Isomerism in Au 28 (SR) 20 Nanocluster and Stable Structures

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1 (Supporting Information) Isomerism in Au 28 (SR) 20 Nanocluster and Stable Structures Yuxiang Chen, Chong Liu, Qing Tang, Chenjie Zeng, Tatsuya Higaki, Anindita Das, De-en Jiang, *, Nathaniel L. Rosi, Rongchao Jin *, Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15213, United States Department of Chemistry, University of California, Riverside, California 92521, United States 1. Chemicals Tetrachloroauric(III) acid (HAuCl 4 3H 2 O, >99.99% metals basis, Aldrich), tetraoctylammonium bromide (TOAB, 98%, Fluka), phenylethanethiol (HSC 2 H 4 Ph, 99%, Acros Organics), 4-tertbutylbenzenethiol (HSPh- t Bu, 97%, Alfa Aesar), cyclohexanethiol (HS-c-C 6 H 11, 97%, Aldrich), sodium borohydride (NaBH 4, 99.99%, metals basis, Aldrich). Solvents: toluene (HPLC grade, 99.9%, Aldrich), methanol (HPLC grade, 99.9%, Aldrich), methylene chloride (HPLC grade, 99.9%, Aldrich), pentane (HPLC grade, 99.9%, Aldrich). All chemicals were used as received. Nanopure water (resistivity: 18.2 MΩ cm) was purified with a Barnstead Nanopure DIwater TM system. All glassware was thoroughly cleaned with aqua regia (HCl: HNO 3 =3:1 vol), rinsed with copious nanopure water, and then dried in an oven prior to use. 2. Syntheses Synthesis of Au 28 (SPh- t Bu) 20 nanocluster. The Au 28 (SPh- t Bu) 20 nanocluster was synthesized based on the previously reported synthetic method. s1 First, Au 25 (SC 2 H 4 Ph) 18 nanoclusters were synthesized using the one-pot method. s2 Then, 5 mg of Au 25 (SC 2 H 4 Ph) 18 nanoclusters was dissolved in 0.5 ml toluene, then mixed with 0.5 ml HSPh- t Bu. The reaction mixture was heated at 80 o C for 2 hours. The reaction product was washed with methanol and the supernatant was discarded. This process was repeated for three times. Finally, the Au 28 (SPh- t Bu) 20 nanoclusters were extracted with CH 2 Cl 2. Synthesis of Au 28 (S-c-C 6 H 11 ) 20 nanocluster. 5 mg of Au 28 (SPh- t Bu) 20 nanoclusters was dissolved in 0.5 ml toluene and mixed with 0.5 ml HS-c-C 6 H 11. The reaction was incubated for 2 hours at 80 o C under stirring. The final reaction product was washed with methanol and the supernatant was discarded. This process was repeated for three times. The Au 28 (S-c-C 6 H 11 ) 20 nanoclusters were extracted with CH 2 Cl 2. Single crystal growth of Au 28 (S-c-C 6 H 11 ) 20 nanocluster was performed via vapor diffusion of pentane into a CH 2 Cl 2 solution of nanoclusters. Dark orange crystals of Au 28 (S-c-C 6 H 11 ) 20 nanocluster were obtained after ~3 days. Reversed isomerization of Au 28 (S-c-C 6 H 11 ) 20 to Au 28 (SPh- t Bu) 20 was achieved with similar synthetic procedures. Briefly, 5 mg of Au 28 (S-c-C 6 H 11 ) 20 nanoclusters were dissolved in 0.5 ml toluene and mixed with 0.5 ml HSPh- t Bu. The reaction mixture was heated at 80 o C. The Au 28 (SPh- t Bu) 20 nanocluster was obtained after 2 hours. 3. X-ray Crystallographic Determination s1

2 Single X-ray diffraction data of Au 28 (S-c-C 6 H 11 ) 20 was collected on a Bruker X8 Prospector Ultra equipped with an Apex II CCD detector and an IµS micro-focus CuKα X-ray source (λ = Å). A piece of brown needle-shaped crystal with dimensions 0.14 x 0.02 x 0.01 mm was mounted onto a MiTeGen MicroMeshes with fluorolube. The data were collected under cold N 2 flow at 240 K. A monoclinic unit cell with dimensions a = (6), b = (9), (7), α = γ = 90, β = (3), was derived from the least-square refinement of 9892 reflections in the range of < θ < Centrosymmetric space group P2/c was determined based on intensity statistics and the systematic absences. The data were collected to 0.95 Å and later truncated to 0.98 Å during integration by Bruker program SAINT s3, empirical absorption correction was applied using program SADABS. s1 Maximum and minimum transmittance (Tmax, Tmin) values are and , respectively. The structure was successfully solved with direct method using Bruker program SHELXS and refined by full-matrix least-squares on F 2 using SHELXL. s4 All the Au, S atoms were located easily, all the C atoms were generated via subsequent difference Fourier syntheses. Idealized atom positions were calculated for all hydrogen atoms (with d-(c-h) = Å for CH2, d-(c-h) = Å for CH). All the Au, S and C atoms were refined anisotropically. All the H atoms were refined isotropically. ADP restraints were applied to cyclohexyl C atoms using SIMU command. Rigid bond restraints were also applied to cyclohexyl rings using DELU command. SADI command was used to restrain cyclohexyl rings. All the refinement parameters are summarized in the following tables. The calculated sin(theta_max)/wavelength is only due to weak diffraction of the small crystal. Solvent accessible void(s) is reasonable considering the size of the cluster and the way they are packed together in the unit cell. 4. DFT Calculations We investigate the ligand effect on the isomer stabilities of four possible Au 28 (SR) 20 structures via dispersion-corrected density functional theory (DFT) computations that incorporate vdw interactions into the DFT energetics. All DFT calculations were done with the quantum chemistry program Turbomole V6.5. s5 Geometry optimizations of the Au 28 (S-c-C 6 H 11 ) 20 (α-structure), Au 28 (S-c-C 6 H 11 ) 20 (β-structure), Au 28 (SPh- t Bu) 20 (α-structure) and Au 28 (SPh- t Bu) 20 (β-structure) isomers were performed using TPSS (Tao, Perdew, Staroverov, and Scuseria) functional for electron exchange and correlation and the def2-sv(p) basis sets. s6 The vdw interactions were included via the DFT-D3 method for structural optimizations. s7 Partial atomic charges were based on the natural population analysis. s8 5. Catalytic Evaluation Preparation of Au 28 (SR) 20 /CeO 2 catalysts. 500 mg CeO 2 support was impregnated by soaking the powders in a CH 2 Cl 2 solution containing 0.32 µmol of Au 28 (S-c-C 6 H 11 ) 20 nanoclusters or Au 28 (SPh- t Bu) 20 nanoclusters in a sealed vial for 24 hours, followed by drying at room temperature, no further treatment was performed unless otherwise noted. Catalytic CO oxidation activity test. 100 mg CeO 2 supported Au 28 (SR) 28 catalysts were mixed with quartz wool and tested for CO oxidation in a fixed-bed, continuous flow reactor (8 mm i.d.) under s2

3 ambient pressure. Prior to CO oxidation reaction, the as-prepared catalysts were pretreated at given temperatures for 1 h and cool to room temperature in an O2/He atmosphere. The reaction gas mixture (3% CO/10% O2/87% He) passed through the catalyst bed at a flow rate of 40 ml min-1. The products were analyzed by an online gas chromatograph (HP 6890 series GC) equipped with a thermal conductivity detector (TCD). 6. Supporting Figures/Tables: Figure S1. (A C) Three different views of the Au28S20 framework. Color labels: magenta = gold atoms in kernel; orange = sulfur; light blue = gold atoms in trimeric staples; light green = gold atoms in monomeric staples. Figure S2. Alternative view of the staple motifs in Au28(S-c-C6H11)20 nanocluster. (A) Au14 kernel; (B) Au14 kernel capped by two monomeric staples; (C) Four trimeric staples nested on Au14. Color codes: magenta = gold; orange = sulfur; light blue = gold atoms on trimeric staples. s3

