 0.074 H71A 0.8581 0.2222 0.7067 0.074 H71B 0.9043 0.2273 0.7695 0.074 H71C 0.9377 0.2434 0.7077 0.074 H72 0.6629 0.3392 0.5912 0.038 H73A 0.7010 0.3859 0.4770 0.066 H73B 0.6293 0.3507 0.4881 0.066 H73C 0.6999 0.3094 0.4959 0.066 H74A 0.6566 0.4496 0.6210 0.075 H74B 0.6065 0.4396 0.5609 0.075 S34

H74C 0.6802 0.4745 0.5575 0.075 H76 0.0172 0.1945 0.8245 0.053 H77-0.0113 0.2381 0.9150 0.053 H78-0.0403 0.1687 0.9927 0.049 H79-0.0385 0.0542 0.9787 0.051 H80-0.0103 0.0101 0.8877 0.055 H81A -0.0228 0.0534 0.7642 0.125 H81B 0.0524 0.0315 0.7921 0.125 H81C 0.0413 0.1030 0.7617 0.125 H83 0.2234 0.0914 0.4242 0.049 H84 0.2019 0.0493 0.5178 0.046 H85 0.2613 0.0922 0.6051 0.046 H86 0.3418 0.1764 0.5968 0.05 H87 0.3620 0.2191 0.5031 0.05 H88A 0.3084 0.1511 0.3635 0.127 H88B 0.3500 0.2122 0.3948 0.127 H88C 0.2682 0.2176 0.3789 0.127 H90 0.8513 0.2179 0.5721 0.088 H91 0.8102 0.1233 0.6206 0.096 H92 0.7266 0.0495 0.5523 0.091 H93 0.7123 0.0866 0.4513 0.084 H94 0.7658 0.1756 0.4204 0.106 H95A 0.8911 0.2515 0.4541 0.21 H95B 0.8372 0.2999 0.4827 0.21 H95C 0.8169 0.2645 0.4194 0.21 S35

Crystal Structure Report for 7 2 C2H3N A specimen of C 80 H 89 K 2 N 7 O 4 S 2, approximate dimensions 0.103 mm x 0.209 mm x 0.211 mm, was used for the X-ray crystallographic analysis. The X-ray intensity data were measured. The integration of the data using a monoclinic unit cell yielded a total of 103461 reflections to a maximum θ angle of 26.80 (0.79 Å resolution), of which 8620 were independent (average redundancy 12.002, completeness = 99.7%, R int = 4.79%, R sig = 2.11%) and 6977 (80.94%) were greater than 2σ(F 2 ). The final cell constants of a = 12.3149(10) Å, b = 18.8123(16) Å, c = 18.4296(16) Å, β = 109.037(3), volume = 4036.1(6) Å 3, are based upon the refinement of the XYZ-centroids of reflections above 20 σ(i). The calculated minimum and maximum transmission coefficients (based on crystal size) are 0.9580 and 1.0000. The structure was solved and refined using the Bruker SHELXTL Software Package, using the space group P 1 21/c 1, with Z = 2 for the formula unit, C 80 H 89 K 2 N 7 O 4 S 2. The final anisotropic full-matrix least-squares refinement on F 2 with 425 variables converged at R1 = 5.61%, for the observed data and wr2 = 19.79% for all data. The goodness-of-fit was 1.069. The largest peak in the final difference electron density synthesis was 1.515 e - /Å 3 and the largest hole was -0.476 e - /Å 3 with an RMS deviation of 0.097 e - /Å 3. On the basis of the final model, the calculated density was 1.115 g/cm 3 and F(000), 1440 e -. Figure S20. Solid state molecular structure of 7 S36

Figure S21. Solid state packing diagram of 7 Table S8. Sample and crystal data for 7. Chemical formula C 80 H 89 K 2 N 7 O 4 S 2 Formula weight Temperature Wavelength Crystal size Crystal system 1354.90 g/mol 100(2) K 0.71073 Å 0.103 x 0.209 x 0.211 mm monoclinic Space group P 1 21/c 1 Unit cell dimensions a = 12.3149(10) Å α = 90 b = 18.8123(16) Å β = 109.037(3) c = 18.4296(16) Å γ = 90 Volume 4036.1(6) Å 3 Z 2 Density (calculated) 1.115 g/cm 3 Absorption coefficient 0.218 mm -1 F(000) 1440 S37

Table S9. Data collection and structure refinement for 7. Theta range for data collection 2.06 to 26.80 Index ranges -14 h 15, -23 k 23, -23 l 23 Reflections collected 103461 Independent reflections 8620 [R(int) = 0.0479] Max. and min. transmission 1.0000 and 0.9580 Structure solution technique direct methods Structure solution program SHELXT-2014 (Sheldrick 2014) Refinement method Full-matrix least-squares on F 2 Refinement program SHELXL-2014 (Sheldrick 2014) Function minimized 2 Σ w(f o - F c2 ) 2 Data / restraints / parameters 8620 / 6 / 425 Goodness-of-fit on F 2 1.069 Δ/σmax 0.001 Final R indices 6977 data; I>2σ(I) R1 = 0.0561, wr2 = 0.1830 all data R1 = 0.0704, wr2 = 0.1979 Weighting scheme w=1/[σ 2 (F o2 )+(0.1153P) 2 +3.6118P] where P=(F o2 +2F c2 )/3 Largest diff. peak and hole 1.515 and -0.476 eå -3 R.M.S. deviation from mean 0.097 eå -3 Table S10. Atomic coordinates and equivalent isotropic atomic displacement parameters (Å 2 ) for 7. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x/a y/b z/c U(eq) K1 0.68874(5) 0.26582(3) 0.50839(3) 0.03338(17) S1 0.42108(5) 0.44905(3) 0.13169(3) 0.02948(17) O1 0.58501(14) 0.31112(9) 0.36954(9) 0.0278(4) O2 0.67480(16) 0.24337(9) 0.14913(9) 0.0325(4) N1 0.55672(16) 0.33653(10) 0.14842(10) 0.0236(4) S38

N2 0.50227(16) 0.36493(10) 0.25396(10) 0.0224(4) C1 0.49619(19) 0.38064(12) 0.18023(12) 0.0225(4) C2 0.58025(19) 0.31392(11) 0.30137(12) 0.0221(4) C3 0.64097(19) 0.27149(11) 0.26509(12) 0.0222(4) C4 0.62799(19) 0.27929(12) 0.18699(12) 0.0234(5) C5 0.71957(19) 0.21592(12) 0.31033(12) 0.0221(4) C6 0.8054(2) 0.23279(12) 0.37934(13) 0.0241(5) C7 0.87514(19) 0.18056(12) 0.42387(12) 0.0243(5) C8 0.86293(18) 0.10928(12) 0.40100(12) 0.0216(4) C9 0.77951(19) 0.09271(12) 0.33091(12) 0.0236(5) C10 0.70953(19) 0.14509(12) 0.28672(12) 0.0245(5) C11 0.93400(18) 0.05295(11) 0.45052(12) 0.0213(4) C12 0.04440(19) 0.06716(12) 0.50027(13) 0.0246(5) C13 0.10890(19) 0.01559(12) 0.54871(13) 0.0248(5) C14 0.4318(2) 0.40505(13) 0.28874(13) 0.0283(5) C15 0.3166(2) 0.38452(15) 0.27205(15) 0.0355(6) C16 0.2509(3) 0.42340(19) 0.30730(17) 0.0485(8) C17 0.2981(3) 0.4791(2) 0.35585(19) 0.0572(10) C18 0.4110(3) 0.49814(17) 0.37049(17) 0.0504(8) C19 0.4806(2) 0.46145(14) 0.33671(15) 0.0361(6) C20 0.2645(2) 0.32513(16) 0.21553(17) 0.0409(6) C21 0.2987(3) 0.25158(18) 0.2502(2) 0.0549(8) C22 0.1341(3) 0.3283(2) 0.1811(2) 0.0585(9) C23 0.6038(3) 0.48501(15) 0.35126(17) 0.0444(7) C24 0.6725(4) 0.4842(2) 0.4370(2) 0.0633(10) C25 0.6085(4) 0.55793(19) 0.3167(2) 0.0615(9) C26 0.5540(2) 0.35069(12) 0.07082(12) 0.0252(5) C27 0.4696(2) 0.31735(14) 0.01045(14) 0.0314(5) C28 0.4719(3) 0.33067(16) 0.93637(14) 0.0400(7) S39

