Supporting Information

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1 SI-1 Supporting Information Aminorifamycins and Sporalactams Produced in Culture by a Micromonospora sp. Isolated from a Northeastern-Pacific Marine Sediment are Potent Antibiotics David E. Williams, Doralyn S. Dalisay, Jessie Chen, Elena Polishchuk, Brian. Patrick, Gagandeep Narula, Mary Ko, Yossef Av-Gay, Haoxin Li, Nathan Magarvey and Raymond J. Andersen* Departments of Chemistry and Earth, cean & Atmospheric Sciences, University of British Columbia, 2036 Main Mall, Vancouver, B. C., CANADA, V6T 1Z1; Infection and Immunity Research Centre, University of British Columbia, ak Street, Vancouver, B.C., Canada V6H 3Z6; Departments of Biochemistry and Biomedical Sciences, McMaster University, Hamilton, ntario, Canada; Department of Pharmacy and Gregor Mendel Research Laboratories, University of San Agustin, Iloilo City, Philippines. Table of contents Pages SI-3 to SI-4: Page SI-5: Experimental section General Experimental Methods. Bacterial Material. Genome sequencing. Extraction of Micromonospora sp. and Isolation of Metabolites 1-6. Table SI1. 1 H NMR data for 3-amino-27-demethoxy-27-hydroxyrifamycin S (1) and 3-aminorifamycin S (2) recorded in DMS-d 6 at 600 MHz. Page SI-6: Table SI2. 13 C and 15 N NMR data for 3-amino-27-demethoxy-27-hydroxyrifamycin S (1) and 3-amino-rifamycin S (2) recorded in DMS-d 6 at 150 MHz. Page SI-7: Table SI3. NMR data for sporalactams A (3) and B (4) recorded in DMS-d 6. Page SI-8: 1 H NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) recorded at 600 MHz in DMS-d 6. Page SI-9: Expanded 1 H NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) with peak picking recorded at 600 MHz in DMS-d 6. Page SI-10: Expanded 1 H NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) with peak picking recorded at 600 MHz in DMS-d 6. Page SI-11: Expanded 1 H NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) with peak picking recorded at 600 MHz in DMS-d 6. Page SI-12: 13 C NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) recorded at 150 MHz in DMS-d 6. Page SI-13: Expanded 13 C NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) with peak picking recorded at 150 MHz in DMS-d 6. Page SI-14: Expanded 13 C NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) with peak picking recorded at 150 MHz in DMS-d 6. Page SI-15: gradcsy60 NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) recorded at 600 MHz in DMS-d 6. Page SI-16: gradhsqc NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) recorded at 600 MHz in DMS-d 6. Page SI-17: gradhmbc NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) recorded at 600 MHz in DMS-d 6. Page SI-18: tresy NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) recorded at 600 MHz in DMS-d 6.

2 SI-2 Page SI-19: grad 15 NHSQC NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) recorded at 600 MHz in DMS-d 6. Page SI-20 to SI-60: Details of the X-ray Diffraction Analysis of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1). Page SI-61: 1 H NMR Spectrum of 3-Amino-rifamycin S (2) recorded at 600 MHz in DMS-d 6. Page SI-62: Expanded 1 H NMR Spectrum of 3-Amino-rifamycin S (2) with peak picking recorded at 600 MHz in DMS-d 6. Page SI-63: Expanded 1 H NMR Spectrum of 3-Amino-rifamycin S (2) with peak picking recorded at 600 MHz in DMS-d 6. Page SI-64: Expanded 1 H NMR Spectrum of 3-Amino-rifamycin S (2) with peak picking recorded at 600 MHz in DMS-d 6. Page SI-65: gradcsy60 NMR Spectrum of 3-Amino-rifamycin S (2) recorded at 600 MHz in DMS-d 6. Page SI-66: gradhsqc NMR Spectrum of 3-Amino-rifamycin S (2) recorded at 600 MHz in DMS-d 6. Page SI-67: gradhmbc NMR Spectrum of 3-Amino-rifamycin S (2) recorded at 600 MHz in DMS-d 6. Page SI-68: tresy NMR Spectrum of 3-Amino-rifamycin S (2) recorded at 600 MHz in DMS-d 6. Page SI-69: grad 15 NHSQC NMR Spectrum of 3-Amino-rifamycin S (2) recorded at 600 MHz in DMS-d 6. Page SI-70: 1 H NMR Spectrum of Sporalactam A (3) recorded at 600 MHz in DMS-d 6. Page SI-71: Expanded 1 H NMR Spectrum of Sporalactam A (3) with peak picking recorded at 600 MHz in DMS-d 6. Page SI-72: Expanded 1 H NMR Spectrum of Sporalactam A (3) with peak picking recorded at 600 MHz in DMS-d 6. Page SI-73: 13 C NMR Spectrum of Sporalactam A (3) recorded at 150 MHz in DMS-d 6. Page SI-74: gradcsy60 NMR Spectrum of Sporalactam A (3) recorded at 600 MHz in DMS-d 6. Page SI-75: gradhsqc NMR Spectrum of Sporalactam A (3) recorded at 600 MHz in DMS-d 6. Page SI-76: gradhmbc NMR Spectrum of Sporalactam A (3) recorded at 600 MHz in DMS-d 6. Page SI-77: tresy NMR Spectrum of Sporalactam A (3) recorded at 600 MHz in DMS-d 6. Page SI-78: grad 15 NHSQC NMR Spectrum of Sporalactam A (3) recorded at 600 MHz in DMS-d 6. Page SI-79: 1 H NMR Spectrum of Page SI-6: 1 H NMR Spectrum of Sporalactam B (4) recorded at 600 MHz in DMS-d 6. Page SI-80: Expanded 1 H NMR Spectrum of Sporalactam B (4) with peak picking recorded at 600 MHz in DMS-d 6. Page SI-81: Expanded 1 H NMR Spectrum of Sporalactam B (4) with peak picking recorded at 600 MHz in DMS-d 6. Page SI-82: 13 C NMR Spectrum of Sporalactam B (4) recorded at 150 MHz in DMS-d 6. Page SI-83: gradcsy60 NMR Spectrum of Sporalactam B (4) recorded at 600 MHz in DMS-d 6. Page SI-84: gradhsqc NMR Spectrum of Sporalactam B (4) recorded at 600 MHz in DMS-d 6. Page SI-85: gradhmbc NMR Spectrum of Sporalactam B (4) recorded at 600 MHz in DMS-d 6. Page SI-86: tresy NMR Spectrum of Sporalactam B (4) recorded at 600 MHz in DMS-d 6. Page SI-87: Table SI4. In vitro broth culture and intracellular MIC 90 s in µm. Page SI-88: Figure SI1. Rifamycin analogue cluster in Micromonospora sp. RJA 4480 identified by PRISM. Page SI-89 Chem3D Calculated MM2 Energy Minimized Conformations for Sporalactam B (4) C-16 to SI-91: Epimers. Figure SI2A) C-16R Epimer; Figure SI2B) C-16S Epimer; Figure SI2C Sporalactam B (4) [16S]: Planes with Hs 1, 8, 21, and 23.