4 Figure S3. Time dependent optical spectroscopic monitoring of the ligand-induced isomerization processes, (A) Au 28 (SPh- t Bu) 20 to Au 28 (S-c-C 6 H 11 ) 20, (B) Au 28 (S-c-C 6 H 11 ) 20 to Au 28 (SPh- t Bu) 20. Figure S4. Most stable adsorption geometry of CO on (a) Au 28 (SPh- t Bu) 20 and (b) Au 28 (S-c- C 6 H 11 ) 20. Au, pink; S, yellow; C, grey; O, red; R groups, lines. s4

5 Table S1. Partial atomic charges on the Au atoms of the Au 28 (S-c-C 6 H 11 ) 20 cluster, based on the Natural Population Analysis (NPA). Au atom type Au atom number Number of S atoms bonded to each Au atom Partial charges staple Au in the two 2 2 monomeric motifs staple Au in the two 6 2 trimeric motifs ~0.268 kernel Au between two 6 2 bridging thiolates ~0.307 kernel Au anchoring the 4 1 two monomeric motifs kernel Au anchoring the 4 1 two trimeric motifs kernel Au anchoring 4 1 bridging thiolates inner kernel Au Table S2. Comparison of Different Bond Length in Au 28 (S-c-C 6 H 11 ) 20 and Au 28 (SPh- t Bu) 20 Crystal Structures a bond length Au 28 (S-c-C 6 H 11 ) 20 (Å) Au 28 (SPh- t Bu) 20 (Å) difference Au Au (kernel) % Au Au (staple to kernel) % Au S % S C % a Bond length difference (%) was calculated using Au 28 (SPh-tBu) 20 as the reference. Table S3. The DFT-calculated total energy difference between two Au 28 (SR) 20 quasi-isomeric structures (α and β) a for two different R groups: c-c 6 H 11 and Ph- t Bu. Au 28 (SR) 20 ΔE total (ev) ΔE dft (ev) ΔE vdw (ev) E total(α) -E total(β) E dft(α) -E dft(β) E vdw(α) -E vdw(β) R=c-C 6 H R= Ph- t Bu a The structural motifs of Au 28 (S-c-C 6 H 11 ) 20 (α) and Au 28 (SPh- t Bu) 20 (β) are from the experimental crystal structures. s5

6 Table S4. Crystal data and structure refinement for Au 28 (S-c-C 6 H 11 ) 20. Identification code Au 28 (S-c-C 6 H 11 ) 20 Empirical formula C120 H220 Au28 S20 Formula weight Temperature 240(2) K Wavelength Å Crystal system Monoclinic Space group P2/c Unit cell dimensions a = (6) Å α= 90. b = (9) Å β= (3). c = (7) Å γ = 90. Volume (6) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 6944 Crystal size 0.14 x 0.02 x 0.01 mm 3 Theta range for data collection 1.66 to Index ranges -17<=h<=17, -26<=k<=26, -22<=l<=22 Reflections collected Independent reflections [R(int) = ] Completeness to theta = % Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / 792 / 757 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 s6

7 Table S5. Atomic coordinates (x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for Au 28 (S-c-C 6 H 11 ) 20. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) Au(1) 4986(1) 7494(1) 3289(1) 47(1) Au(2) 5866(1) 8193(1) 2420(1) 46(1) Au(3) 6608(1) 7441(1) 1855(1) 53(1) Au(4) 4987(1) 7496(1) 4841(1) 53(1) Au(5) 4133(1) 8175(1) 3850(1) 49(1) Au(6) 6572(1) 7555(1) 3466(1) 53(1) Au(7) 5822(1) 8465(1) 3965(1) 52(1) Au(8) 4139(1) 6801(1) 2249(1) 55(1) Au(9) 5830(1) 6814(1) 4013(1) 55(1) Au(10) 4143(2) 6532(1) 3802(1) 60(1) Au(11) 4184(2) 8522(1) 5446(1) 64(1) Au(12) 4987(2) 7504(1) 6399(1) 70(1) Au(13) 5780(2) 6476(1) 5598(1) 71(1) Au(14) 8007(2) 7491(1) 2817(1) 79(1) S(1) 5845(8) 8180(5) 4966(5) 57(4) S(2) 3559(9) 8727(5) 4506(6) 64(4) S(3) 5879(8) 8903(4) 3073(5) 56(4) S(4) 6394(10) 6260(5) 4762(6) 75(5) S(5) 4807(10) 8353(5) 6423(6) 78(5) S(6) 5201(11) 6649(5) 6459(6) 79(5) S(7) 4105(10) 6092(5) 2884(6) 76(5) S(8) 7918(8) 7691(6) 3833(8) 88(5) S(9) 7992(9) 7290(6) 1785(8) 83(5) S(10) 4113(9) 6824(4) 4797(5) 57(4) C(1) 6860(30) 8002(18) 5170(20) 93(13) C(2) 6900(20) 7750(20) 5800(20) 101(14) C(3) 7740(30) 7622(18) 6040(20) 109(14) C(4) 8250(30) 8090(20) 6070(20) 111(14) C(5) 8210(20) 8340(20) 5450(20) 97(13) C(6) 7370(30) 8469(17) 5200(20) 99(13) s7

8 C(7) 3970(40) 9373(12) 4340(17) 103(14) C(8) 3920(40) 9497(13) 3682(17) 102(14) C(9) 4230(40) 10000(14) 3570(20) 111(14) C(10) 3900(40) 10397(13) 3930(19) 111(14) C(11) 3970(40) 10277(13) 4590(18) 109(14) C(12) 3660(40) 9771(13) 4711(18) 106(14) C(13) 6840(30) 9240(20) 3130(40) 180(20) C(14) 7510(30) 8940(20) 3090(40) 180(20) C(15) 8210(30) 9230(20) 3120(30) 190(20) C(16) 8300(30) 9550(20) 3640(40) 190(20) C(17) 7620(30) 9850(20) 3680(40) 190(20) C(18) 6920(30) 9570(20) 3650(30) 170(20) C(19) 5910(40) 5615(13) 4550(17) 94(13) C(20) 6130(40) 5498(12) 3911(16) 95(13) C(21) 5800(40) 4978(13) 3731(17) 106(14) C(22) 6240(40) 4601(13) 4173(17) 104(13) C(23) 6000(40) 4716(13) 4811(17) 102(13) C(24) 6340(40) 5235(14) 4993(16) 104(13) C(25) 4110(20) 8470(13) 7010(30) 93(12) C(26) 3890(30) 9018(13) 6990(30) 101(13) C(27) 3290(30) 9113(15) 7430(20) 109(14) C(28) 2570(20) 8799(16) 7250(30) 118(14) C(29) 2780(30) 8252(15) 7240(30) 119(14) C(30) 3380(30) 8160(14) 6810(30) 106(14) C(31) 5880(20) 6532(12) 7230(20) 74(12) C(32) 6590(20) 6836(14) 7120(20) 94(13) C(33) 7130(30) 6769(14) 7700(20) 113(15) C(34) 7400(20) 6237(15) 7670(30) 123(15) C(35) 6700(30) 5928(15) 7760(20) 111(15) C(36) 6160(30) 6002(12) 7190(20) 91(13) C(37) 3220(30) 5770(20) 2770(40) 180(20) C(38) 3100(30) 5430(20) 3320(30) 180(20) C(39) 2330(40) 5130(20) 3180(40) 180(20) C(40) 1630(30) 5490(20) 3060(40) 190(20) C(41) 1750(30) 5830(20) 2510(30) 190(20) C(42) 2520(30) 6140(20) 2650(40) 180(20) s8