C29 0.5554(3) 0.37350(15) 0.92375(15) 0.0407(7) C30 0.6373(2) 0.40522(15) 0.98467(16) 0.0377(6) C31 0.6385(2) 0.39488(13) 0.06009(14) 0.0296(5) C32 0.3801(2) 0.26839(16) 0.02313(16) 0.0401(6) C33 0.2592(3) 0.2940(2) 0.9781(3) 0.0672(10) C34 0.3986(3) 0.19159(18) 0.0017(2) 0.0573(8) C35 0.7290(2) 0.43118(14) 0.12612(16) 0.0350(6) C36 0.7267(3) 0.51161(17) 0.1150(2) 0.0576(9) C37 0.8476(3) 0.4004(2) 0.1360(2) 0.0553(8) N3 0.8983(5) 0.3272(3) 0.5851(4) 0.0628(16) C38 0.9299(5) 0.3328(4) 0.6513(5) 0.0557(18) C39 0.9671(5) 0.3350(5) 0.7354(4) 0.065(2) Table S11. Bond lengths (Å) for 7. K1-O1 2.6026(16) K1-O2 2.6603(17) K1-N3 2.760(5) K1-C27 3.130(2) K1-C28 3.142(3) K1-C26 3.182(2) K1-C29 3.214(3) K1-C6 3.215(2) K1-C30 3.281(3) K1-C31 3.289(2) K1-C38 3.498(6) S1-C1 1.665(2) O1-C2 1.240(3) O2-C4 1.240(3) O2-K1 2.6604(17) N1-C1 1.369(3) N1-C4 1.424(3) N1-C26 1.444(3) N2-C1 1.369(3) N2-C2 1.435(3) N2-C14 1.448(3) C2-C3 1.404(3) C3-C4 1.403(3) C3-C5 1.483(3) C5-C10 1.395(3) C5-C6 1.399(3) C6-C7 1.385(3) C6-H6 0.95 C7-C8 1.399(3) C7-H7 0.95 S40

C8-C9 1.398(3) C8-C11 1.483(3) C9-C10 1.385(3) C9-H9 0.95 C10-H10 0.95 C11-C13 1.395(3) C11-C12 1.395(3) C12-C13 1.381(3) C12-H12 0.95 C13-C11 1.395(3) C13-H13 0.95 C14-C19 1.386(4) C14-C15 1.404(4) C15-C16 1.398(4) C15-C20 1.520(4) C16-C17 1.378(5) C16-H16 0.95 C17-C18 1.374(5) C17-H17 0.95 C18-C19 1.395(4) C18-H18 0.95 C19-C23 1.518(4) C20-C22 1.524(4) C20-C21 1.525(4) C20-H20 1.0 C21-H21A 0.98 C21-H21B 0.98 C21-H21C 0.98 C22-H22A 0.98 C22-H22B 0.98 C22-H22C 0.98 C23-C25 1.521(5) C23-C24 1.530(4) C23-H23 1.0 C24-H24A 0.98 C24-H24B 0.98 C24-H24C 0.98 C25-H25A 0.98 C25-H25B 0.98 C25-H25C 0.98 C26-C31 1.396(4) C26-C27 1.399(4) C26-K1 3.182(2) C27-C28 1.398(3) C27-C32 1.511(4) C27-K1 3.130(2) C28-C29 1.384(4) C28-K1 3.142(3) C28-H28 0.95 C29-C30 1.377(4) C29-K1 3.214(3) C29-H29 0.95 C30-C31 1.399(3) C30-K1 3.281(3) C30-H30 0.95 C31-C35 1.518(4) C31-K1 3.289(2) C32-C33 1.528(4) S41

C32-C34 1.534(4) C32-H32 1.0 C33-H33A 0.98 C33-H33B 0.98 C33-H33C 0.98 C34-H34A 0.98 C34-H34B 0.98 C34-H34C 0.98 C35-C37 1.525(4) C35-C36 1.526(4) C35-H35 1.0 C36-H36A 0.98 C36-H36B 0.98 C36-H36C 0.98 C37-H37A 0.98 C37-H37B 0.98 C37-H37C 0.98 N3-C38 1.157(10) C38-C39 1.468(11) C39-H39A 0.98 C39-H39B 0.98 C39-H39C 0.98 Table S12. Bond angles ( ) for 7. O1-K1-O2 144.37(6) O1-K1-N3 116.34(16) O2-K1-N3 82.80(15) O1-K1-C27 91.54(6) O2-K1-C27 68.01(6) N3-K1-C27 150.34(16) O1-K1-C28 72.35(6) O2-K1-C28 93.33(6) N3-K1-C28 169.17(16) C27-K1-C28 25.75(6) O1-K1-C26 115.74(6) O2-K1-C26 52.82(5) N3-K1-C26 127.88(16) C27-K1-C26 25.59(6) C28-K1-C26 44.22(6) O1-K1-C29 77.33(7) O2-K1-C29 103.59(6) N3-K1-C29 146.59(16) C27-K1-C29 44.94(7) C28-K1-C29 25.12(8) C26-K1-C29 50.92(6) O1-K1-C6 61.99(5) O2-K1-C6 153.54(6) N3-K1-C6 83.75(15) C27-K1-C6 120.49(6) C28-K1-C6 95.68(7) C26-K1-C6 123.09(6) C29-K1-C6 76.37(6) O1-K1-C30 100.29(7) O2-K1-C30 89.73(6) S42

N3-K1-C30 125.91(16) C27-K1-C30 51.82(7) C28-K1-C30 43.68(8) C26-K1-C30 43.29(6) C29-K1-C30 24.45(8) C6-K1-C30 79.93(6) O1-K1-C31 120.50(6) O2-K1-C31 65.15(6) N3-K1-C31 117.99(16) C27-K1-C31 44.98(7) C28-K1-C31 51.47(7) C26-K1-C31 24.85(6) C29-K1-C31 43.64(6) C6-K1-C31 102.03(6) C30-K1-C31 24.59(6) O1-K1-C38 130.25(14) O2-K1-C38 66.33(13) N3-K1-C38 16.48(19) C27-K1-C38 133.98(14) C28-K1-C38 157.18(14) C26-K1-C38 113.00(14) C29-K1-C38 146.40(14) C6-K1-C38 98.74(13) C30-K1-C38 122.20(14) C31-K1-C38 107.86(14) C2-O1-K1 148.89(15) C4-O2-K1 140.68(14) C1-N1-C4 125.29(18) C1-N1-C26 118.19(17) C4-N1-C26 116.44(17) C1-N2-C2 123.92(18) C1-N2-C14 118.70(18) C2-N2-C14 117.25(17) N2-C1-N1 115.68(18) N2-C1-S1 122.77(17) N1-C1-S1 121.54(16) O1-C2-C3 127.0(2) O1-C2-N2 116.53(19) C3-C2-N2 116.42(18) C4-C3-C2 121.94(19) C4-C3-C5 119.05(19) C2-C3-C5 118.99(19) O2-C4-C3 127.0(2) O2-C4-N1 117.07(19) C3-C4-N1 115.89(19) C10-C5-C6 117.65(19) C10-C5-C3 121.5(2) C6-C5-C3 120.8(2) C7-C6-C5 121.1(2) C7-C6-K1 92.24(14) C5-C6-K1 109.21(15) C7-C6-H6 119.5 C5-C6-H6 119.5 K1-C6-H6 68.0 C6-C7-C8 121.1(2) C6-C7-H7 119.4 C8-C7-H7 119.4 C9-C8-C7 117.80(19) S43