3 Experimental Section SI-3 General Experimental Methods. ptical rotations were measured using a Jasco P-1010 Polarimeter with sodium light (589 nm). UV spectra were recorded with a Waters 996 Photodiode Array Detector. The 1 H and 13 C NMR spectra were recorded on a Bruker AV-600 spectrometer with a 5 mm CPTCI cryoprobe. 1 H chemical shifts are referenced to the residual DMS-d 6 (δ 2.49 ppm) and 13 C chemical shifts are referenced to the DMS-d 6 solvent peak (δ 39.5 ppm). Low and high resolution ESI-QIT-MS were recorded on a Bruker-Hewlett Packard 1100 Esquire LC system mass spectrometer. Merck Type 5554 silica gel plates and Whatman MKC18F plates were used for analytical thin layer chromatography. Reversed-phase HPLC purifications were performed on a Waters 600E System Controller liquid chromatography attached to a Waters 996 Photodiode Array Detector. All solvents used for HPLC were Fisher HPLC grade. Bacterial Material. Isolate RJA4480, Micromonospora sp., was isolated on Marine Medium 10 (10.0 g of glucose, 4.0 g of yeast extract, 2.0 g of peptone, 100 ug/ml of cyclohexamide, 5 ug/ml of rifampicin, 15.0 g of agar, 1L of sea water) from a marine sediment collected at Barkley Sound, British Columbia, Canada at a depth of 85 metres (N , W ). NCBI BLAST analysis of the partial 16S rrna sequence of Micromonospora sp. RJA4480 (deposited in GenBank with an accession number KY129664) is 99% identical to Micromonospora matsumotoense strain LS279 (FJ ) and to Micromonosporaceae bacterium (GU ). Genome sequencing. A single colony of RJA4480, Micromonospora sp., was grown in 3 ml marine medium 1 for four days at 28 C with shaking at 250 r.p.m. Genomic DNA was harvested using a GenElute Bacterial Genomic DNA Kit (Sigma), and sequenced at the Farncombe Metagenomics Facility (McMaster University), using an Illumina MiSeq DNA sequencer. Contigs were assembled using the ABySS genome assembly program. Secondary metabolite biosynthetic gene clusters were predicted using PRISM. Extraction of Micromonospora sp. and Isolation of Metabolites 1-6. The strain RJA4480 was cultured on 7 trays of solid agar, equivalent to 2.2 L volume of the marine medium 1 (MM1) (10.0 g of soluble starch, 4.0 g of yeast extract, 2.0 g of peptone, 0.001g of FeS 4.7H 2, g of KBr, 18.0 g agar, 1 L sea water) at RT for 14 days. The mature cultures were sliced into small squares containing the micromonospora biomass and the media, and extracted twice with EtAc. The combined EtAc extracts were concentrated in vacuo and partitioned between H 2 (300 ml) and EtAc (3 x 150 ml). The EtAc extracts were combined and concentrated in vacuo and the EtAc soluble material was chromatographed on Sephadex LH20 with 4:1 methanol/ch 2 Cl 2 as eluent. A fraction responsible for the strong MRSA and E. coli inhibitory activity was subjected to Si gel flash chromatography (step gradient: 19:1 hexanes/etac to EtAc to 1:9 MeH/EtAc and to MeH, 2 g Sep pak). The 1:1 hexanes/etac fraction elicited antimicrobial activity. Pure samples of 3-amino-27-demethoxy-27- hydroxyrifamycin S (1) (3.6 mg), 3-amino-rifamycin S (2) (0.6 mg), rifamycin W-lactone (5) 1 (2.2 mg), 27-demethoxy-27-hydroxyrifamycin S (6) 2 (0.8 mg) and impure samples of sporalactams A (3) and B (4) were obtained from this fraction via C 18 reversed-phase HPLC using a InertSustain, 5 µm, 25 x 1 cm column, with 11:9 H 2 /MeCN as eluent. The HPLC fractions containing 3 and 4 were further purified on C 18 reversed-phase HPLC using the same column but with 3:2 H 2 /MeCN and 13:7 MeH/H 2 as eluent, respectively. This resulted in clean samples of sporalactam A (3) (0.6 mg) and sporalactam B (4) (0.7 mg). 3-Amino-27-Demethoxy-27-Hydroxyrifamycin S (1): Isolated as red prism crystals; mp >300 C likely decomposed; [α] 25 D +6.5 x 10 2 (c 2.0, MeH); UV [11:9 H 2 )/MeCN] λ max 211, 229, 266,