9 C(43) 8280(30) 7133(16) 4240(20) 109(15) C(44) 9190(30) 7186(18) 4400(30) 124(16) C(45) 9490(30) 6734(19) 4810(30) 148(18) C(46) 9310(30) 6237(18) 4450(30) 156(18) C(47) 8420(30) 6185(17) 4270(30) 141(17) C(48) 8110(30) 6638(17) 3870(20) 127(16) C(49) 8390(30) 7830(15) 1470(30) 102(13) C(50) 8160(30) 8328(16) 1720(30) 95(13) C(51) 8540(30) 8748(16) 1400(30) 110(14) C(52) 9420(20) 8693(17) 1500(30) 127(15) C(53) 9650(30) 8195(18) 1260(30) 134(15) C(54) 9270(30) 7773(16) 1570(30) 119(14) C(55) 3130(30) 7020(20) 4740(30) 156(19) C(56) 2600(30) 6550(19) 4720(30) 160(20) C(57) 1750(30) 6700(20) 4830(30) 160(20) C(58) 1770(30) 6970(20) 5460(30) 170(20) C(59) 2310(30) 7430(20) 5490(30) 170(20) C(60) 3150(30) 7300(20) 5350(30) 150(20) s9

10 Table S6. Bond lengths [Å] and angles [ ] for Au 28 (S-c-C 6 H 11 ) 20. Au(1)-Au(6) 2.707(3) Au(1)-Au(9) 2.708(3) Au(1)-Au(5) 2.709(3) Au(1)-Au(3)# (3) Au(1)-Au(8)# (3) Au(1)-Au(2)# (3) Au(1)-Au(8) 3.146(3) Au(1)-Au(2) 3.164(3) Au(1)-Au(10) 3.205(3) Au(1)-Au(7) 3.223(3) Au(2)-S(3) 2.366(12) Au(2)-Au(1)# (3) Au(2)-Au(3) 2.738(3) Au(2)-Au(5)# (3) Au(2)-Au(6) 2.989(3) Au(2)-Au(2)# (4) Au(3)-S(9) 2.430(15) Au(3)-Au(5)# (3) Au(3)-Au(1)# (3) Au(3)-Au(8)# (3) Au(3)-Au(14) 3.005(3) Au(3)-Au(10)# (3) Au(4)-S(10) 2.326(13) Au(4)-S(1) 2.332(13) Au(4)-Au(9) 3.047(3) Au(4)-Au(5) 3.058(3) Au(4)-Au(13) 3.375(3) Au(5)-S(2) 2.347(13) Au(5)-Au(3)# (3) Au(5)-Au(2)# (3) Au(5)-Au(7) 2.979(3) Au(6)-S(8) 2.381(14) Au(6)-Au(9) 2.698(3) Au(6)-Au(8)# (3) s10

11 Au(6)-Au(14) 2.990(3) Au(6)-Au(7) 3.004(3) Au(7)-S(3) 2.285(12) Au(7)-S(1) 2.314(12) Au(8)-S(7) 2.344(13) Au(8)-Au(1)# (3) Au(8)-Au(6)# (3) Au(8)-Au(9)# (3) Au(8)-Au(3)# (3) Au(8)-Au(8)# (5) Au(9)-S(4) 2.327(13) Au(9)-Au(8)# (3) Au(9)-Au(10) 2.973(3) Au(10)-S(7) 2.318(13) Au(10)-S(10) 2.319(12) Au(10)-Au(3)# (3) Au(11)-S(2) 2.271(12) Au(11)-S(5) 2.320(14) Au(12)-S(5) 2.276(14) Au(12)-S(6) 2.302(14) Au(13)-S(6) 2.280(15) Au(13)-S(4) 2.289(14) Au(14)-S(8) 2.310(18) Au(14)-S(9) 2.317(17) S(1)-C(1) 1.80(5) S(2)-C(7) 1.91(4) S(3)-C(13) 1.86(5) S(4)-C(19) 1.93(5) S(5)-C(25) 1.89(5) S(6)-C(31) 1.95(4) S(7)-C(37) 1.74(6) S(8)-C(43) 1.80(4) S(9)-C(49) 1.76(5) S(10)-C(55) 1.75(6) C(1)-C(6) 1.52(3) C(1)-C(2) 1.52(3) s11

12 C(1)-H(1) C(2)-C(3) 1.52(3) C(2)-H(2A) C(2)-H(2B) C(3)-C(4) 1.52(3) C(3)-H(3A) C(3)-H(3B) C(4)-C(5) 1.52(3) C(4)-H(4A) C(4)-H(4B) C(5)-C(6) 1.52(3) C(5)-H(5A) C(5)-H(5B) C(6)-H(6A) C(6)-H(6B) C(7)-C(8) 1.47(3) C(7)-C(12) 1.47(3) C(7)-H(7) C(8)-C(9) 1.47(3) C(8)-H(8A) C(8)-H(8B) C(9)-C(10) 1.47(3) C(9)-H(9A) C(9)-H(9B) C(10)-C(11) 1.47(3) C(10)-H(10A) C(10)-H(10B) C(11)-C(12) 1.48(3) C(11)-H(11A) C(11)-H(11B) C(12)-H(12A) C(12)-H(12B) C(13)-C(14) 1.41(3) C(13)-C(18) 1.41(3) C(13)-H(13) C(14)-C(15) 1.42(4) s12

13 C(14)-H(14A) C(14)-H(14B) C(15)-C(16) 1.42(3) C(15)-H(15A) C(15)-H(15B) C(16)-C(17) 1.41(3) C(16)-H(16A) C(16)-H(16B) C(17)-C(18) 1.41(4) C(17)-H(17A) C(17)-H(17B) C(18)-H(18A) C(18)-H(18B) C(19)-C(24) 1.52(3) C(19)-C(20) 1.52(3) C(19)-H(19) C(20)-C(21) 1.53(3) C(20)-H(20A) C(20)-H(20B) C(21)-C(22) 1.52(3) C(21)-H(21A) C(21)-H(21B) C(22)-C(23) 1.53(3) C(22)-H(22A) C(22)-H(22B) C(23)-C(24) 1.53(3) C(23)-H(23A) C(23)-H(23B) C(24)-H(24A) C(24)-H(24B) C(25)-C(26) 1.50(3) C(25)-C(30) 1.51(3) C(25)-H(25) C(26)-C(27) 1.50(3) C(26)-H(26A) C(26)-H(26B) s13

14 C(27)-C(28) 1.50(3) C(27)-H(27A) C(27)-H(27B) C(28)-C(29) 1.50(3) C(28)-H(28A) C(28)-H(28B) C(29)-C(30) 1.50(3) C(29)-H(29A) C(29)-H(29B) C(30)-H(30A) C(30)-H(30B) C(31)-C(36) 1.49(3) C(31)-C(32) 1.50(3) C(31)-H(31) C(32)-C(33) 1.49(3) C(32)-H(32A) C(32)-H(32B) C(33)-C(34) 1.49(3) C(33)-H(33A) C(33)-H(33B) C(34)-C(35) 1.48(3) C(34)-H(34A) C(34)-H(34B) C(35)-C(36) 1.49(3) C(35)-H(35A) C(35)-H(35B) C(36)-H(36A) C(36)-H(36B) C(37)-C(42) 1.54(4) C(37)-C(38) 1.55(4) C(37)-H(37) C(38)-C(39) 1.54(4) C(38)-H(38A) C(38)-H(38B) C(39)-C(40) 1.54(4) C(39)-H(39A) s14