C9-C8-C11 121.1(2) C7-C8-C11 121.04(19) C10-C9-C8 120.9(2) C10-C9-H9 119.6 C8-C9-H9 119.6 C9-C10-C5 121.4(2) C9-C10-H10 119.3 C5-C10-H10 119.3 C13-C11-C12 117.47(19) C13-C11-C8 121.13(19) C12-C11-C8 121.3(2) C13-C12-C11 121.5(2) C13-C12-H12 119.3 C11-C12-H12 119.3 C12-C13-C11 121.1(2) C12-C13-H13 119.5 C11-C13-H13 119.5 C19-C14-C15 123.2(2) C19-C14-N2 118.9(2) C15-C14-N2 117.9(2) C16-C15-C14 116.8(3) C16-C15-C20 121.6(3) C14-C15-C20 121.5(2) C17-C16-C15 120.9(3) C17-C16-H16 119.5 C15-C16-H16 119.5 C18-C17-C16 120.8(3) C18-C17-H17 119.6 C16-C17-H17 119.6 C17-C18-C19 120.9(3) C17-C18-H18 119.6 C19-C18-H18 119.6 C14-C19-C18 117.5(3) C14-C19-C23 122.5(2) C18-C19-C23 120.0(3) C15-C20-C22 114.1(3) C15-C20-C21 112.5(2) C22-C20-C21 108.7(3) C15-C20-H20 107.1 C22-C20-H20 107.1 C21-C20-H20 107.1 C20-C21-H21A 109.5 C20-C21-H21B 109.5 H21A-C21-H21B 109.5 C20-C21-H21C 109.5 H21A-C21-H21C 109.5 H21B-C21-H21C 109.5 C20-C22-H22A 109.5 C20-C22-H22B 109.5 H22A-C22-H22B 109.5 C20-C22-H22C 109.5 H22A-C22-H22C 109.5 H22B-C22-H22C 109.5 C19-C23-C25 111.2(3) C19-C23-C24 111.3(3) C25-C23-C24 111.0(3) C19-C23-H23 107.7 C25-C23-H23 107.7 S44

C24-C23-H23 107.7 C23-C24-H24A 109.5 C23-C24-H24B 109.5 H24A-C24-H24B 109.5 C23-C24-H24C 109.5 H24A-C24-H24C 109.5 H24B-C24-H24C 109.5 C23-C25-H25A 109.5 C23-C25-H25B 109.5 H25A-C25-H25B 109.5 C23-C25-H25C 109.5 H25A-C25-H25C 109.5 H25B-C25-H25C 109.5 C31-C26-C27 123.3(2) C31-C26-N1 118.2(2) C27-C26-N1 118.4(2) C31-C26-K1 81.83(13) C27-C26-K1 75.13(13) N1-C26-K1 112.61(13) C28-C27-C26 116.7(3) C28-C27-C32 120.6(2) C26-C27-C32 122.7(2) C28-C27-K1 77.60(15) C26-C27-K1 79.28(14) C32-C27-K1 111.84(16) C29-C28-C27 121.4(3) C29-C28-K1 80.33(16) C27-C28-K1 76.65(14) C29-C28-H28 119.3 C27-C28-H28 119.3 K1-C28-H28 114.1 C30-C29-C28 120.2(2) C30-C29-K1 80.50(15) C28-C29-K1 74.55(15) C30-C29-H29 119.9 C28-C29-H29 119.9 K1-C29-H29 115.6 C29-C30-C31 121.1(3) C29-C30-K1 75.05(16) C31-C30-K1 78.01(14) C29-C30-H30 119.4 C31-C30-H30 119.4 K1-C30-H30 118.3 C26-C31-C30 117.2(2) C26-C31-C35 122.7(2) C30-C31-C35 120.0(2) C26-C31-K1 73.32(13) C30-C31-K1 77.40(15) C35-C31-K1 119.17(15) C27-C32-C33 110.7(3) C27-C32-C34 110.9(2) C33-C32-C34 111.0(3) C27-C32-H32 108.0 C33-C32-H32 108.0 C34-C32-H32 108.0 C32-C33-H33A 109.5 C32-C33-H33B 109.5 H33A-C33-H33B 109.5 S45

C32-C33-H33C 109.5 H33A-C33-H33C 109.5 H33B-C33-H33C 109.5 C32-C34-H34A 109.5 C32-C34-H34B 109.5 H34A-C34-H34B 109.5 C32-C34-H34C 109.5 H34A-C34-H34C 109.5 H34B-C34-H34C 109.5 C31-C35-C37 110.4(2) C31-C35-C36 111.2(2) C37-C35-C36 111.6(3) C31-C35-H35 107.8 C37-C35-H35 107.8 C36-C35-H35 107.8 C35-C36-H36A 109.5 C35-C36-H36B 109.5 H36A-C36-H36B 109.5 C35-C36-H36C 109.5 H36A-C36-H36C 109.5 H36B-C36-H36C 109.5 C35-C37-H37A 109.5 C35-C37-H37B 109.5 H37A-C37-H37B 109.5 C35-C37-H37C 109.5 H37A-C37-H37C 109.5 H37B-C37-H37C 109.5 C38-N3-K1 120.9(5) N3-C38-C39 176.2(8) N3-C38-K1 42.6(3) C39-C38-K1 134.5(5) C38-C39-H39A 109.5 C38-C39-H39B 109.5 H39A-C39-H39B 109.5 C38-C39-H39C 109.5 H39A-C39-H39C 109.5 H39B-C39-H39C 109.5 Table S13. Anisotropic atomic displacement parameters (Å 2 ) for 7. The anisotropic atomic displacement factor exponent takes the form: -2π 2 [ h 2 a *2 U 11 +... + 2 h k a * b * U 12 ] U11 U22 U33 U23 U13 U12 K1 0.0414(3) 0.0384(3) 0.0193(3) 0.0033(2) 0.0086(2) -0.0104(2) S1 0.0348(3) 0.0291(3) 0.0256(3) 0.0104(2) 0.0113(2) 0.0154(2) O1 0.0364(9) 0.0310(9) 0.0169(7) 0.0050(6) 0.0099(7) 0.0082(7) O2 0.0457(10) 0.0336(9) 0.0206(8) 0.0067(7) 0.0140(7) 0.0195(8) N1 0.0302(10) 0.0248(9) 0.0167(9) 0.0063(7) 0.0088(7) 0.0097(8) N2 0.0265(9) 0.0232(9) 0.0185(9) 0.0043(7) 0.0088(7) 0.0072(7) C1 0.0245(11) 0.0232(11) 0.0196(10) 0.0039(8) 0.0069(8) 0.0044(8) S46

C2 0.0251(11) 0.0214(10) 0.0193(10) 0.0040(8) 0.0064(8) 0.0020(8) C3 0.0253(11) 0.0210(10) 0.0181(10) 0.0048(8) 0.0044(8) 0.0058(8) C4 0.0271(11) 0.0230(11) 0.0201(10) 0.0051(8) 0.0077(9) 0.0086(9) C5 0.0236(10) 0.0231(11) 0.0183(10) 0.0050(8) 0.0050(8) 0.0057(8) C6 0.0273(11) 0.0200(10) 0.0231(11) 0.0004(8) 0.0058(9) 0.0016(8) C7 0.0236(11) 0.0250(11) 0.0199(10) 0.0021(8) 0.0012(8) 0.0020(8) C8 0.0212(10) 0.0231(10) 0.0196(10) 0.0049(8) 0.0054(8) 0.0042(8) C9 0.0268(11) 0.0204(10) 0.0212(10) 0.0003(8) 0.0043(9) 0.0036(8) C10 0.0267(11) 0.0254(11) 0.0176(10) 0.0021(8) 0.0020(8) 0.0029(9) C11 0.0208(10) 0.0226(10) 0.0193(10) 0.0042(8) 0.0049(8) 0.0044(8) C12 0.0220(10) 0.0216(10) 0.0276(11) 0.0046(9) 0.0043(9) 0.0004(8) C13 0.0190(10) 0.0242(11) 0.0264(11) 0.0033(9) 0.0009(8) 0.0021(8) C14 0.0366(13) 0.0301(12) 0.0211(11) 0.0080(9) 0.0133(9) 0.0138(10) C15 0.0358(13) 0.0434(15) 0.0322(13) 0.0150(11) 0.0176(11) 0.0158(11) C16 0.0459(16) 0.065(2) 0.0431(16) 0.0169(15) 0.0261(13) 0.0226(15) C17 0.074(2) 0.067(2) 0.0443(17) 0.0114(16) 0.0377(17) 0.0375(19) C18 0.078(2) 0.0425(16) 0.0369(15) -0.0009(13) 0.0274(15) 0.0208(16) C19 0.0519(16) 0.0332(13) 0.0257(12) 0.0033(10) 0.0162(11) 0.0138(12) C20 0.0308(13) 0.0527(17) 0.0399(15) 0.0135(13) 0.0123(11) 0.0038(12) C21 0.0394(16) 0.0512(18) 0.063(2) 0.0157(16) 0.0015(15) -0.0012(14) C22 0.0356(16) 0.076(2) 0.058(2) 0.0264(18) 0.0083(14) 0.0056(15) C23 0.0583(18) 0.0343(14) 0.0370(15) -0.0072(11) 0.0108(13) 0.0010(13) C24 0.076(2) 0.054(2) 0.0449(18) -0.0077(15) -0.0007(17) -0.0038(18) C25 0.077(2) 0.050(2) 0.055(2) -0.0003(16) 0.0174(18) -0.0118(17) C26 0.0324(12) 0.0278(11) 0.0169(10) 0.0079(8) 0.0098(9) 0.0141(9) C27 0.0378(13) 0.0341(13) 0.0221(11) 0.0035(9) 0.0097(10) 0.0141(10) C28 0.0499(16) 0.0468(16) 0.0203(12) 0.0038(11) 0.0073(11) 0.0212(13) C29 0.0586(18) 0.0457(16) 0.0236(12) 0.0149(11) 0.0212(12) 0.0258(13) C30 0.0479(15) 0.0369(14) 0.0374(14) 0.0170(11) 0.0264(12) 0.0189(12) S47