4 SI-4 307, 363 nm; 1 H NMR see Table SI1; 13 C NMR, see Table SI2; positive ion HRESIMS [M + Na] + m/z (calcd for C 36 H 44 N 2 12 Na, ). 3-Amino-Rifamycin S (2): Isolated as a dark red glass; [α] 25 D +3.1 x 10 2 (c 0.4, MeH); UV [11:9 H 2 )/MeCN] λ max 211, 266, 308 sh, 371 nm; 1 H NMR see Table SI1; 13 C NMR, see Table SI2; positive ion HRESIMS [M + Na] + m/z (calcd for C 37 H 46 N 2 12 Na, ). Sporalactam A (3): Isolated as a dark red glass; [α] 25 D +1.9 x 10 2 (c 0.4, MeH); UV [3:2 H 2 )/MeCN] λ max 203, 269, 311, 361, 409 sh nm; 1 H and 13 C NMR, see Table SI3; positive ion HRESIMS [M + Na] + m/z (calcd for C 36 H 41 N 14 Na, ). Sporalactam B (4): Isolated as a dark red glass; [α] 25 D +4.8 x 10 2 (c 0.5, MeH); UV [13:7 MeH/H 2 ] λ max 206, 266, 309, 364 nm; 1 H and 13 C NMR, see Table SI3; positive ion HRESIMS [M + Na] + m/z (calcd forna, ). 27-Demethoxy-27-hydroxyrifamycin S (6) 3 : Isolated as a orange glass; [α] 25 D +2.4 x (c 0.3, MeH); UV [11:9 H 2 /MeCN] λ max 226, 284, 331 sh, 388 nm; 13 C/ 15 N NMR (DMS-d 6 ) δ (C- 11), (C-6), (C-15), (25-C()Me), (C-8), (C-19), (C-29), (C-17), (C-16), (C-18), (C-28), (C-3), (C-7), (C-12), 76.4 (C-23), 72.8 (C-25), 72.3 (C-21), 67.0 (C-27), 40.1 (C-26), 39.7 (C-20), 36.4 (C-24), 32.4 (C-22) 21.2 (C-13), 20.9 (25-C()Me), 20.1 (C-30), 17.2 (C-31), 11.4 (C-32), 9.9 (C-33), 9.6 (C-34), 7.6 (C-15), (3-N) ppm (C-1, C-2, C-4, C-5, C-9 and C-10 were not observed); 1 H NMR (DMS-d 6 ) δ (bs, 8- H), 9.84 (bs, 2-NH), 7.22 (bs, 3-H), 6.13 (d, J = 11.0 Hz, H-17), 6.03 (d, J = 12.0 Hz, H-29), 6.00 (dd, J = 14.9, 11.0 Hz, H-18), 5.78 (dd, J = 14.9, 7.9 Hz, H-19), 5.11 (bd, J = 7.3 Hz, H-25), 5.09 (dd, J = 12.0, 6.5 Hz, H-28), 4.37 (d, J = 3.48 Hz, 21-H), 4.33 (d, J = 4.9 Hz, 27-H), 4.31 (bs, 23-H), 3.71 (m, H-27), 3.48 (bd, J = 9.5 Hz, H-21), 2.90 (bt, J = 8.5 Hz, H-23), 2.16 (s, Me-14), 2.03 (obscured, H- 20), 1.99 (s, Me-30), 1.95 (s, 25-C()Me), 1.63 (s, Me-13), 1.62 (obscured, H-22), 1.52 (m, H-24), 1.44 (m, H-26), 0.83 (d, J = 7.1 Hz, Me-32), 0.77 (d, J = 6.7 Hz, Me-31), 0.61 (d, J = 6.7 Hz, Me-33), 0.22 (bd, J = 5.2 Hz, Me-34) ppm; positive ion HRESIMS [M + Na] + m/z (calcd for C 36 H 43 N 12 Na, ). References 1) a). Schupp, T.; Taxler, P.; Auden, J. A. L. J. Antibiotics 1981, 34, ; b). Taxler, P.; Schupp, T.; Fuhrer, H.; Richter, W. L. J. Antibiotics 1981, 34, ; c). Also referred to as rifamycin Z in Cricchio, R.; Antonini, P.; Ferrari, P.; Ripamonti, A.; Tuan, G.; Martinelli, E. J. Antibiotics 1981, 34, ) Lancini, G. C.; Hengeiler, C.; Sensi, P. Progr. Antimicrob. Anticancer Chemother., Proc. Int. Congr. Chemother. 1970, 2, ) 27-Demethoxy-27-hydroxyrifamycin S (6) is fully characterized here since the structure was only provisionally assigned in reference 2.

5 Table SI1. 1 H NMR data for 3-amino-27-demethoxy-27-hydroxyrifamycin S (1) and 3-aminorifamycin S (2) recorded in DMS-d 6 at 600 MHz. 1 major isomer 1 minor isomer 2 major isomer 2 minor isomer Position δ, multiplicity (J Hz) δ, multiplicity (J Hz) δ, multiplicity (J Hz) δ, multiplicity (J Hz) , s 1.64, bs 1.68, s 1.57, s , bs 2.15, bs 2.18, s 2.11,s , bd (11.6) 6.24, bd (10.1) 6.25, d (11.1) 5.86, d (11.8) , dd (14.1, 11.6) 6.80, bs 6.79, dd (15.3, 11.1) 5.72, dd (14.5, 11.8) a 5.94 a 5.94, dd (15.3, 7.0) 5.24 a , m 2.22, m 2.22 a 1.80 a , m 3.80 a 3.77, m 3.14 a a 1.68 a 1.66 a 1.62 a , bt (10.1) 2.92, bt (8.0) 2.86, bt (8.5) 2.77, bt (9.6) a 1.58 a 1.53 a 1.52 a , bs 5.18 a 5.19 a 5.22 a , m 1.11, m 0.98, m 1.99 a , m 3.81 a 3.30 a 3.10 a , t (11.2) 5.06, dd (12.2, 4.2) 4.93, dd (12.5) 4.78, t (11.3) , d (11.2) 6.05, d (12.2) 6.13, d (12.5) 5.99, d (11.3) , bs 1.97, bs 1.96, s 1.93, s , d (6.7) 0.82, d (7.0) 0.84, d (7.4) 0.67, d (6.7) , d (7.0) 0.90, d (6.9) 0.89, d (6.4) 0.81, d (6.7) , d (6.4) 0.57, d (6.5) 0.53, d (6.4) 0.71, d (6.4) d (6.9) -0.04, bs d (7.1) 0.90, d (6.4) 2-NH 8.79, s 8.73, s 8.72, bs 8.80, bs 3-NH , bs 7.56, bs 7.55, bs 7.55, bs 8-H 14.81, s 14.56, bs 14.59, s 14.81, bs 21-H 4.42, d (3.9) 4.70, bs 4.75 a 4.33 a 23-H 3.51, d (10.1) 4.37 a 4.29, d (8.5) 3.51, d (9.6) 25-Ac 1.95, s 1.95, s 1.96, s 1.96, s 27-H/Me 4.35, d (5.6) 4.24, bs 2.92, s 3.05, s a Multiplicity not determined due to overlapping signals - chemical shifts determined from 2D data. SI-5

6 SI-6 Table SI2. 13 C and 15 N a NMR data for 3-amino-27-demethoxy-27-hydroxyrifamycin S (1) and 3-aminorifamycin S (2) recorded in DMS-d 6 at 150 MHz. 1 major 1 minor 2 major 2 minor 1 major 1 minor 2 major 2 minor Position δ δ δ δ Position δ δ δ δ no no no no no no br no no br no no no no br no no no no br br br no br no 2-NH br ,9 3-NH br Ac 169.8, , , , Me / / a The 15 N assignments were not calibrated with an external standard. The δ value has an accuracy of about 1 ppm in reference to CH 3 N 2 (0 ppm) and are assigned on the basis of 15 NHSQC and 15 NlrHMQC correlations. no not observed. 1,2,3,4 Assignments maybe interchanged.