15 C(39)-H(39B) C(40)-C(41) 1.55(4) C(40)-H(40A) C(40)-H(40B) C(41)-C(42) 1.55(4) C(41)-H(41A) C(41)-H(41B) C(42)-H(42A) C(42)-H(42B) C(43)-C(48) 1.56(3) C(43)-C(44) 1.56(3) C(43)-H(43) C(44)-C(45) 1.56(3) C(44)-H(44A) C(44)-H(44B) C(45)-C(46) 1.55(3) C(45)-H(45A) C(45)-H(45B) C(46)-C(47) 1.55(3) C(46)-H(46A) C(46)-H(46B) C(47)-C(48) 1.55(3) C(47)-H(47A) C(47)-H(47B) C(48)-H(48A) C(48)-H(48B) C(49)-C(54) 1.50(3) C(49)-C(50) 1.50(3) C(49)-H(49) C(50)-C(51) 1.50(3) C(50)-H(50A) C(50)-H(50B) C(51)-C(52) 1.50(3) C(51)-H(51A) C(51)-H(51B) C(52)-C(53) 1.50(3) s15

16 C(52)-H(52A) C(52)-H(52B) C(53)-C(54) 1.50(3) C(53)-H(53A) C(53)-H(53B) C(54)-H(54A) C(54)-H(54B) C(55)-C(60) 1.54(3) C(55)-C(56) 1.54(3) C(55)-H(55) C(56)-C(57) 1.55(3) C(56)-H(56A) C(56)-H(56B) C(57)-C(58) 1.54(3) C(57)-H(57A) C(57)-H(57B) C(58)-C(59) 1.54(3) C(58)-H(58A) C(58)-H(58B) C(59)-C(60) 1.54(3) C(59)-H(59A) C(59)-H(59B) C(60)-H(60A) C(60)-H(60B) Au(6)-Au(1)-Au(9) 59.76(8) Au(6)-Au(1)-Au(5) (9) Au(9)-Au(1)-Au(5) (9) Au(6)-Au(1)-Au(3)# (10) Au(9)-Au(1)-Au(3)# (10) Au(5)-Au(1)-Au(3)# (7) Au(6)-Au(1)-Au(8)# (8) Au(9)-Au(1)-Au(8)# (8) Au(5)-Au(1)-Au(8)# (10) Au(3)#1-Au(1)-Au(8)# (9) Au(6)-Au(1)-Au(2)# (10) s16

17 Au(9)-Au(1)-Au(2)# (11) Au(5)-Au(1)-Au(2)# (7) Au(3)#1-Au(1)-Au(2)# (7) Au(8)#1-Au(1)-Au(2)# (9) Au(6)-Au(1)-Au(8) (9) Au(9)-Au(1)-Au(8) (9) Au(5)-Au(1)-Au(8) (9) Au(3)#1-Au(1)-Au(8) 60.87(7) Au(8)#1-Au(1)-Au(8) 61.57(9) Au(2)#1-Au(1)-Au(8) 79.34(7) Au(6)-Au(1)-Au(2) 60.61(7) Au(9)-Au(1)-Au(2) (9) Au(5)-Au(1)-Au(2) (8) Au(3)#1-Au(1)-Au(2) (8) Au(8)#1-Au(1)-Au(2) 79.04(8) Au(2)#1-Au(1)-Au(2) 61.46(9) Au(8)-Au(1)-Au(2) 96.89(8) Au(6)-Au(1)-Au(10) (9) Au(9)-Au(1)-Au(10) 59.67(7) Au(5)-Au(1)-Au(10) 94.73(9) Au(3)#1-Au(1)-Au(10) 60.62(7) Au(8)#1-Au(1)-Au(10) 84.70(8) Au(2)#1-Au(1)-Au(10) (9) Au(8)-Au(1)-Au(10) 66.31(7) Au(2)-Au(1)-Au(10) (9) Au(6)-Au(1)-Au(7) 60.11(7) Au(9)-Au(1)-Au(7) 94.94(8) Au(5)-Au(1)-Au(7) 59.54(7) Au(3)#1-Au(1)-Au(7) (9) Au(8)#1-Au(1)-Au(7) (9) Au(2)#1-Au(1)-Au(7) 84.13(7) Au(8)-Au(1)-Au(7) (9) Au(2)-Au(1)-Au(7) 65.80(6) Au(10)-Au(1)-Au(7) (8) S(3)-Au(2)-Au(1)# (4) S(3)-Au(2)-Au(3) 151.9(4) s17

18 Au(1)#1-Au(2)-Au(3) 59.65(7) S(3)-Au(2)-Au(5)# (3) Au(1)#1-Au(2)-Au(5)# (7) Au(3)-Au(2)-Au(5)# (7) S(3)-Au(2)-Au(6) 90.8(3) Au(1)#1-Au(2)-Au(6) (8) Au(3)-Au(2)-Au(6) 76.44(8) Au(5)#1-Au(2)-Au(6) (9) S(3)-Au(2)-Au(2)#1 82.5(3) Au(1)#1-Au(2)-Au(2)# (7) Au(3)-Au(2)-Au(2)# (7) Au(5)#1-Au(2)-Au(2)# (10) Au(6)-Au(2)-Au(2)# (9) S(3)-Au(2)-Au(1) 94.3(3) Au(1)#1-Au(2)-Au(1) 71.46(9) Au(3)-Au(2)-Au(1) 97.15(8) Au(5)#1-Au(2)-Au(1) (9) Au(6)-Au(2)-Au(1) 52.12(6) Au(2)#1-Au(2)-Au(1) 52.19(6) S(9)-Au(3)-Au(5)# (4) S(9)-Au(3)-Au(1)# (4) Au(5)#1-Au(3)-Au(1)# (7) S(9)-Au(3)-Au(2) 131.1(4) Au(5)#1-Au(3)-Au(2) 61.38(7) Au(1)#1-Au(3)-Au(2) 60.00(7) S(9)-Au(3)-Au(8)# (4) Au(5)#1-Au(3)-Au(8)# (10) Au(1)#1-Au(3)-Au(8)# (8) Au(2)-Au(3)-Au(8)# (8) S(9)-Au(3)-Au(14) 49.1(4) Au(5)#1-Au(3)-Au(14) (10) Au(1)#1-Au(3)-Au(14) (10) Au(2)-Au(3)-Au(14) 91.52(9) Au(8)#1-Au(3)-Au(14) 86.24(9) S(9)-Au(3)-Au(10)# (4) Au(5)#1-Au(3)-Au(10)# (8) s18

19 Au(1)#1-Au(3)-Au(10)# (8) Au(2)-Au(3)-Au(10)# (10) Au(8)#1-Au(3)-Au(10)# (7) Au(14)-Au(3)-Au(10)# (10) S(10)-Au(4)-S(1) 175.5(4) S(10)-Au(4)-Au(9) 82.4(3) S(1)-Au(4)-Au(9) 101.2(3) S(10)-Au(4)-Au(5) 99.8(3) S(1)-Au(4)-Au(5) 82.4(3) Au(9)-Au(4)-Au(5) 98.57(8) S(10)-Au(4)-Au(13) 68.0(3) S(1)-Au(4)-Au(13) 110.7(3) Au(9)-Au(4)-Au(13) 67.85(7) Au(5)-Au(4)-Au(13) (9) S(2)-Au(5)-Au(3)# (4) S(2)-Au(5)-Au(1) 169.0(3) Au(3)#1-Au(5)-Au(1) 60.26(7) S(2)-Au(5)-Au(2)# (3) Au(3)#1-Au(5)-Au(2)# (7) Au(1)-Au(5)-Au(2)# (7) S(2)-Au(5)-Au(7) 105.1(4) Au(3)#1-Au(5)-Au(7) (10) Au(1)-Au(5)-Au(7) 68.85(8) Au(2)#1-Au(5)-Au(7) 88.04(8) S(2)-Au(5)-Au(4) 97.7(3) Au(3)#1-Au(5)-Au(4) 97.70(8) Au(1)-Au(5)-Au(4) 71.94(7) Au(2)#1-Au(5)-Au(4) (9) Au(7)-Au(5)-Au(4) 73.30(7) S(8)-Au(6)-Au(9) 116.8(4) S(8)-Au(6)-Au(1) 167.3(5) Au(9)-Au(6)-Au(1) 60.13(8) S(8)-Au(6)-Au(8)# (4) Au(9)-Au(6)-Au(8)# (8) Au(1)-Au(6)-Au(8)# (8) S(8)-Au(6)-Au(2) 117.5(4) s19