C31 0.0352(13) 0.0271(12) 0.0298(12) 0.0090(9) 0.0150(10) 0.0150(10) C32 0.0412(15) 0.0458(16) 0.0307(13) -0.0043(11) 0.0080(11) 0.0034(12) C33 0.0391(17) 0.066(2) 0.092(3) 0.001(2) 0.0158(18) 0.0070(16) C34 0.061(2) 0.0419(17) 0.067(2) -0.0014(16) 0.0192(17) 0.0016(15) C35 0.0361(13) 0.0352(13) 0.0386(14) 0.0046(11) 0.0188(11) 0.0058(11) C36 0.062(2) 0.0368(16) 0.077(2) 0.0021(16) 0.0274(18) 0.0020(15) C37 0.0393(16) 0.066(2) 0.059(2) 0.0002(17) 0.0145(14) 0.0141(15) N3 0.037(2) 0.071(3) 0.075(3) -0.018(3) 0.011(2) -0.037(2) C38 0.016(2) 0.060(4) 0.089(5) -0.020(4) 0.014(3) -0.012(2) C39 0.038(3) 0.115(7) 0.047(4) -0.025(4) 0.022(3) 0.021(4) Table S14. Hydrogen atomic coordinates and isotropic atomic displacement parameters (Å 2 ) for 7. x/a y/b z/c U(eq) H6 0.8160 0.2809 0.3959 0.029 H7 0.9323 0.1933 0.4707 0.029 H9 0.7707 0.0449 0.3134 0.028 H10 0.6535 0.1325 0.2393 0.029 H12 1.0759 0.1133 0.5008 0.03 H13 1.1837 0.0270 0.5821 0.03 H16 0.1726 0.4112 0.2976 0.058 H17 0.2522 0.5047 0.3795 0.069 H18 0.4420 0.5368 0.4040 0.06 H20 0.2959 0.3301 0.1721 0.049 H21A 0.2681 0.2444 0.2925 0.082 H21B 0.3827 0.2478 0.2696 0.082 H21C 0.2675 0.2153 0.2107 0.082 H22A 0.1078 0.2937 0.1394 0.088 H22B 0.1107 0.3762 0.1610 0.088 H22C 0.0998 0.3173 0.2209 0.088 S48

H23 0.6403 0.4503 0.3253 0.053 H24A 0.6366 0.5163 0.4643 0.095 H24B 0.7514 0.4998 0.4446 0.095 H24C 0.6737 0.4358 0.4570 0.095 H25A 0.5658 0.5568 0.2616 0.092 H25B 0.6887 0.5707 0.3246 0.092 H25C 0.5742 0.5933 0.3417 0.092 H28 0.4150 0.3099-0.1063 0.048 H29 0.5561 0.3811-0.1271 0.049 H30 0.6941 0.4346-0.0247 0.045 H32 0.3887 0.2695 0.0790 0.048 H33A 0.2534 0.3452-0.0137 0.101 H33B 0.2031 0.2686-0.0042 0.101 H33C 0.2435 0.2848-0.0767 0.101 H34A 0.3982 0.1900-0.0515 0.086 H34B 0.3367 0.1615 0.0070 0.086 H34C 0.4726 0.1742 0.0359 0.086 H35 0.7107 0.4212 0.1741 0.042 H36A 0.7445 0.5229 0.0682 0.086 H36B 0.7839 0.5338 0.1593 0.086 H36C 0.6502 0.5298 0.1104 0.086 H37A 0.8480 0.3495 0.1476 0.083 H37B 0.9052 0.4248 0.1783 0.083 H37C 0.8658 0.4071 0.0885 0.083 H39A 0.9000 0.3303 0.7526 0.097 H39B 1.0056 0.3803 0.7535 0.097 H39C 1.0205 0.2958 0.7564 0.097 S49

Crystal Structure Report for 8 (C110H110Au2N4O4P2 C7H8) A specimen of C 117 H 118 Au 2 N 4 O 4 P 2, approximate dimensions 0.034 mm x 0.176 mm x 0.391 mm, was used for the X-ray crystallographic analysis. The X-ray intensity data were measured. The integration of the data using a monoclinic unit cell yielded a total of 70789 reflections to a maximum θ angle of 27.00 (0.78 Å resolution), of which 11407 were independent (average redundancy 6.206, completeness = 99.9%, R int = 5.26%, R sig = 3.62%) and 9290 (81.44%) were greater than 2σ(F 2 ). The final cell constants of a = 33.0879(14) Å, b = 14.4747(6) Å, c = 26.0816(10) Å, β = 123.1660(10), volume = 10456.5(7) Å 3, are based upon the refinement of the XYZ-centroids of reflections above 20 σ(i). The calculated minimum and maximum transmission coefficients (based on crystal size) are 0.7000 and 1.0000. The structure was solved and refined using the Bruker SHELXTL Software Package, using the space group C 1 2/c 1, with Z = 4 for the formula unit, C 117 H 118 Au 2 N 4 O 4 P 2. The final anisotropic full-matrix least-squares refinement on F 2 with 622 variables converged at R1 = 3.87%, for the observed data and wr2 = 12.28% for all data. The goodness-of-fit was 1.061. The largest peak in the final difference electron density synthesis was 2.420 e - /Å 3 and the largest hole was -1.274 e - /Å 3 with an RMS deviation of 0.211 e - /Å 3. On the basis of the final model, the calculated density was 1.334 g/cm 3 and F(000), 4272 e -. Figure S22. Solid state molecular structure of 8 Table S15. Sample and crystal data for 8 (C 110 H 110 Au 2 N 4 O 4 P 2 C 7 H 8 ) Chemical formula C 117 H 118 Au 2 N 4 O 4 P 2 Formula weight Temperature Wavelength Crystal size Crystal system 2100.02 g/mol 100(2) K 0.71073 Å 0.034 x 0.176 x 0.391 mm monoclinic Space group C 1 2/c 1 S50