7 Table SI3. NMR data for sporalactams A (3) and B (4) recorded in DMS-d Position 13 C/ 15 N a (δ) 1 H (δ, multiplicity (J Hz)) 13 C/ 15 N a 1 H (δ, multiplicity (J Hz)) (δ) br / no / / no / / no / / no / / no / br / / / / / / / no / / no / / / / / , bs , bs , bs , bs / / / 80.1 / , d (15.4) 3.18, d (15.4) , d (15.8) 3.21, d (15.8) / / , ddd (8.1, 8.1, 5.4) , ddd (8.0, 8.0, 5.9) , m b b , bd (9.6) b b , dd (9.7, 5.3) b , m b , d (10.5) , d (10.2) , m b , m , bd (6.3) br 5.20, dd (12.1, 3.8) , dd (12.4, 6.3) , dd (12.1, 1.6) , dd (12.4, 0.8) , bs , bs , ddd (8.1, 5.4, 5.4) 1.07, ddd (8.1, 8.1, 4.1) b 1.02, m , d (7.3) , d (7.1) , d (6.8) , d (6.8) , d (7.0) , d (6.9) 2-NH , bs no 10.69, bs 8-H / 13.03, bs / 12.98, bs 21-H / 3.60 b / 3.86, d (2.6) 23-H / 4.48, d (5.0) / 4.37, d (6.0) 25-Ac 171.6, , s 170.2, , s 27-H/Me / 4.25, d (4.7) , s a The 15 N assignments were not calibrated with an external standard. The δ value has an accuracy of about 1 ppm in reference to CH 3 N 2 (0 ppm) and are assigned on the basis of 15 NHSQC and 15 NlrHMQC correlations. no not observed. b Multiplicity not determined due to overlapping signals - chemical shifts determined from 2D data. 1 Assignments maybe interchanged. SI-7

8 1 H NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) recorded at 600 MHz in DMS-d 6 SI-8 H Ac H NH 2 H H 1 N H

9 SI-9 Expanded 1 H NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) with peak picking recorded at 600 MHz in DMS-d 6 H Ac H NH 2 H H 1 N H

10 SI-10 Expanded 1 H NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) with peak picking recorded at 600 MHz in DMS-d 6 H Ac H NH 2 H H 1 N H

11 SI-11 Expanded 1 H NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) with peak picking recorded at 600 MHz in DMS-d 6 H Ac H NH 2 H H 1 N H

12 13 C NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) recorded SI-12 at 150 MHz in DMS-d 6 H Ac H NH 2 H H 1 N H

13 SI-13 Expanded 13 C NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) with peak picking recorded at 150 MHz in DMS-d 6 H Ac H NH 2 H H 1 N H

14 SI-14 Expanded 13 C NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) with peak picking recorded at 150 MHz in DMS-d 6 H Ac H NH 2 H H 1 N H

15 SI-15 gradcsy60 NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) recorded at 600 MHz in DMS-d 6 H Ac H NH 2 H H 1 N H

16 SI-16 gradhsqc NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) recorded at 600 MHz in DMS-d 6 H Ac H NH 2 H H 1 N H

17 SI-17 gradhmbc NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) recorded at 600 MHz in DMS-d 6 H Ac H NH 2 H H 1 N H

18 SI-18 tresy NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) recorded at 600 MHz in DMS-d 6 H Ac H NH 2 H H 1 N H

19 SI-19 grad 15 NHSQC NMR Spectrum of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1) recorded at 600 MHz in DMS-d 6 H Ac H NH 2 H H 1 N H

20 SI-20 Details of the X-ray Diffraction Analysis of 3-Amino-27-demethoxy-27-hydroxyrifamycin S (1). Fig. 1. RTEP-style image of molecule A Fig. 2. RTEP-style image of molecule B

21 SI-21 Fig. 3. RTEP-style image of molecule C Fig. 4. RTEP-style image of molecule D

22 SI-22 Fig. 5 verlay of molecule A and B. Molecule A is the isomer as C, B is the same as D Fig. 6. RTEP-style image of all four molecule in the asymmetric unit. Solvent molecules (11 MeH and one H2) have been omitted.

23 SI-23 Experimental Data Collection A red prism crystal of 4[C 36 H 44 N 2 12 ].10.5MeH.H 2, having approximate dimensions of 0.15 x 0.24 x 0.25 mm was mounted on a glass fiber. All measurements were made on a Bruker APEX DU diffractometer with cross- coupled multilayer optics Cu-Kα radiation. The data were collected at a temperature of o C to a maximum 2θ value of o. Data were collected in a series of φ and ω scans in 1.0 o oscillations using 10.0-second exposures. The crystal-to-detector distance was mm. Data Reduction f the reflections that were collected, were unique (Rint = 0.036); equivalent reflections were merged. Data were collected and integrated using the Bruker SAINT 1 software package. The linear absorption coefficient, µ, for Cu-Kα radiation is 7.70 cm -1. Data were corrected for absorption effects using the multi-scan technique (SADABS 2 ), with minimum and maximum transmission coefficients of and 0.891, respectively. The data were corrected for Lorentz and polarization effects. Structure Solution and Refinement The structure was solved by direct methods 3. The material crystallizes with four independent molecules, as well as at least 12 sites contain whole or partially occupied MeH molecules and one water molecule in the asymmetric unit. Additional MeH solvent sites were too disordered to properly model, and the PLATN/SQUEEZE 12 program was used to produce a data set free of solvent contributions at those sites. All non-hydrogen atoms were refined anisotropically. Some N H and H hydrogen atoms were located in difference maps and refined isotropically, other were modeled in calculated positions. All C H hydrogen atoms were placed in calculated positions. The absolute configuration of the structure was determined on the basis of the refined Flack x-parameter 13 [0.07(6)]. The final cycle of full-matrix least-

24 SI-24 squares refinement 4 on F 2 was based on reflections and 2229 variable parameters and converged (largest parameter shift was 0.00 times its esd) with unweighted and weighted agreement factors of: R1 (I>2.00σ(I)) = Σ Fo - Fc / Σ Fo = wr2 = [ Σ ( w (Fo 2 - Fc 2 ) 2 )/ Σ w(fo 2 ) 2 ] 1/2 = The standard deviation of an observation of unit weight 5 was The weighting scheme was based on counting statistics. The maximum and minimum peaks on the final difference Fourier map corresponded to 0.76 and e - /Å 3, respectively. Neutral atom scattering factors were taken from Cromer and Waber 6. Anomalous dispersion effects were included in Fcalc 7 ; the values for Δf' and Δf" were those of Creagh and McAuley 8. The values for the mass attenuation coefficients are those of Creagh and Hubbell 9. All refinements were performed using the SHELXL via the lex2 11 interface. References (1) SAINT. Version 8.34A. Bruker AXS Inc., Madison, Wisconsin, USA. ( ). (2) SADABS-2014/5. Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Crystallogr. 48. (3) SHELXT: Sheldrick, G. M.; Acta Cryst., A71, 3-8 (2015). (4) Least Squares function minimized: Σw(Fo 2 -Fc 2 ) 2 (5) Standard deviation of an observation of unit weight: [Σw(Fo 2 -Fc 2 ) 2 /(No-Nv)] 1/2 where: No = number of observations Nv = number of variables (6) Cromer, D. T. & Waber, J. T.; "International Tables for X-ray Crystallography", Vol. IV, The Kynoch Press, Birmingham, England, Table 2.2 A (1974).