20 Au(9)-Au(6)-Au(2) (10) Au(1)-Au(6)-Au(2) 67.28(7) Au(8)#1-Au(6)-Au(2) 82.07(8) S(8)-Au(6)-Au(14) 49.4(4) Au(9)-Au(6)-Au(14) (10) Au(1)-Au(6)-Au(14) (10) Au(8)#1-Au(6)-Au(14) 91.33(9) Au(2)-Au(6)-Au(14) 87.08(8) S(8)-Au(6)-Au(7) 101.2(4) Au(9)-Au(6)-Au(7) (9) Au(1)-Au(6)-Au(7) 68.50(8) Au(8)#1-Au(6)-Au(7) (10) Au(2)-Au(6)-Au(7) 70.77(7) Au(14)-Au(6)-Au(7) (10) S(3)-Au(7)-S(1) 168.0(4) S(3)-Au(7)-Au(5) 101.4(4) S(1)-Au(7)-Au(5) 84.5(3) S(3)-Au(7)-Au(6) 92.0(3) S(1)-Au(7)-Au(6) 96.9(3) Au(5)-Au(7)-Au(6) (8) S(3)-Au(7)-Au(1) 94.3(3) S(1)-Au(7)-Au(1) 97.5(3) Au(5)-Au(7)-Au(1) 51.61(6) Au(6)-Au(7)-Au(1) 51.39(6) S(7)-Au(8)-Au(1)# (5) S(7)-Au(8)-Au(6)# (5) Au(1)#1-Au(8)-Au(6)# (7) S(7)-Au(8)-Au(9)# (3) Au(1)#1-Au(8)-Au(9)# (7) Au(6)#1-Au(8)-Au(9)# (7) S(7)-Au(8)-Au(3)#1 91.4(4) Au(1)#1-Au(8)-Au(3)# (9) Au(6)#1-Au(8)-Au(3)# (8) Au(9)#1-Au(8)-Au(3)# (10) S(7)-Au(8)-Au(8)#1 82.9(4) Au(1)#1-Au(8)-Au(8)# (8) s20

21 Au(6)#1-Au(8)-Au(8)# (8) Au(9)#1-Au(8)-Au(8)# (12) Au(3)#1-Au(8)-Au(8)# (9) S(7)-Au(8)-Au(1) 94.7(3) Au(1)#1-Au(8)-Au(1) 71.77(9) Au(6)#1-Au(8)-Au(1) 97.10(8) Au(9)#1-Au(8)-Au(1) (9) Au(3)#1-Au(8)-Au(1) 52.50(6) Au(8)#1-Au(8)-Au(1) 52.38(6) S(4)-Au(9)-Au(6) 126.5(4) S(4)-Au(9)-Au(1) 169.6(4) Au(6)-Au(9)-Au(1) 60.11(7) S(4)-Au(9)-Au(8)# (3) Au(6)-Au(9)-Au(8)# (7) Au(1)-Au(9)-Au(8)# (7) S(4)-Au(9)-Au(10) 105.4(4) Au(6)-Au(9)-Au(10) (9) Au(1)-Au(9)-Au(10) 68.50(8) Au(8)#1-Au(9)-Au(10) 88.55(9) S(4)-Au(9)-Au(4) 98.2(3) Au(6)-Au(9)-Au(4) 96.46(9) Au(1)-Au(9)-Au(4) 72.14(8) Au(8)#1-Au(9)-Au(4) (9) Au(10)-Au(9)-Au(4) 73.76(8) S(7)-Au(10)-S(10) 169.0(5) S(7)-Au(10)-Au(9) 100.9(5) S(10)-Au(10)-Au(9) 84.2(4) S(7)-Au(10)-Au(3)#1 91.3(3) S(10)-Au(10)-Au(3)#1 97.2(3) Au(9)-Au(10)-Au(3)# (8) S(7)-Au(10)-Au(1) 93.7(4) S(10)-Au(10)-Au(1) 97.1(3) Au(9)-Au(10)-Au(1) 51.83(6) Au(3)#1-Au(10)-Au(1) 51.71(6) S(2)-Au(11)-S(5) 177.1(5) S(5)-Au(12)-S(6) 175.4(5) s21

22 S(6)-Au(13)-S(4) 176.4(5) S(6)-Au(13)-Au(4) 93.2(4) S(4)-Au(13)-Au(4) 90.4(3) S(8)-Au(14)-S(9) 175.5(5) S(8)-Au(14)-Au(6) 51.4(4) S(9)-Au(14)-Au(6) 124.1(4) S(8)-Au(14)-Au(3) 123.1(4) S(9)-Au(14)-Au(3) 52.4(4) Au(6)-Au(14)-Au(3) 72.60(8) C(1)-S(1)-Au(7) 103.5(15) C(1)-S(1)-Au(4) 113.6(15) Au(7)-S(1)-Au(4) 101.7(5) C(7)-S(2)-Au(11) 103.9(16) C(7)-S(2)-Au(5) 104.6(15) Au(11)-S(2)-Au(5) 102.6(5) C(13)-S(3)-Au(7) 108(3) C(13)-S(3)-Au(2) 111.8(16) Au(7)-S(3)-Au(2) 96.5(4) C(19)-S(4)-Au(13) 101.0(15) C(19)-S(4)-Au(9) 105.1(14) Au(13)-S(4)-Au(9) 102.3(6) C(25)-S(5)-Au(12) 106.0(12) C(25)-S(5)-Au(11) 109.8(17) Au(12)-S(5)-Au(11) 102.7(5) C(31)-S(6)-Au(13) 113.9(16) C(31)-S(6)-Au(12) 106.3(11) Au(13)-S(6)-Au(12) 103.4(6) C(37)-S(7)-Au(10) 108(3) C(37)-S(7)-Au(8) 113(2) Au(10)-S(7)-Au(8) 96.3(5) C(43)-S(8)-Au(14) 103(2) C(43)-S(8)-Au(6) 107.8(16) Au(14)-S(8)-Au(6) 79.2(5) C(49)-S(9)-Au(14) 104(2) C(49)-S(9)-Au(3) 108.6(16) Au(14)-S(9)-Au(3) 78.5(5) s22

23 C(55)-S(10)-Au(10) 99.1(19) C(55)-S(10)-Au(4) 112.7(19) Au(10)-S(10)-Au(4) 102.1(5) C(6)-C(1)-C(2) 111(2) C(6)-C(1)-S(1) 109(3) C(2)-C(1)-S(1) 106(3) C(6)-C(1)-H(1) C(2)-C(1)-H(1) S(1)-C(1)-H(1) C(3)-C(2)-C(1) 110(2) C(3)-C(2)-H(2A) C(1)-C(2)-H(2A) C(3)-C(2)-H(2B) C(1)-C(2)-H(2B) H(2A)-C(2)-H(2B) C(2)-C(3)-C(4) 111(2) C(2)-C(3)-H(3A) C(4)-C(3)-H(3A) C(2)-C(3)-H(3B) C(4)-C(3)-H(3B) H(3A)-C(3)-H(3B) C(5)-C(4)-C(3) 111(2) C(5)-C(4)-H(4A) C(3)-C(4)-H(4A) C(5)-C(4)-H(4B) C(3)-C(4)-H(4B) H(4A)-C(4)-H(4B) C(4)-C(5)-C(6) 111(2) C(4)-C(5)-H(5A) C(6)-C(5)-H(5A) C(4)-C(5)-H(5B) C(6)-C(5)-H(5B) H(5A)-C(5)-H(5B) C(1)-C(6)-C(5) 111(2) C(1)-C(6)-H(6A) C(5)-C(6)-H(6A) s23