Unit cell dimensions a = 33.0879(14) Å α = 90 b = 14.4747(6) Å β = 123.1660(10) c = 26.0816(10) Å γ = 90 Volume 10456.5(7) Å 3 Z 4 Density (calculated) 1.334 g/cm 3 Absorption coefficient 2.886 mm -1 F(000) 4272 Table S16. Data collection and structure refinement for 8. Theta range for data collection 2.04 to 27.00 Index ranges -42 h 42, -18 k 18, -33 l 28 Reflections collected 70789 Independent reflections 11407 [R(int) = 0.0526] Max. and min. transmission 1.0000 and 0.7000 Structure solution technique direct methods Structure solution program SHELXT-2014 (Sheldrick 2014) Refinement method Full-matrix least-squares on F 2 Refinement program SHELXL-2014 (Sheldrick 2014) Function minimized 2 Σ w(f o - F c2 ) 2 Data / restraints / parameters 11407 / 44 / 622 Goodness-of-fit on F 2 1.061 Δ/σmax 0.001 Final R indices 9290 data; I>2σ(I) R1 = 0.0387, wr2 = 0.1081 all data R1 = 0.0541, wr2 = 0.1228 Weighting scheme w=1/[σ 2 (F o2 )+(0.0608P) 2 +104.7210P] where P=(F o2 +2F c2 )/3 Largest diff. peak and hole 2.420 and -1.274 eå -3 R.M.S. deviation from mean 0.211 eå -3 S51

Table S17. Atomic coordinates and equivalent isotropic atomic displacement parameters (Å 2 ) for 8. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x/a y/b z/c U(eq) Au1 0.18959(2) 0.52440(2) 0.36128(2) 0.01721(7) P1 0.12875(5) 0.50041(9) 0.37685(6) 0.0181(3) O1 0.24907(15) 0.4930(4) 0.21381(19) 0.0386(11) O2 0.36983(14) 0.5363(3) 0.42320(18) 0.0316(9) N1 0.28965(14) 0.5311(3) 0.38687(19) 0.0173(8) N2 0.23129(15) 0.5160(3) 0.28544(19) 0.0175(8) C1 0.24265(18) 0.5252(3) 0.3429(2) 0.0177(10) C2 0.26600(19) 0.5055(4) 0.2682(2) 0.0214(10) C3 0.31477(18) 0.5104(3) 0.3164(2) 0.0185(10) C4 0.32885(18) 0.5260(3) 0.3773(2) 0.0198(10) C5 0.35250(18) 0.5017(3) 0.3023(2) 0.0199(10) C6 0.3452(2) 0.5370(4) 0.2481(3) 0.0253(11) C7 0.3809(2) 0.5324(4) 0.2354(3) 0.0243(11) C8 0.42474(19) 0.4905(4) 0.2756(3) 0.0224(11) C9 0.43222(19) 0.4523(4) 0.3294(3) 0.0244(11) C10 0.3970(2) 0.4575(4) 0.3427(3) 0.0251(11) C11 0.46337(19) 0.4886(3) 0.2627(3) 0.0223(11) C12 0.51212(19) 0.4892(4) 0.3100(3) 0.0228(11) C13 0.45216(19) 0.4890(4) 0.2028(3) 0.0238(11) C14 0.18046(19) 0.5071(4) 0.2364(2) 0.0212(10) C15 0.15332(19) 0.5862(4) 0.2096(2) 0.0247(11) C16 0.1047(2) 0.5737(5) 0.1621(3) 0.0330(13) C17 0.0859(2) 0.4864(5) 0.1432(3) 0.0379(15) C18 0.1143(2) 0.4089(5) 0.1703(3) 0.0329(13) C19 0.16241(19) 0.4175(4) 0.2181(2) 0.0256(11) C20 0.1731(2) 0.6832(4) 0.2290(3) 0.0313(13) C21 0.1457(3) 0.7391(5) 0.2502(3) 0.0504(18) S52

C22 0.1741(3) 0.7349(5) 0.1782(3) 0.0444(16) C23 0.1935(2) 0.3322(4) 0.2486(3) 0.0321(13) C24 0.1812(3) 0.2847(5) 0.2905(3) 0.0474(17) C25 0.1915(3) 0.2644(6) 0.2027(4) 0.058(2) C26 0.30277(18) 0.5420(4) 0.4496(2) 0.0218(11) C27 0.3065(2) 0.6315(4) 0.4719(3) 0.0304(12) C28 0.3173(2) 0.6394(5) 0.5312(3) 0.0408(15) C29 0.3249(2) 0.5627(6) 0.5665(3) 0.0434(17) C30 0.3225(2) 0.4748(5) 0.5434(3) 0.0374(15) C31 0.3114(2) 0.4626(4) 0.4840(3) 0.0297(12) C32 0.3000(3) 0.7164(4) 0.4342(3) 0.0392(15) C33 0.3445(3) 0.7780(6) 0.4660(5) 0.068(2) C34 0.2558(3) 0.7709(6) 0.4190(4) 0.065(2) C35 0.3101(3) 0.3672(5) 0.4598(3) 0.0449(17) C36 0.3610(3) 0.3295(6) 0.4878(4) 0.066(2) C37 0.2798(3) 0.3004(5) 0.4699(4) 0.064(2) C38 0.1491(2) 0.4810(4) 0.4563(2) 0.0257(11) C39 0.1983(2) 0.4834(4) 0.5012(3) 0.0338(14) C40 0.2134(3) 0.4721(5) 0.5619(3) 0.0483(19) C41 0.1810(3) 0.4601(5) 0.5787(3) 0.051(2) C42 0.1326(3) 0.4580(6) 0.5345(3) 0.054(2) C43 0.1160(3) 0.4680(5) 0.4727(3) 0.0416(16) C44 0.09717(18) 0.3971(3) 0.3347(2) 0.0210(10) C45 0.1007(2) 0.3138(4) 0.3629(3) 0.0268(11) C46 0.0793(2) 0.2349(4) 0.3282(3) 0.0347(14) C47 0.0547(2) 0.2390(4) 0.2656(3) 0.0333(13) C48 0.0507(2) 0.3218(4) 0.2367(3) 0.0327(13) C49 0.0722(2) 0.4008(4) 0.2711(3) 0.0281(12) C50 0.08298(19) 0.5892(4) 0.3510(2) 0.0225(10) S53

C51 0.0354(2) 0.5678(4) 0.3323(3) 0.0298(12) C52 0.0025(2) 0.6379(5) 0.3182(3) 0.0382(14) C53 0.0169(2) 0.7287(5) 0.3239(3) 0.0433(16) C54 0.0633(3) 0.7509(4) 0.3418(3) 0.0449(16) C55 0.0961(2) 0.6806(4) 0.3551(3) 0.0316(13) C56 0.9824(6) 0.2931(14) 0.4882(9) 0.071(4) C57 0.0140(4) 0.3269(12) 0.4724(8) 0.052(3) C58 0.0242(6) 0.2814(12) 0.4422(8) 0.073(4) C59 0.0031(6) 0.1984(12) 0.4103(8) 0.072(4) C60 0.9664(6) 0.1771(10) 0.4089(8) 0.066(4) C61 0.9636(6) 0.2095(12) 0.4640(9) 0.069(4) C62 0.9781(8) 0.3373(17) 0.5245(8) 0.090(6) Table S18. Bond lengths (Å) for 8. Au1-C1 2.057(5) Au1-P1 2.2872(13) P1-C44 1.810(5) P1-C50 1.812(5) P1-C38 1.816(5) O1-C2 1.220(7) O2-C4 1.232(6) N1-C1 1.337(6) N1-C4 1.450(6) N1-C26 1.453(6) N2-C1 1.339(6) N2-C2 1.453(6) N2-C14 1.459(6) C2-C3 1.404(7) C3-C4 1.408(7) C3-C5 1.489(7) C5-C6 1.393(8) C5-C10 1.410(8) C6-C7 1.392(7) C6-H6 0.95 C7-C8 1.381(8) C7-H7 0.95 C8-C9 1.399(8) C8-C11 1.488(7) C9-C10 1.388(7) C9-H9 0.95 C10-H10 0.95 C11-C13 1.394(8) C11-C12 1.395(8) C12-C13 1.394(7) S54