25 (7) Ibers, J. A. & Hamilton, W. C.; Acta Crystallogr., 17, 781 (1964). SI-25 (8) Creagh, D. C. & McAuley, W.J.; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table , pages (1992). (9) Creagh, D. C. & Hubbell, J.H..; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table , pages (1992). (10) SHELXL-2016, Sheldrick, G.M, Acta Crystallogr., C71, 3-8 (2015). (11) lex2 V1.2.6 Dolomanov,.V.; Bourhis, L.J.;Gildea, R.J.;Howard, J.A.K.;Puschmann, H., J. Appl. Cryst., 42, (2009). (12) P. v.d. Sluis and A. L. Spek, Acta Crystallogr., Sect. A: Found. Crystallogr., 1990, 46, (13) Parsons, Flack and Wagner, Acta Cryst. B69 (2013)

26 EXPERIMENTAL DETAILS SI-26 A. Crystal Data Empirical Formula C H 220 N Formula Weight Crystal Colour, Habit Crystal Dimensions Crystal System Lattice Type Lattice Parameters red, prism 0.15 x 0.24 x 0.25 mm monoclinic Primitive a = (6) Å b = (10) Å c = (7) Å α = 90 o β = (2) o γ = 90 o V = (5) Å 3 Space Group P2 1 (#4) Z value 2 Dcalc g/cm 3 F µ(cu-kα) 7.70 cm -1

27 B. Intensity Measurements SI-27 Diffractometer Bruker APEX DU Radiation Cu-Kα (λ = Å) Data Images Detector Position 2θmax seconds mm o No. of Reflections Measured Total: Unique: (Rint = 0.036) Corrections Absorption (T min = 0.810, T max = 0.891) Lorentz-polarization

28 C. Structure Solution and Refinement SI-28 Structure Solution Direct Methods (XL) Refinement Full-matrix least-squares on F 2 Function Minimized Σ w (Fo 2 - Fc 2 ) 2 Least Squares Weights Anomalous Dispersion w=1/(σ 2 (Fo 2 )+(0.1202P) P) All non-hydrogen atoms No. bservations (I>0.00σ(I)) No. Variables 2229 Reflection/Parameter Ratio Residuals (refined on F 2, all data): R1; wr ; Goodness of Fit Indicator 1.03 No. bservations (I>2.00σ(I)) Residuals (refined on F 2 ): R1; wr ; Max Shift/Error in Final Cycle 0.00 Maximum peak in Final Diff. Map 0.76 e - /Å 3 Minimum peak in Final Diff. Map e - /Å 3

29 SI-29 Table 2 Fractional Atomic Coordinates ( 10 4 ) and Equivalent Isotropic Displacement Parameters (Å ) for platon_sq. U eq is defined as 1/3 of of the trace of the orthogonalised U IJ tensor. Atom x y z U(eq) 1A -663(2) (13) 5937(2) 33.6(8) 2A 2507(2) (12) 6474(2) 31.4(7) 3A -1292(2) (13) 5926(2) 36.7(8) 4A 2673(2) (12) 6794(2) 32.8(8) 5A 624(2) (12) 6620(2) 30.7(7) 6A 1921(3) (12) 7512(2) 35.5(8) 7A 749(2) (12) (19) 29.2(7) 8A 1773(2) (14) 8734(2) 38.0(8) 9A 2540(3) (13) (19) 35.0(8) 10A 3370(30) 5717(17) 9480(20) 32(4) 11A 2860(30) 5440(30) 10340(40) 41(3) 12A 1403(4) (16) 9220(3) 53.2(11) N1A 640(3) (14) 6166(2) 26.9(8) N2A 2290(3) (16) 6267(2) 29.9(9) C1A 79(3) (17) 6048(3) 26.8(9) C2A 796(3) (16) 6135(3) 25.3(9) C3A 1597(3) (17) 6218(2) 25.4(9) C4A 1766(3) (16) 6320(2) 24.9(9) C5A 1159(3) (17) 6419(3) 26.6(9) C6A 449(3) (17) 6413(3) 29.2(10) C7A -386(3) (18) 6236(3) 31.7(10) C8A -495(3) (17) 6088(3) 28.6(10) C9A 214(3) (17) 6115(3) 26.0(9) C10A 1039(3) (16) 6270(2) 24.7(9) C11A 1915(3) (16) 6669(2) 25.7(9) C12A 1536(3) (16) 6785(3) 28.4(10) C13A 1652(3) (17) 6282(3) 30.6(10) C14A -1121(4) (19) 6244(4) 42.3(13) C15A 610(3) (16) 5632(3) 25.4(9) C16A 344(3) (16) 5772(3) 27.1(9) C17A 775(3) (17) 6375(3) 31.9(10) C18A 1561(3) (18) 6973(3) 33.2(11) C19A 1867(4) (19) 7635(3) 40.4(12) C20A 2676(4) 7845(2) 8249(3) 45.5(14) C21A 2514(4) (19) 8495(3) 35.7(11) C22A 3275(4) 7154(2) 9114(3) 40.4(12) C23A 3082(3) 6677(2) 9354(3) 34.2(11) C24A 2686(4) 6332(2) 8720(3) 35.7(11) C25A 2487(4) (19) 9038(3) 34.5(11) C26A 1978(4) (19) 8446(3) 36.5(11) C27A 1937(4) 5049(2) 8783(3) 42.8(13) C28A 1598(4) 4691(2) 8189(3) 44.4(13)