24 C(1)-C(6)-H(6B) C(5)-C(6)-H(6B) H(6A)-C(6)-H(6B) C(8)-C(7)-C(12) 113(2) C(8)-C(7)-S(2) 114(3) C(12)-C(7)-S(2) 112(3) C(8)-C(7)-H(7) C(12)-C(7)-H(7) S(2)-C(7)-H(7) C(7)-C(8)-C(9) 113(2) C(7)-C(8)-H(8A) C(9)-C(8)-H(8A) C(7)-C(8)-H(8B) C(9)-C(8)-H(8B) H(8A)-C(8)-H(8B) C(10)-C(9)-C(8) 112(2) C(10)-C(9)-H(9A) C(8)-C(9)-H(9A) C(10)-C(9)-H(9B) C(8)-C(9)-H(9B) H(9A)-C(9)-H(9B) C(11)-C(10)-C(9) 113(2) C(11)-C(10)-H(10A) C(9)-C(10)-H(10A) C(11)-C(10)-H(10B) C(9)-C(10)-H(10B) H(10A)-C(10)-H(10B) C(10)-C(11)-C(12) 113(2) C(10)-C(11)-H(11A) C(12)-C(11)-H(11A) C(10)-C(11)-H(11B) C(12)-C(11)-H(11B) H(11A)-C(11)-H(11B) C(7)-C(12)-C(11) 113(2) C(7)-C(12)-H(12A) C(11)-C(12)-H(12A) s24

25 C(7)-C(12)-H(12B) C(11)-C(12)-H(12B) H(12A)-C(12)-H(12B) C(14)-C(13)-C(18) 113(3) C(14)-C(13)-S(3) 116(4) C(18)-C(13)-S(3) 111(4) C(14)-C(13)-H(13) C(18)-C(13)-H(13) S(3)-C(13)-H(13) C(13)-C(14)-C(15) 113(3) C(13)-C(14)-H(14A) C(15)-C(14)-H(14A) C(13)-C(14)-H(14B) C(15)-C(14)-H(14B) H(14A)-C(14)-H(14B) C(14)-C(15)-C(16) 112(3) C(14)-C(15)-H(15A) C(16)-C(15)-H(15A) C(14)-C(15)-H(15B) C(16)-C(15)-H(15B) H(15A)-C(15)-H(15B) C(17)-C(16)-C(15) 112(3) C(17)-C(16)-H(16A) C(15)-C(16)-H(16A) C(17)-C(16)-H(16B) C(15)-C(16)-H(16B) H(16A)-C(16)-H(16B) C(18)-C(17)-C(16) 113(3) C(18)-C(17)-H(17A) C(16)-C(17)-H(17A) C(18)-C(17)-H(17B) C(16)-C(17)-H(17B) H(17A)-C(17)-H(17B) C(17)-C(18)-C(13) 113(3) C(17)-C(18)-H(18A) C(13)-C(18)-H(18A) s25

26 C(17)-C(18)-H(18B) C(13)-C(18)-H(18B) H(18A)-C(18)-H(18B) C(24)-C(19)-C(20) 107(3) C(24)-C(19)-S(4) 106(3) C(20)-C(19)-S(4) 105(3) C(24)-C(19)-H(19) C(20)-C(19)-H(19) S(4)-C(19)-H(19) C(19)-C(20)-C(21) 107(3) C(19)-C(20)-H(20A) C(21)-C(20)-H(20A) C(19)-C(20)-H(20B) C(21)-C(20)-H(20B) H(20A)-C(20)-H(20B) C(22)-C(21)-C(20) 107(3) C(22)-C(21)-H(21A) C(20)-C(21)-H(21A) C(22)-C(21)-H(21B) C(20)-C(21)-H(21B) H(21A)-C(21)-H(21B) C(21)-C(22)-C(23) 107(3) C(21)-C(22)-H(22A) C(23)-C(22)-H(22A) C(21)-C(22)-H(22B) C(23)-C(22)-H(22B) H(22A)-C(22)-H(22B) C(24)-C(23)-C(22) 107(3) C(24)-C(23)-H(23A) C(22)-C(23)-H(23A) C(24)-C(23)-H(23B) C(22)-C(23)-H(23B) H(23A)-C(23)-H(23B) C(19)-C(24)-C(23) 107(3) C(19)-C(24)-H(24A) C(23)-C(24)-H(24A) s26

27 C(19)-C(24)-H(24B) C(23)-C(24)-H(24B) H(24A)-C(24)-H(24B) C(26)-C(25)-C(30) 109(2) C(26)-C(25)-S(5) 108(3) C(30)-C(25)-S(5) 106(3) C(26)-C(25)-H(25) C(30)-C(25)-H(25) S(5)-C(25)-H(25) C(27)-C(26)-C(25) 109(2) C(27)-C(26)-H(26A) C(25)-C(26)-H(26A) C(27)-C(26)-H(26B) C(25)-C(26)-H(26B) H(26A)-C(26)-H(26B) C(28)-C(27)-C(26) 110(2) C(28)-C(27)-H(27A) C(26)-C(27)-H(27A) C(28)-C(27)-H(27B) C(26)-C(27)-H(27B) H(27A)-C(27)-H(27B) C(27)-C(28)-C(29) 110(3) C(27)-C(28)-H(28A) C(29)-C(28)-H(28A) C(27)-C(28)-H(28B) C(29)-C(28)-H(28B) H(28A)-C(28)-H(28B) C(28)-C(29)-C(30) 110(3) C(28)-C(29)-H(29A) C(30)-C(29)-H(29A) C(28)-C(29)-H(29B) C(30)-C(29)-H(29B) H(29A)-C(29)-H(29B) C(29)-C(30)-C(25) 109(2) C(29)-C(30)-H(30A) C(25)-C(30)-H(30A) s27

28 C(29)-C(30)-H(30B) C(25)-C(30)-H(30B) H(30A)-C(30)-H(30B) C(36)-C(31)-C(32) 103(3) C(36)-C(31)-S(6) 105(3) C(32)-C(31)-S(6) 101(3) C(36)-C(31)-H(31) C(32)-C(31)-H(31) S(6)-C(31)-H(31) C(33)-C(32)-C(31) 104(3) C(33)-C(32)-H(32A) C(31)-C(32)-H(32A) C(33)-C(32)-H(32B) C(31)-C(32)-H(32B) H(32A)-C(32)-H(32B) C(34)-C(33)-C(32) 104(3) C(34)-C(33)-H(33A) C(32)-C(33)-H(33A) C(34)-C(33)-H(33B) C(32)-C(33)-H(33B) H(33A)-C(33)-H(33B) C(35)-C(34)-C(33) 105(3) C(35)-C(34)-H(34A) C(33)-C(34)-H(34A) C(35)-C(34)-H(34B) C(33)-C(34)-H(34B) H(34A)-C(34)-H(34B) C(34)-C(35)-C(36) 105(3) C(34)-C(35)-H(35A) C(36)-C(35)-H(35A) C(34)-C(35)-H(35B) C(36)-C(35)-H(35B) H(35A)-C(35)-H(35B) C(35)-C(36)-C(31) 104(3) C(35)-C(36)-H(36A) C(31)-C(36)-H(36A) s28