C12-H12 0.95 C13-C12 1.395(7) C13-H13 0.95 C14-C15 1.386(8) C14-C19 1.397(8) C15-C16 1.405(8) C15-C20 1.514(8) C16-C17 1.375(10) C16-H16 0.95 C17-C18 1.384(9) C17-H17 0.95 C18-C19 1.390(8) C18-H18 0.95 C19-C23 1.523(8) C20-C21 1.527(9) C20-C22 1.537(8) C20-H20 1.0 C21-H21A 0.98 C21-H21B 0.98 C21-H21C 0.98 C22-H22A 0.98 C22-H22B 0.98 C22-H22C 0.98 C23-C24 1.520(9) C23-C25 1.522(9) C23-H23 1.0 C24-H24A 0.98 C24-H24B 0.98 C24-H24C 0.98 C25-H25A 0.98 C25-H25B 0.98 C25-H25C 0.98 C26-C31 1.389(8) C26-C27 1.397(8) C27-C28 1.387(8) C27-C32 1.515(9) C28-C29 1.377(10) C28-H28 0.95 C29-C30 1.392(10) C29-H29 0.95 C30-C31 1.392(8) C30-H30 0.95 C31-C35 1.509(9) C32-C34 1.512(11) C32-C33 1.520(10) C32-H32 1.0 C33-H33A 0.98 C33-H33B 0.98 C33-H33C 0.98 C34-H34A 0.98 C34-H34B 0.98 C34-H34C 0.98 C35-C37 1.517(11) C35-C36 1.525(11) C35-H35 1.0 C36-H36A 0.98 C36-H36B 0.98 C36-H36C 0.98 S55

C37-H37A 0.98 C37-H37B 0.98 C37-H37C 0.98 C38-C43 1.389(9) C38-C39 1.392(9) C39-C40 1.385(9) C39-H39 0.95 C40-C41 1.371(12) C40-H40 0.95 C41-C42 1.369(12) C41-H41 0.95 C42-C43 1.397(9) C42-H42 0.95 C43-H43 0.95 C44-C45 1.385(7) C44-C49 1.392(7) C45-C46 1.386(8) C45-H45 0.95 C46-C47 1.369(9) C46-H46 0.95 C47-C48 1.383(9) C47-H47 0.95 C48-C49 1.386(8) C48-H48 0.95 C49-H49 0.95 C50-C55 1.378(8) C50-C51 1.404(7) C51-C52 1.382(8) C51-H51 0.95 C52-C53 1.377(10) C52-H52 0.95 C53-C54 1.378(10) C53-H53 0.95 C54-C55 1.387(9) C54-H54 0.95 C55-H55 0.95 C56-C62 1.21(2) C56-C61 1.35(2) C56-C57 1.40(2) C57-C58 1.21(2) C57-H57 0.95 C58-C59 1.409(16) C58-H58 0.95 C59-C60 1.235(16) C59-H59 0.95 C60-C61 1.56(3) C60-H60 0.95 C61-H61 0.95 C62-H62A 0.98 C62-H62B 0.98 C62-H62C 0.98 S56

Table S19. Bond angles ( ) for 8. C1-Au1-P1 171.21(13) C44-P1-C50 105.8(2) C44-P1-C38 107.2(2) C50-P1-C38 104.3(3) C44-P1-Au1 106.81(16) C50-P1-Au1 117.64(18) C38-P1-Au1 114.4(2) C1-N1-C4 125.4(4) C1-N1-C26 117.6(4) C4-N1-C26 117.0(4) C1-N2-C2 124.9(4) C1-N2-C14 118.3(4) C2-N2-C14 116.5(4) N1-C1-N2 116.6(4) N1-C1-Au1 122.8(3) N2-C1-Au1 120.5(4) O1-C2-C3 128.4(5) O1-C2-N2 116.0(5) C3-C2-N2 115.6(4) C2-C3-C4 121.9(4) C2-C3-C5 118.8(5) C4-C3-C5 119.3(4) O2-C4-C3 128.6(5) O2-C4-N1 116.1(4) C3-C4-N1 115.3(4) C6-C5-C10 117.1(5) C6-C5-C3 121.1(5) C10-C5-C3 121.8(5) C7-C6-C5 121.6(5) C7-C6-H6 119.2 C5-C6-H6 119.2 C8-C7-C6 121.1(5) C8-C7-H7 119.4 C6-C7-H7 119.4 C7-C8-C9 118.0(5) C7-C8-C11 120.8(5) C9-C8-C11 121.1(5) C10-C9-C8 121.2(5) C10-C9-H9 119.4 C8-C9-H9 119.4 C9-C10-C5 120.9(5) C9-C10-H10 119.6 C5-C10-H10 119.6 C13-C11-C12 117.5(5) C13-C11-C8 121.1(5) C12-C11-C8 121.4(5) C13-C12-C11 120.6(5) C13-C12-H12 119.7 C11-C12-H12 119.7 C11-C13-C12 121.9(5) C11-C13-H13 119.0 C12-C13-H13 119.0 C15-C14-C19 123.8(5) C15-C14-N2 119.1(5) C19-C14-N2 117.0(5) C14-C15-C16 116.8(5) S57

C14-C15-C20 123.7(5) C16-C15-C20 119.5(5) C17-C16-C15 120.7(6) C17-C16-H16 119.7 C15-C16-H16 119.7 C16-C17-C18 120.9(5) C16-C17-H17 119.6 C18-C17-H17 119.6 C17-C18-C19 120.7(6) C17-C18-H18 119.7 C19-C18-H18 119.7 C18-C19-C14 117.1(5) C18-C19-C23 120.7(5) C14-C19-C23 122.3(5) C15-C20-C21 112.1(5) C15-C20-C22 111.9(5) C21-C20-C22 110.5(5) C15-C20-H20 107.3 C21-C20-H20 107.3 C22-C20-H20 107.3 C20-C21-H21A 109.5 C20-C21-H21B 109.5 H21A-C21-H21B 109.5 C20-C21-H21C 109.5 H21A-C21-H21C 109.5 H21B-C21-H21C 109.5 C20-C22-H22A 109.5 C20-C22-H22B 109.5 H22A-C22-H22B 109.5 C20-C22-H22C 109.5 H22A-C22-H22C 109.5 H22B-C22-H22C 109.5 C24-C23-C25 111.1(6) C24-C23-C19 111.9(5) C25-C23-C19 112.7(6) C24-C23-H23 106.9 C25-C23-H23 106.9 C19-C23-H23 106.9 C23-C24-H24A 109.5 C23-C24-H24B 109.5 H24A-C24-H24B 109.5 C23-C24-H24C 109.5 H24A-C24-H24C 109.5 H24B-C24-H24C 109.5 C23-C25-H25A 109.5 C23-C25-H25B 109.5 H25A-C25-H25B 109.5 C23-C25-H25C 109.5 H25A-C25-H25C 109.5 H25B-C25-H25C 109.5 C31-C26-C27 123.9(5) C31-C26-N1 117.9(5) C27-C26-N1 118.3(5) C28-C27-C26 116.8(6) C28-C27-C32 120.9(6) C26-C27-C32 122.2(5) C29-C28-C27 121.4(6) C29-C28-H28 119.3 S58

C27-C28-H28 119.3 C28-C29-C30 120.0(6) C28-C29-H29 120.0 C30-C29-H29 120.0 C29-C30-C31 121.1(6) C29-C30-H30 119.5 C31-C30-H30 119.5 C26-C31-C30 116.8(5) C26-C31-C35 122.5(5) C30-C31-C35 120.7(6) C34-C32-C27 111.5(6) C34-C32-C33 110.3(6) C27-C32-C33 111.8(6) C34-C32-H32 107.7 C27-C32-H32 107.7 C33-C32-H32 107.7 C32-C33-H33A 109.5 C32-C33-H33B 109.5 H33A-C33-H33B 109.5 C32-C33-H33C 109.5 H33A-C33-H33C 109.5 H33B-C33-H33C 109.5 C32-C34-H34A 109.5 C32-C34-H34B 109.5 H34A-C34-H34B 109.5 C32-C34-H34C 109.5 H34A-C34-H34C 109.5 H34B-C34-H34C 109.5 C31-C35-C37 112.4(6) C31-C35-C36 110.9(7) C37-C35-C36 110.6(6) C31-C35-H35 107.6 C37-C35-H35 107.6 C36-C35-H35 107.6 C35-C36-H36A 109.5 C35-C36-H36B 109.5 H36A-C36-H36B 109.5 C35-C36-H36C 109.5 H36A-C36-H36C 109.5 H36B-C36-H36C 109.5 C35-C37-H37A 109.5 C35-C37-H37B 109.5 H37A-C37-H37B 109.5 C35-C37-H37C 109.5 H37A-C37-H37C 109.5 H37B-C37-H37C 109.5 C43-C38-C39 119.9(5) C43-C38-P1 120.6(5) C39-C38-P1 119.4(4) C40-C39-C38 119.0(7) C40-C39-H39 120.5 C38-C39-H39 120.5 C41-C40-C39 121.5(7) C41-C40-H40 119.3 C39-C40-H40 119.3 C42-C41-C40 119.5(6) C42-C41-H41 120.2 C40-C41-H41 120.2 S59