30 SI-30 C29A 2123(4) (19) 8081(3) 38.9(12) C30A -454(3) (18) 5171(3) 35.5(11) C31A 3457(4) 7847(3) 7997(4) 59.0(19) C32A 3622(4) 7472(2) 9787(3) 47.6(14) C33A 3278(4) 6269(2) 8273(3) 46.2(14) C34A 1064(4) 5715(2) 8035(3) 42.4(13) C35A 3461(14) 5535(11) 10138(18) 34(5) C36A 4374(12) 5429(11) 10571(8) 44(6) 1B 6435(2) (14) 5562(2) 35.8(8) 2B 3655(2) (12) 5774(2) 30.8(7) 3B 7229(2) (15) 5758(2) 41.4(9) 4B 4140(2) (12) 6830(2) 33.3(8) 5B 6039(2) (13) 6671(2) 40.4(9) 6B 4086(2) (12) (18) 29.2(7) 7B 6360(3) (16) 8204(2) 45.7(10) 8B 6719(3) (16) 9388(2) 51.0(11) 9B 5868(3) (19) 9698(2) 55.2(12) 10B 7307(4) 5587(2) 10224(3) 80.0(18) 11B 7013(4) 6158(2) 8678(4) 75.6(16) 12B 5654(3) (15) 7706(2) 45.7(10) N1B 5212(3) (16) 5721(3) 29.8(9) N2B 3764(2) (14) 5949(2) 28.7(8) C1B 5814(3) (18) 5701(3) 29.8(10) C2B 5127(3) (17) 5753(3) 29.1(10) C3B 4417(3) (18) 5866(2) 28.1(10) C4B 4355(3) (17) 5894(3) 27.2(9) C5B 5237(3) (18) 6297(3) 30.9(10) C6B 5990(3) (19) 6358(3) 36.8(11) C7B 6661(3) 6703(2) 6167(3) 37.5(12) C8B 6575(3) 6243(2) 5926(3) 36.1(11) C9B 5842(3) (19) 5875(3) 31.6(10) C10B 5153(3) (18) 6028(3) 29.7(10) C11B 4771(3) (18) 6665(3) 32.4(10) C12B 5323(3) (19) 6938(3) 35.4(11) C13B 4835(4) (18) 6649(3) 34.9(11) C14B 7454(4) 6986(2) 6223(5) 50.1(16) C15B 4715(3) (18) 5173(3) 28.3(10) C16B 4999(3) (19) 5225(3) 32.9(11) C17B 5107(3) (19) 5801(3) 35.5(11) C18B 4974(3) (19) 6487(3) 35.1(11) C19B 5156(4) 3481(2) 7036(3) 44.7(13) C20B 5032(4) 3557(2) 7766(3) 47.6(14) C21B 5457(4) 4006(2) 8132(3) 41.6(13) C22B 5382(4) 4109(2) 8884(3) 48.4(14) C23B 5795(4) 4573(2) 9196(3) 47.6(14) C24B 5436(4) 4986(2) 8678(3) 45.6(14)

31 SI-31 C25B 5950(4) 5427(2) 8982(3) 45.0(13) C26B 5634(5) 5847(2) 8503(3) 54.6(16) C27B 6238(4) 6261(3) 8799(3) 50.4(15) C28B 5811(4) 6688(2) 8436(4) 48.4(14) C29B 6094(4) 6941(2) 8033(4) 47.6(14) C30B 5161(4) 3793(2) 4540(3) 39.5(12) C31B 4061(5) 3556(4) 7657(5) 70(2) C32B 5754(5) 3729(3) 9455(4) 60.4(18) C33B 4457(5) 5036(3) 8495(4) 58.4(18) C35B 6617(5) 5601(3) 10282(4) 56.9(16) C36B 6410(7) 5713(4) 10946(4) 88(3) C34B 5464(9) 5747(3) 7698(4) 94(4) 1C 4474(2) (12) 4810(2) 33.6(8) 2C 2634(2) (13) 3976(2) 34.3(8) 3C 5746(2) (13) 4601(2) 39.0(9) 4C 3418(2) (12) (19) 30.6(7) 5C 4532(2) (14) 2556(2) 36.9(8) 6C 5469(2) (13) 3540(2) 32.5(7) 7C 2672(2) (12) (19) 29.0(7) 8C 936(3) (18) 2327(3) 58.0(12) 9C 1099(5) (18) 1149(3) 72.1(16) 10C 1424(3) (17) 1046(2) 51.1(11) 11C 1029(3) 6973(2) 50(2) 58.4(12) 12C 3591(3) (19) 1216(2) 53.5(11) N1C 2788(3) (14) 4710(2) 29.1(8) N2C 1925(3) (16) 4448(2) 27.4(8) C1C 4041(3) (17) 4623(3) 27.5(9) C2C 3180(3) (17) 4609(3) 26.7(9) C3C 2720(3) (17) 4449(3) 25.2(9) C4C 3089(3) (16) 4196(2) 23.4(9) C5C 4363(3) (18) 3920(3) 26.6(9) C6C 5179(3) (18) 3871(3) 28.7(10) C7C 5676(3) (19) 4112(3) 32.7(11) C8C 5293(3) (18) 4387(3) 31.1(10) C9C 4452(3) (17) 4417(3) 27.3(9) C10C 3989(3) (17) 4190(3) 25.3(9) C11C 4066(3) (17) 3571(2) 25.3(9) C12C 4813(3) (18) 3322(3) 28.6(10) C13C 5201(3) (18) 3693(3) 31.8(10) C14C 6556(3) 6580(2) 4060(4) 41.1(13) C15C 2568(3) (16) 5308(3) 26.7(9) C16C 2204(3) (17) 5301(3) 29.9(10) C17C 1502(3) (17) 4752(3) 31.5(10) C18C 990(3) (17) 4092(3) 32.7(10) C19C 369(4) (17) 3532(3) 36.0(11) C20C -168(4) (19) 2834(3) 39.8(12)