29 C(35)-C(36)-H(36B) C(31)-C(36)-H(36B) H(36A)-C(36)-H(36B) C(42)-C(37)-C(38) 109(3) C(42)-C(37)-S(7) 111(4) C(38)-C(37)-S(7) 112(4) C(42)-C(37)-H(37) C(38)-C(37)-H(37) S(7)-C(37)-H(37) C(39)-C(38)-C(37) 110(3) C(39)-C(38)-H(38A) C(37)-C(38)-H(38A) C(39)-C(38)-H(38B) C(37)-C(38)-H(38B) H(38A)-C(38)-H(38B) C(38)-C(39)-C(40) 109(3) C(38)-C(39)-H(39A) C(40)-C(39)-H(39A) C(38)-C(39)-H(39B) C(40)-C(39)-H(39B) H(39A)-C(39)-H(39B) C(39)-C(40)-C(41) 109(3) C(39)-C(40)-H(40A) C(41)-C(40)-H(40A) C(39)-C(40)-H(40B) C(41)-C(40)-H(40B) H(40A)-C(40)-H(40B) C(42)-C(41)-C(40) 109(3) C(42)-C(41)-H(41A) C(40)-C(41)-H(41A) C(42)-C(41)-H(41B) C(40)-C(41)-H(41B) H(41A)-C(41)-H(41B) C(37)-C(42)-C(41) 109(3) C(37)-C(42)-H(42A) C(41)-C(42)-H(42A) s29

30 C(37)-C(42)-H(42B) C(41)-C(42)-H(42B) H(42A)-C(42)-H(42B) C(48)-C(43)-C(44) 108(3) C(48)-C(43)-S(8) 114(3) C(44)-C(43)-S(8) 108(3) C(48)-C(43)-H(43) C(44)-C(43)-H(43) S(8)-C(43)-H(43) C(45)-C(44)-C(43) 109(3) C(45)-C(44)-H(44A) C(43)-C(44)-H(44A) C(45)-C(44)-H(44B) C(43)-C(44)-H(44B) H(44A)-C(44)-H(44B) C(46)-C(45)-C(44) 109(3) C(46)-C(45)-H(45A) C(44)-C(45)-H(45A) C(46)-C(45)-H(45B) C(44)-C(45)-H(45B) H(45A)-C(45)-H(45B) C(47)-C(46)-C(45) 110(3) C(47)-C(46)-H(46A) C(45)-C(46)-H(46A) C(47)-C(46)-H(46B) C(45)-C(46)-H(46B) H(46A)-C(46)-H(46B) C(46)-C(47)-C(48) 110(3) C(46)-C(47)-H(47A) C(48)-C(47)-H(47A) C(46)-C(47)-H(47B) C(48)-C(47)-H(47B) H(47A)-C(47)-H(47B) C(47)-C(48)-C(43) 109(3) C(47)-C(48)-H(48A) C(43)-C(48)-H(48A) s30

31 C(47)-C(48)-H(48B) C(43)-C(48)-H(48B) H(48A)-C(48)-H(48B) C(54)-C(49)-C(50) 110(3) C(54)-C(49)-S(9) 107(3) C(50)-C(49)-S(9) 116(3) C(54)-C(49)-H(49) C(50)-C(49)-H(49) S(9)-C(49)-H(49) C(49)-C(50)-C(51) 110(2) C(49)-C(50)-H(50A) C(51)-C(50)-H(50A) C(49)-C(50)-H(50B) C(51)-C(50)-H(50B) H(50A)-C(50)-H(50B) C(52)-C(51)-C(50) 110(3) C(52)-C(51)-H(51A) C(50)-C(51)-H(51A) C(52)-C(51)-H(51B) C(50)-C(51)-H(51B) H(51A)-C(51)-H(51B) C(53)-C(52)-C(51) 110(3) C(53)-C(52)-H(52A) C(51)-C(52)-H(52A) C(53)-C(52)-H(52B) C(51)-C(52)-H(52B) H(52A)-C(52)-H(52B) C(52)-C(53)-C(54) 110(3) C(52)-C(53)-H(53A) C(54)-C(53)-H(53A) C(52)-C(53)-H(53B) C(54)-C(53)-H(53B) H(53A)-C(53)-H(53B) C(53)-C(54)-C(49) 110(3) C(53)-C(54)-H(54A) C(49)-C(54)-H(54A) s31

32 C(53)-C(54)-H(54B) C(49)-C(54)-H(54B) H(54A)-C(54)-H(54B) C(60)-C(55)-C(56) 112(2) C(60)-C(55)-S(10) 100(3) C(56)-C(55)-S(10) 109(4) C(60)-C(55)-H(55) C(56)-C(55)-H(55) S(10)-C(55)-H(55) C(55)-C(56)-C(57) 111(2) C(55)-C(56)-H(56A) C(57)-C(56)-H(56A) C(55)-C(56)-H(56B) C(57)-C(56)-H(56B) H(56A)-C(56)-H(56B) C(58)-C(57)-C(56) 110(2) C(58)-C(57)-H(57A) C(56)-C(57)-H(57A) C(58)-C(57)-H(57B) C(56)-C(57)-H(57B) H(57A)-C(57)-H(57B) C(59)-C(58)-C(57) 112(2) C(59)-C(58)-H(58A) C(57)-C(58)-H(58A) C(59)-C(58)-H(58B) C(57)-C(58)-H(58B) H(58A)-C(58)-H(58B) C(58)-C(59)-C(60) 112(2) C(58)-C(59)-H(59A) C(60)-C(59)-H(59A) C(58)-C(59)-H(59B) C(60)-C(59)-H(59B) H(59A)-C(59)-H(59B) C(59)-C(60)-C(55) 111(2) C(59)-C(60)-H(60A) C(55)-C(60)-H(60A) s32

33 C(59)-C(60)-H(60B) C(55)-C(60)-H(60B) H(60A)-C(60)-H(60B) Symmetry transformations used to generate equivalent atoms: #1 -x+1,y,-z+1/2 s33

34 Table S7. Anisotropic displacement parameters (Å 2 x 10 3 ) for Au 28 (S-c-C 6 H 11 ) 20. The anisotropic displacement factor exponent takes the form: -2π 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 Au(1) 55(1) 32(1) 52(1) 1(1) -4(1) 5(1) Au(2) 54(1) 45(1) 36(1) -3(1) -6(1) 0(1) Au(3) 59(1) 45(1) 52(1) -1(1) -2(1) 8(1) Au(4) 67(2) 42(1) 49(1) 3(1) -2(1) -4(1) Au(5) 63(2) 45(1) 36(1) -9(1) -4(1) 0(1) Au(6) 58(2) 46(1) 50(1) 3(1) -6(1) 2(1) Au(7) 66(2) 43(1) 46(1) -2(1) -6(1) -3(1) Au(8) 79(2) 45(1) 40(1) -1(1) 2(1) -8(1) Au(9) 82(2) 42(1) 40(1) 12(1) 0(1) 5(1) Au(10) 85(2) 42(1) 51(1) 2(1) 1(1) -8(1) Au(11) 98(2) 54(1) 39(1) 1(1) 1(1) 2(1) Au(12) 95(2) 55(1) 57(1) 2(1) -3(1) 5(1) Au(13) 114(2) 54(1) 42(1) 5(1) -5(1) 7(1) Au(14) 74(2) 94(2) 66(2) 4(2) -2(1) 9(2) S(1) 71(9) 60(8) 38(7) 11(6) 4(7) -6(7) S(2) 85(11) 65(8) 40(7) 0(7) 0(7) 17(8) S(3) 78(10) 42(7) 46(8) 5(6) 5(7) -11(7) S(4) 122(13) 65(9) 37(7) 6(7) 1(8) 25(9) S(5) 127(14) 53(8) 51(8) 0(7) 1(9) 1(9) S(6) 130(14) 55(9) 50(8) 0(7) -2(9) 12(9) S(7) 136(14) 43(8) 49(8) -2(6) 6(9) -6(9) S(8) 46(9) 104(12) 108(13) 0(10) -19(9) -4(8) S(9) 56(10) 99(12) 95(12) 0(10) 10(9) 19(9) S(10) 87(10) 41(7) 44(7) 6(6) 12(7) 4(7) C(1) 90(30) 90(30) 90(30) 30(20) -20(20) -10(20) C(2) 100(30) 110(30) 90(30) 30(20) 0(30) -10(20) C(3) 110(30) 120(30) 90(30) 40(20) -20(30) 0(20) C(4) 90(30) 130(30) 100(30) 20(30) -10(30) -10(20) C(5) 80(20) 110(30) 100(30) 10(20) 20(30) -10(20) C(6) 90(30) 110(30) 100(30) 20(20) 0(20) -20(20) s34