C41-C42-C43 120.7(7) C41-C42-H42 119.7 C43-C42-H42 119.7 C38-C43-C42 119.3(7) C38-C43-H43 120.3 C42-C43-H43 120.3 C45-C44-C49 119.3(5) C45-C44-P1 123.0(4) C49-C44-P1 117.5(4) C44-C45-C46 120.3(5) C44-C45-H45 119.8 C46-C45-H45 119.8 C47-C46-C45 120.1(5) C47-C46-H46 119.9 C45-C46-H46 119.9 C46-C47-C48 120.3(5) C46-C47-H47 119.9 C48-C47-H47 119.9 C47-C48-C49 120.0(6) C47-C48-H48 120.0 C49-C48-H48 120.0 C48-C49-C44 120.0(5) C48-C49-H49 120.0 C44-C49-H49 120.0 C55-C50-C51 119.1(5) C55-C50-P1 119.2(4) C51-C50-P1 121.5(4) C52-C51-C50 120.0(6) C52-C51-H51 120.0 C50-C51-H51 120.0 C53-C52-C51 119.9(6) C53-C52-H52 120.1 C51-C52-H52 120.1 C52-C53-C54 120.9(6) C52-C53-H53 119.6 C54-C53-H53 119.6 C53-C54-C55 119.4(6) C53-C54-H54 120.3 C55-C54-H54 120.3 C50-C55-C54 120.9(6) C50-C55-H55 119.6 C54-C55-H55 119.6 C62-C56-C61 128.(2) C62-C56-C57 118.(2) C61-C56-C57 113.5(18) C58-C57-C56 121.4(18) C58-C57-H57 119.3 C56-C57-H57 119.3 C57-C58-C59 129.(2) C57-C58-H58 115.6 C59-C58-H58 115.6 C60-C59-C58 112.9(18) C60-C59-H59 123.5 C58-C59-H59 123.5 C59-C60-C61 116.8(16) C59-C60-H60 121.6 C61-C60-H60 121.6 C56-C61-C60 117.3(17) S60

C56-C61-H61 121.4 C60-C61-H61 121.4 C56-C62-H62A 109.5 C56-C62-H62B 109.5 H62A-C62-H62B 109.5 C56-C62-H62C 109.5 H62A-C62-H62C 109.5 H62B-C62-H62C 109.5 Table S20. Anisotropic atomic displacement parameters (Å 2 ) for 8. The anisotropic atomic displacement factor exponent takes the form: -2π 2 [ h 2 a *2 U 11 +... + 2 h k a * b * U 12 ] U11 U22 U33 U23 U13 U12 Au1 0.01642(11) 0.01974(11) 0.02053(11) -0.00122(7) 0.01334(8) -0.00043(7) P1 0.0193(6) 0.0204(6) 0.0210(6) -0.0015(5) 0.0151(5) -0.0016(5) O1 0.021(2) 0.078(3) 0.024(2) -0.007(2) 0.0161(18) -0.005(2) O2 0.0197(19) 0.049(3) 0.029(2) -0.0049(18) 0.0150(17) -0.0036(17) N1 0.0141(19) 0.020(2) 0.018(2) -0.0020(16) 0.0091(17) 0.0001(16) N2 0.0130(19) 0.022(2) 0.020(2) 0.0002(16) 0.0110(17) 0.0006(16) C1 0.023(2) 0.016(2) 0.021(2) -0.0022(19) 0.016(2) -0.0054(19) C2 0.020(2) 0.030(3) 0.023(3) -0.003(2) 0.017(2) -0.002(2) C3 0.015(2) 0.020(2) 0.025(3) -0.0014(19) 0.014(2) -0.0001(19) C4 0.018(2) 0.020(2) 0.026(3) -0.001(2) 0.015(2) 0.0002(19) C5 0.017(2) 0.020(2) 0.027(3) -0.004(2) 0.015(2) -0.0012(19) C6 0.022(3) 0.028(3) 0.032(3) 0.004(2) 0.019(2) 0.004(2) C7 0.024(3) 0.026(3) 0.032(3) 0.001(2) 0.021(2) 0.001(2) C8 0.022(3) 0.021(2) 0.033(3) -0.004(2) 0.021(2) -0.002(2) C9 0.019(2) 0.023(3) 0.036(3) -0.001(2) 0.019(2) -0.001(2) C10 0.026(3) 0.024(3) 0.032(3) 0.002(2) 0.020(2) -0.001(2) C11 0.021(3) 0.015(2) 0.041(3) -0.001(2) 0.024(2) -0.0013(19) C12 0.022(3) 0.023(3) 0.030(3) 0.002(2) 0.018(2) 0.001(2) C13 0.018(2) 0.022(3) 0.036(3) -0.004(2) 0.018(2) -0.003(2) C14 0.019(2) 0.033(3) 0.019(2) -0.003(2) 0.016(2) 0.000(2) C15 0.020(3) 0.035(3) 0.025(3) 0.004(2) 0.016(2) 0.004(2) C16 0.020(3) 0.051(4) 0.028(3) 0.012(3) 0.013(2) 0.008(3) S61

C17 0.018(3) 0.066(4) 0.027(3) -0.001(3) 0.010(2) -0.009(3) C18 0.029(3) 0.043(3) 0.031(3) -0.010(3) 0.018(3) -0.008(3) C19 0.021(3) 0.038(3) 0.026(3) -0.008(2) 0.018(2) -0.007(2) C20 0.031(3) 0.031(3) 0.034(3) 0.007(2) 0.018(3) 0.006(2) C21 0.074(5) 0.036(4) 0.054(4) 0.009(3) 0.043(4) 0.012(4) C22 0.057(4) 0.037(3) 0.054(4) 0.011(3) 0.039(4) 0.003(3) C23 0.031(3) 0.025(3) 0.046(3) -0.012(3) 0.024(3) -0.004(2) C24 0.057(4) 0.036(4) 0.060(4) 0.006(3) 0.038(4) 0.013(3) C25 0.064(5) 0.052(4) 0.073(5) -0.021(4) 0.047(5) 0.005(4) C26 0.016(2) 0.034(3) 0.017(2) -0.002(2) 0.010(2) -0.001(2) C27 0.023(3) 0.038(3) 0.033(3) -0.012(3) 0.017(2) -0.007(2) C28 0.038(3) 0.052(4) 0.036(3) -0.019(3) 0.023(3) -0.008(3) C29 0.031(3) 0.079(5) 0.021(3) -0.007(3) 0.015(3) 0.001(3) C30 0.029(3) 0.048(4) 0.026(3) 0.013(3) 0.009(3) 0.009(3) C31 0.022(3) 0.042(3) 0.022(3) 0.002(2) 0.010(2) 0.004(2) C32 0.057(4) 0.026(3) 0.047(4) -0.013(3) 0.036(3) -0.009(3) C33 0.074(6) 0.051(5) 0.093(7) -0.011(5) 0.054(5) -0.020(4) C34 0.062(5) 0.045(4) 0.084(6) 0.008(4) 0.037(5) 0.001(4) C35 0.062(5) 0.034(3) 0.039(4) 0.011(3) 0.028(3) 0.013(3) C36 0.087(6) 0.064(5) 0.065(5) 0.027(4) 0.053(5) 0.039(5) C37 0.087(6) 0.038(4) 0.069(5) 0.008(4) 0.043(5) -0.003(4) C38 0.037(3) 0.023(3) 0.024(3) -0.004(2) 0.021(2) -0.005(2) C39 0.035(3) 0.036(3) 0.022(3) 0.002(2) 0.011(3) -0.005(3) C40 0.062(5) 0.039(4) 0.026(3) -0.002(3) 0.012(3) -0.014(3) C41 0.085(6) 0.041(4) 0.021(3) -0.003(3) 0.024(4) -0.020(4) C42 0.079(6) 0.066(5) 0.038(4) -0.001(3) 0.046(4) -0.014(4) C43 0.048(4) 0.057(4) 0.029(3) -0.002(3) 0.028(3) -0.009(3) C44 0.020(2) 0.020(2) 0.030(3) -0.002(2) 0.018(2) 0.002(2) C45 0.030(3) 0.022(3) 0.033(3) 0.002(2) 0.020(2) -0.003(2) S62