32 SI-32 C21C 443(4) 7858(2) 2453(3) 45.2(13) C22C 13(5) 7607(3) 1726(3) 54.7(17) C23C 642(5) 7399(3) 1400(4) 60.2(18) C24C 1363(4) 7091(2) 1933(3) 45.0(14) C25C 1923(5) 6871(2) 1534(3) 47.5(14) C26C 2772(4) 6657(2) 2047(3) 46.4(14) C27C 3237(4) 6394(2) 1605(3) 46.5(14) C28C 3980(4) 6108(2) 2105(3) 41.4(12) C29C 3932(4) 5664(2) 2100(3) 42.9(13) C30C 2668(3) (18) 5978(3) 33.7(11) C31C -704(4) 7653(2) 2985(4) 48.9(14) C32C -657(7) 7915(4) 1135(4) 84(3) C33C 980(4) 6727(2) 2296(3) 44.9(13) C35C 1022(4) 6596(3) 328(3) 52.6(15) C36C 592(5) 6169(3) -81(4) 65.9(19) C34C 3366(5) 7025(3) 2537(3) 57.2(18) 1D 169(2) (12) 4492(2) 34.1(8) 2D 1522(2) (11) (18) 25.7(7) 3D -1270(2) (13) 4413(2) 37.4(9) 4D 240(2) (11) (18) 26.6(7) 5D -1612(2) (12) 2993(2) 31.6(7) 6D -1734(2) (12) 3971(2) 29.5(7) 7D 2929(2) (12) (19) 28.9(7) 8D 1315(3) (19) 1830(3) 57.3(12) 9D 200(3) (19) 914(3) 61.9(13) 10D -359(3) (17) 590(2) 49.7(10) 11D -1264(4) 4697(3) 149(3) 79.9(17) 12D -1469(3) (16) 1892(2) 47.3(10) N1D 1763(3) (14) 4378(2) 27.4(8) N2D 2397(3) (17) 4342(2) 27.0(8) C1D 460(3) (17) 4464(3) 28.5(10) C2D 1317(3) (17) 4438(3) 25.4(9) C3D 1651(3) (16) 4416(2) 23.1(9) C4D 1147(3) (16) 4505(2) 23.0(9) C5D -358(3) (17) 4226(2) 24.6(9) C6D -1215(3) (17) 4160(3) 26.4(9) C7D -1552(3) (18) 4241(3) 30.1(10) C8D -974(3) (17) 4355(3) 29(1) C9D -93(3) (17) 4406(3) 25.4(9) C10D 211(3) (16) 4368(2) 22.6(9) C11D -325(3) (16) 3974(2) 23.5(9) C12D -1256(3) (17) 3770(3) 26.9(9) C13D -1308(3) (17) 4153(3) 28.1(10) C14D -2470(3) 5111(2) 4176(4) 38.4(12) C15D 2527(3) (17) 4887(3) 26.7(9) C16D 2821(3) (17) 4771(3) 29.4(10)

33 SI-33 C17D 2953(3) (19) 4156(3) 34.7(11) C18D 2871(3) 3665(2) 3509(3) 37.5(11) C19D 2927(4) 3497(2) 2890(3) 43.9(13) C20D 2839(4) 3770(3) 2212(3) 51.9(16) C21D 1934(4) 3989(3) 1900(3) 48.0(14) C22D 1720(5) 4242(3) 1168(3) 64(2) C23D 865(4) 4512(3) 951(3) 54.8(16) C24D 867(4) 4907(2) 1492(3) 44.7(13) C25D -21(4) 5103(2) 1349(3) 39.7(12) C26D -90(4) 5493(2) 1844(3) 37.2(12) C27D -1052(4) 5608(2) 1703(3) 43.1(13) C28D -1118(4) 6020(2) 2153(3) 38.8(12) C29D -1571(3) (19) 2587(3) 35.0(11) C30D 2970(3) (18) 5423(3) 33.9(11) C31D 3538(5) 4135(4) 2367(4) 73(2) C32D 1703(7) 3919(5) 524(4) 103(4) C33D 1549(5) 5264(3) 1503(5) 66(2) C35D -1011(5) 5081(3) 72(3) 53.2(15) C36D -1321(6) 5335(3) -631(4) 72(2) C34D 395(4) 5384(2) 2666(3) 37.4(12) (8) 3975(5) 10784(7) 123(4) C (20) 3554(8) 11222(15) 180(12) (3) (19) 13036(2) 54.6(11) C (5) 3973(3) 12667(5) 62.3(18) (4) 6516(3) 8056(4) 84.0(18) C (8) 6164(4) 7729(6) 114(5) (3) (19) 7125(3) 57.7(12) C (5) 4858(4) 7414(5) 81(3) (6) 6551(3) 9714(6) 67(3) C (14) 6627(6) 10402(9) 95(6) (4) (19) 6577(4) 66.2(14) C (6) 3714(3) 6385(7) 83(3) (3) (17) 7556(3) 54.5(11) C (5) 7526(3) 7395(6) 68(2) (15) 7199(6) 9056(7) 118(9) C (16) 6831(8) 8948(15) 114(10) (6) 4519(4) 11285(4) 109(3) C (14) 4570(7) 12075(7) 166(8) (9) 7677(9) 8655(9) 131(8) C (13) 7768(7) 8989(11) 81(5) (3) (17) 10922(3) 56.7(12) C (7) 4167(3) 11218(6) 85(3) C (9) 4266(5) 8595(9) 63(4) (9) 4747(5) 8517(11) 115(6) (5) 3206(2) 7964(4) 88.3(19) 10' 3260(30) 5652(16) 9490(20) 32(4)

34 SI-34 C35' 3304(17) 5439(12) 10114(18) 35(5) 11' 2710(30) 5430(30) 10350(30) 41(3) C36' 4137(18) 5203(12) 10501(13) 59(6) 54A 589(12) 8084(9) -683(9) 100(7) 54B 86(11) 7953(7) -276(9) 79(5) C54B 886(14) 7882(6) -401(11) 61(5) C54A 1508(15) 8068(16) -296(17) 138(15)