35 C(7) 180(40) 45(18) 80(20) -2(19) -20(30) 20(30) C(8) 160(40) 60(20) 80(20) 0(20) 10(30) 0(30) C(9) 150(40) 60(20) 120(30) 10(20) 20(30) 0(30) C(10) 160(40) 60(20) 110(30) 0(20) 10(30) 0(30) C(11) 170(40) 47(18) 100(20) 0(20) -20(30) 20(30) C(12) 180(40) 50(20) 80(20) -5(19) -10(30) 10(30) C(13) 80(30) 110(40) 320(60) -110(40) -70(40) 0(20) C(14) 80(30) 110(40) 340(60) -120(40) -70(40) 0(20) C(15) 80(30) 130(40) 340(60) -110(40) -80(40) -10(20) C(16) 70(30) 130(40) 340(60) -110(40) -80(40) -20(20) C(17) 90(30) 120(40) 330(60) -100(40) -70(40) -20(20) C(18) 70(30) 100(30) 320(60) -110(30) -70(40) -10(20) C(19) 150(40) 54(19) 90(20) 15(18) 30(30) 0(30) C(20) 150(40) 55(19) 70(20) -10(20) 0(30) 0(20) C(21) 160(40) 60(20) 90(20) 9(18) 0(30) -20(20) C(22) 150(40) 70(20) 100(30) 16(19) 40(30) 0(30) C(23) 150(40) 63(19) 100(20) 30(20) 50(30) 20(30) C(24) 160(40) 70(20) 90(20) 21(19) 40(30) 20(20) C(25) 100(30) 36(18) 140(30) 40(20) 10(20) 17(18) C(26) 100(30) 47(17) 150(30) 0(30) 0(20) 30(20) C(27) 100(30) 80(20) 140(30) 10(30) 0(30) 30(20) C(28) 110(30) 100(30) 140(30) 20(30) 0(30) 10(20) C(29) 100(30) 90(20) 160(40) 20(30) 10(30) 10(20) C(30) 110(30) 60(20) 140(30) 30(30) 10(20) 0(20) C(31) 50(20) 50(20) 110(30) -30(20) -30(20) 34(17) C(32) 70(30) 90(20) 110(30) -10(20) -50(20) 10(19) C(33) 80(30) 100(20) 140(30) 10(30) -70(20) 20(20) C(34) 100(30) 110(30) 150(30) 0(30) -50(30) 30(20) C(35) 120(30) 80(20) 120(30) 20(30) -20(30) 40(20) C(36) 80(30) 59(19) 130(30) -10(20) -20(20) 48(18) C(37) 190(50) 80(40) 260(50) 40(30) 0(50) -60(30) C(38) 190(50) 90(40) 250(50) 40(30) 10(50) -40(30) C(39) 190(50) 90(40) 270(60) 50(30) 20(50) -50(30) C(40) 180(50) 90(40) 280(60) 40(40) 20(50) -50(30) C(41) 180(50) 90(40) 290(60) 50(30) 0(50) -60(30) C(42) 190(50) 70(30) 280(60) 40(30) 0(40) -60(30) s35

36 C(43) 80(20) 150(30) 90(30) 90(20) -30(20) -30(20) C(44) 80(20) 170(30) 110(30) 80(30) -30(30) -20(30) C(45) 110(30) 180(40) 140(40) 70(30) -50(30) 10(30) C(46) 120(30) 180(30) 150(40) 70(30) -50(30) 20(30) C(47) 120(30) 160(30) 140(30) 90(30) -40(30) -10(30) C(48) 100(30) 150(30) 120(30) 90(20) -50(30) -20(30) C(49) 100(30) 110(30) 100(30) -10(30) 20(30) -10(30) C(50) 90(30) 100(30) 100(30) 10(30) 20(30) 0(20) C(51) 90(30) 120(30) 130(30) 0(30) 20(30) -20(30) C(52) 90(30) 130(30) 160(40) 0(30) 20(30) -10(30) C(53) 100(30) 140(30) 160(40) 0(30) 40(30) -10(30) C(54) 100(30) 130(30) 140(30) -10(30) 50(30) 10(30) C(55) 120(30) 120(30) 210(40) -60(30) -90(30) 10(30) C(56) 100(30) 130(30) 210(40) -50(30) -80(40) 10(30) C(57) 120(30) 150(40) 210(40) -50(30) -70(40) 20(30) C(58) 130(30) 140(40) 220(50) -60(30) -80(40) 50(30) C(59) 120(30) 130(30) 240(50) -50(30) -90(40) 60(30) C(60) 110(30) 110(30) 210(40) -60(30) -120(30) 70(30) s36

37 Table S8. Hydrogen coordinates (x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for Au 28 (S-c-C 6 H 11 ) 20. x y z U(eq) H(1) H(2A) H(2B) H(3A) H(3B) H(4A) H(4B) H(5A) H(5B) H(6A) H(6B) H(7) H(8A) H(8B) H(9A) H(9B) H(10A) H(10B) H(11A) H(11B) H(12A) H(12B) H(13) H(14A) H(14B) H(15A) H(15B) H(16A) H(16B) H(17A) s37

38 H(17B) H(18A) H(18B) H(19) H(20A) H(20B) H(21A) H(21B) H(22A) H(22B) H(23A) H(23B) H(24A) H(24B) H(25) H(26A) H(26B) H(27A) H(27B) H(28A) H(28B) H(29A) H(29B) H(30A) H(30B) H(31) H(32A) H(32B) H(33A) H(33B) H(34A) H(34B) H(35A) H(35B) H(36A) H(36B) s38

39 H(37) H(38A) H(38B) H(39A) H(39B) H(40A) H(40B) H(41A) H(41B) H(42A) H(42B) H(43) H(44A) H(44B) H(45A) H(45B) H(46A) H(46B) H(47A) H(47B) H(48A) H(48B) H(49) H(50A) H(50B) H(51A) H(51B) H(52A) H(52B) H(53A) H(53B) H(54A) H(54B) H(55) H(56A) H(56B) s39

40 H(57A) H(57B) H(58A) H(58B) H(59A) H(59B) H(60A) H(60B) Supporting references: s1. Zeng, C.; Li, T.; Das, A.; Rosi, N.; Jin, R. J. Am. Chem. Soc. 2013, 135, s2. Wu, Z.; Suhan, J.; Jin, R. J. Mater. Chem. 2009, 19, 622. s3. APEX II software suite, Bruker-AXS, s4. SHELXTL, G. M. Sheldrick, Acta Crystallogr. Sect A, 2008, 64, 112. s5. Ahlrichs, R.; Bar, M.; Haser, M.; Horn, H.; Kolmel, C. Chem. Phys. Lett. 1989, 162, 165. s6. Tao, J.; Perdew, J. P.; Staroverov, V. N.; Scuseria, G. E. Phys. Rev. Lett. 2003, 91, s7. Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. J. Chem. Phys. 2010, 132, s8. Reed, A. E.; Weinstock, R. B.; Weinhold, F. J. Chem. Phys. 1985, 83, 735. s40