C46 0.039(3) 0.021(3) 0.050(4) 0.002(3) 0.029(3) -0.002(2) C47 0.027(3) 0.025(3) 0.046(4) -0.012(3) 0.019(3) -0.004(2) C48 0.033(3) 0.033(3) 0.032(3) -0.008(2) 0.017(3) -0.002(3) C49 0.031(3) 0.024(3) 0.031(3) -0.003(2) 0.019(2) -0.003(2) C50 0.021(2) 0.025(3) 0.026(3) -0.004(2) 0.016(2) 0.001(2) C51 0.025(3) 0.033(3) 0.036(3) -0.005(2) 0.020(3) -0.001(2) C52 0.032(3) 0.042(4) 0.046(4) -0.005(3) 0.025(3) 0.005(3) C53 0.038(4) 0.041(4) 0.048(4) -0.003(3) 0.022(3) 0.013(3) C54 0.053(4) 0.025(3) 0.055(4) -0.002(3) 0.028(4) 0.006(3) C55 0.030(3) 0.025(3) 0.040(3) -0.002(2) 0.019(3) -0.001(2) C56 0.042(6) 0.074(7) 0.081(7) -0.013(6) 0.023(6) 0.004(6) C57 0.017(5) 0.056(7) 0.073(7) 0.023(6) 0.019(5) -0.004(5) C58 0.045(6) 0.066(7) 0.073(8) 0.023(6) 0.011(6) 0.001(6) C59 0.055(7) 0.062(7) 0.072(7) 0.006(6) 0.016(6) 0.016(6) C60 0.049(6) 0.028(6) 0.083(7) -0.016(6) 0.012(6) 0.000(5) C61 0.051(6) 0.057(7) 0.102(8) -0.007(6) 0.044(6) -0.018(6) C62 0.095(12) 0.127(14) 0.034(8) -0.017(9) 0.027(8) -0.002(11) Table S21. Hydrogen atomic coordinates and isotropic atomic displacement parameters (Å 2 ) for 8. x/a y/b z/c U(eq) H6 0.3151 0.5649 0.2191 0.03 H7 0.3750 0.5585 0.1985 0.029 H9 0.4619 0.4223 0.3574 0.029 H10 0.4029 0.4310 0.3795 0.03 H12 0.5211 0.4898 0.3514 0.027 H13 0.4192 0.4891 0.1698 0.029 H16 0.0847 0.6261 0.1429 0.04 H17 0.0529 0.4793 0.1110 0.045 S63

H18 0.1008 0.3492 0.1562 0.04 H20 0.2073 0.6775 0.2647 0.038 H21A 0.1124 0.7485 0.2157 0.076 H21B 0.1615 0.7991 0.2658 0.076 H21C 0.1457 0.7054 0.2828 0.076 H22A 0.1945 0.7012 0.1680 0.067 H22B 0.1872 0.7971 0.1924 0.067 H22C 0.1412 0.7394 0.1417 0.067 H23 0.2276 0.3539 0.2751 0.039 H24A 0.1801 0.3307 0.3173 0.071 H24B 0.2059 0.2384 0.3154 0.071 H24C 0.1497 0.2545 0.2656 0.071 H25A 0.1587 0.2396 0.1768 0.087 H25B 0.2142 0.2137 0.2247 0.087 H25C 0.2004 0.2963 0.1771 0.087 H28 0.3196 0.6991 0.5477 0.049 H29 0.3317 0.5697 0.6067 0.052 H30 0.3286 0.4223 0.5685 0.045 H32 0.2952 0.6951 0.3947 0.047 H33A 0.3391 0.8317 0.4401 0.102 H33B 0.3725 0.7430 0.4730 0.102 H33C 0.3505 0.7988 0.5053 0.102 H34A 0.2604 0.7964 0.4567 0.098 H34B 0.2275 0.7302 0.3993 0.098 H34C 0.2507 0.8215 0.3911 0.098 H35 0.2950 0.3727 0.4146 0.054 H36A 0.3794 0.3713 0.4784 0.099 H36B 0.3594 0.2683 0.4707 0.099 H36C 0.3771 0.3247 0.5323 0.099 S64

H37A 0.2942 0.2925 0.5140 0.096 H37B 0.2785 0.2406 0.4515 0.096 H37C 0.2470 0.3250 0.4508 0.096 H39 0.2211 0.4926 0.4904 0.041 H40 0.2470 0.4728 0.5927 0.058 H41 0.1921 0.4532 0.6206 0.061 H42 0.1101 0.4497 0.5460 0.065 H43 0.0824 0.4660 0.4422 0.05 H45 0.1178 0.3106 0.4063 0.032 H46 0.0818 0.1780 0.3478 0.042 H47 0.0402 0.1848 0.2420 0.04 H48 0.0332 0.3245 0.1933 0.039 H49 0.0700 0.4574 0.2513 0.034 H51 0.0258 0.5051 0.3293 0.036 H52-0.0299 0.6235 0.3046 0.046 H53-0.0056 0.7767 0.3154 0.052 H54 0.0727 0.8137 0.3450 0.054 H55 0.1281 0.6956 0.3671 0.038 H57 0.0276 0.3867 0.4858 0.062 H58 0.0498 0.3047 0.4395 0.087 H59 0.0159 0.1625 0.3918 0.087 H60-0.0590 0.1428 0.3759 0.079 H61-0.0507 0.1719 0.4797 0.083 H62A -0.0531 0.3693 0.5028 0.135 H62B 0.0042 0.3828 0.5450 0.135 H62C -0.0203 0.2955 0.5552 0.135 S65

Crystal Structure Report for 9 (C110H110Ag2N4O4P2 C7H8) A specimen of C 117 H 118 Ag 2 N 4 O 4 P 2, approximate dimensions 0.056 mm x 0.456 mm x 0.568 mm, was used for the X-ray crystallographic analysis. The X-ray intensity data were measured. The integration of the data using a monoclinic unit cell yielded a total of 174301 reflections to a maximum θ angle of 26.51 (0.80 Å resolution), of which 10829 were independent (average redundancy 16.096, completeness = 99.6%, R int = 6.89%, R sig = 2.47%) and 8892 (82.11%) were greater than 2σ(F 2 ). The final cell constants of a = 33.218(5) Å, b = 14.445(2) Å, c = 26.047(4) Å, β = 123.072(11), volume = 10473.(3) Å 3, are based upon the refinement of the XYZ-centroids of reflections above 20 σ(i). The calculated minimum and maximum transmission coefficients (based on crystal size) are 0.8825 and 1.0000. The structure was solved and refined using the Bruker SHELXTL Software Package, using the space group C 1 2/c 1, with Z = 4 for the formula unit, C 117 H 118 Ag 2 N 4 O 4 P 2. The final anisotropic full-matrix least-squares refinement on F 2 with 622 variables converged at R1 = 6.09%, for the observed data and wr2 = 20.45% for all data. The goodness-of-fit was 1.092. The largest peak in the final difference electron density synthesis was 2.218 e - /Å 3 and the largest hole was -1.206 e - /Å 3 with an RMS deviation of 0.199 e - /Å 3. On the basis of the final model, the calculated density was 1.219 g/cm 3 and F(000), 4016 e -. Figure S23. Solid state molecular structure of 9 S66

Figure S24. Solid state packing diagram of 9 Table S22. Sample and crystal data for 9. Chemical formula C 117 H 118 Ag 2 N 4 O 4 P 2 Formula weight Temperature Wavelength Crystal size Crystal system 1921.83 g/mol 100(2) K 0.71073 Å 0.056 x 0.456 x 0.568 mm monoclinic Space group C 1 2/c 1 Unit cell dimensions a = 33.218(5) Å α = 90 b = 14.445(2) Å β = 123.072(11) S67