35 SI-35 Table 3 Anisotropic Displacement Parameters (Å ) for platon_sq. The Anisotropic displacement factor exponent takes the form: -2π 2 [h 2 a* 2 U 11 +2hka*b*U 12 + ]. Atom U 11 U 22 U 33 U 23 U 13 U 12 1A 25.8(16) 30.1(18) 47(2) 1.3(15) 15.6(15) 3.5(14) 2A 27.0(17) 25.0(17) 44.7(19) 5.0(15) 15.7(14) 3.2(14) 3A 27.0(17) 28.1(18) 60(2) -5.2(16) 21.4(16) 1.9(14) 4A 27.6(17) 22.1(16) 47(2) 0.5(15) 10.9(15) 0.3(13) 5A 30.0(17) 22.1(16) 44.2(19) 0.5(14) 18.1(15) -0.6(13) 6A 47(2) 26.9(17) 31.0(17) 0.1(14) 11.3(15) 2.7(15) 7A 28.0(16) 27.0(17) 34.5(17) 0.0(13) 13.4(14) 2.3(14) 8A 37.9(19) 37(2) 39.2(19) -0.4(16) 13.4(16) 2.7(16) 9A 45(2) 36.2(19) 27.6(17) -3.6(14) 17.2(15) 4.0(16) 10A 37(8) 35(10) 26.8(18) -3(4) 14(4) 4(6) 11A 48(10) 48(3) 28(3) -1(2) 16(7) 3(10) 12A 77(3) 48(2) 40(2) -7.6(19) 26(2) -8(2) N1A 29(2) 21.5(19) 34(2) 0.0(16) 15.4(17) 1.9(16) N2A 28(2) 23(2) 41(2) 2.3(17) 14.2(17) -0.1(17) C1A 28(2) 25(2) 29(2) 0.0(18) 11.4(18) 2.9(18) C2A 28(2) 22(2) 27(2) 0.2(17) 10.5(18) 2.3(18) C3A 26(2) 27(2) 22(2) 1.1(17) 7.4(17) -0.9(18) C4A 26(2) 25(2) 26(2) -1.6(17) 12.0(17) 5.1(18) C5A 29(2) 26(2) 26(2) -3.8(17) 11.0(18) 1.1(19) C6A 34(2) 21(2) 35(2) -3.2(18) 16(2) 0.1(19) C7A 33(2) 25(2) 44(3) -8(2) 22(2) -5.1(19) C8A 26(2) 28(2) 36(2) -5.8(19) 14.6(19) 1.2(19) C9A 25(2) 24(2) 30(2) -1.4(18) 10.7(18) 2.2(18) C10A 26(2) 23(2) 25(2) -2.5(17) 10.5(17) 1.0(17) C11A 30(2) 22(2) 26(2) -4.2(17) 11.8(18) 1.3(18) C12A 33(2) 21(2) 34(2) 1.6(18) 14.9(19) 2.2(18) C13A 36(3) 21(2) 36(3) -3.5(19) 14(2) -1.7(19) C14A 37(3) 27(3) 73(4) -4(3) 31(3) -3(2) C15A 18(2) 24(2) 33(2) -1.6(18) 7.6(17) 1.3(17) C16A 29(2) 20(2) 34(2) 2.6(18) 14.0(19) 0.8(18) C17A 40(3) 22(2) 36(2) 2.1(19) 16(2) 2(2) C18A 34(3) 27(2) 38(3) 1(2) 13(2) -5(2) C19A 47(3) 30(3) 41(3) -3(2) 11(2) -6(2) C20A 48(3) 42(3) 39(3) -2(2) 5(2) -13(3) C21A 39(3) 34(3) 35(3) -3(2) 14(2) -7(2) C22A 43(3) 45(3) 32(3) -4(2) 10(2) -7(2) C23A 34(2) 42(3) 28(2) 2(2) 12(2) 8(2) C24A 38(3) 39(3) 31(2) -2(2) 14(2) 4(2) C25A 40(3) 35(3) 28(2) -4(2) 12(2) 7(2) C26A 45(3) 35(3) 28(2) -4(2) 11(2) 3(2) C27A 55(3) 40(3) 31(3) -5(2) 12(2) -1(3) C28A 57(3) 38(3) 36(3) -8(2) 14(3) 0(3)

36 SI-36 C29A 51(3) 29(3) 34(3) 0(2) 11(2) -3(2) C30A 31(2) 26(2) 45(3) 0(2) 8(2) 4(2) C31A 40(3) 76(5) 52(4) 21(3) 6(3) -17(3) C32A 49(3) 48(3) 39(3) -2(3) 7(3) -10(3) C33A 56(3) 50(4) 41(3) -7(3) 27(3) 3(3) C34A 43(3) 46(3) 35(3) -4(2) 10(2) 5(3) C35A 41(8) 37(12) 26(6) -12(7) 12(6) -1(7) C36A 39(7) 67(14) 27(6) 6(7) 11(5) 15(8) 1B 23.6(16) 40(2) 46(2) -3.8(16) 14.4(15) 5.4(15) 2B 22.1(16) 30.5(18) 38.1(18) 2.1(14) 8.2(13) 2.8(14) 3B 29.0(18) 40(2) 60(3) 1.1(18) 21.8(18) 2.2(16) 4B 24.3(16) 31.3(18) 43(2) -2.1(15) 10.5(14) 0.1(14) 5B 26.4(17) 28.0(18) 64(2) -2.2(17) 13.1(17) -2.0(14) 6B 24.6(16) 34.1(18) 29.3(16) -2.9(13) 9.9(13) 3.3(14) 7B 41(2) 48(2) 44(2) -4.3(18) 9.9(17) -6.5(18) 8B 41(2) 49(2) 45(2) -6.5(19) -7.3(18) 6.2(19) 9B 51(2) 77(3) 30(2) -13(2) 4.5(18) 1(2) 10B 56(3) 96(4) 65(3) -21(3) -8(3) 7(3) 11B 61(3) 72(4) 95(4) 20(3) 29(3) 19(3) 12B 43(2) 42(2) 41(2) 0.0(17) 1.7(17) -8.5(18) N1B 20(2) 32(2) 33(2) -4.5(18) 3.5(18) 4.7(17) N2B 21.8(18) 25(2) 39(2) -3.7(16) 11.0(16) 0.4(15) C1B 21(2) 34(3) 32(2) 1.2(19) 5.8(18) 2.0(19) C2B 29(2) 28(2) 28(2) -3.3(18) 7.0(18) -0.2(19) C3B 22(2) 34(2) 25(2) -2.8(19) 4.5(17) 0.0(19) C4B 27(2) 31(2) 25(2) 0.8(18) 11.3(18) 1.9(19) C5B 22(2) 29(2) 38(3) 4(2) 6.4(19) 1.8(19) C6B 25(2) 29(2) 50(3) 1(2) 5(2) 1(2) C7B 23(2) 33(3) 53(3) 5(2) 9(2) -2(2) C8B 24(2) 36(3) 45(3) 4(2) 8(2) 6(2) C9B 23(2) 36(3) 34(2) 1(2) 8.0(19) 4.4(19) C10B 23(2) 31(2) 30(2) 0.5(19) 2.5(18) 0.7(19) C11B 23(2) 32(3) 34(2) 0(2) 0.1(18) 1.7(19) C12B 24(2) 34(3) 42(3) -1(2) 5(2) -1(2) C13B 38(3) 28(2) 42(3) 0(2) 17(2) -4(2) C14B 28(3) 37(3) 88(5) 2(3) 25(3) 0(2) C15B 22(2) 32(2) 32(2) -4.6(19) 11.0(18) -2.1(19) C16B 23(2) 34(3) 39(3) -8(2) 8.5(19) 3(2) C17B 30(2) 31(3) 40(3) -5(2) 5(2) 2(2) C18B 29(2) 35(3) 36(3) -3(2) 6(2) 4(2) C19B 41(3) 42(3) 41(3) 1(2) 1(2) -1(3) C20B 44(3) 54(4) 41(3) 6(3) 9(2) -9(3) C21B 35(3) 47(3) 39(3) 3(2) 8(2) 0(2) C22B 48(3) 61(4) 33(3) 4(3) 10(2) 2(3) C23B 46(3) 62(4) 31(3) -1(2) 7(2) 9(3) C24B 46(3) 59(4) 27(2) -2(2) 6(2) 17(3)

37 SI-37 C25B 45(3) 59(3) 24(2) -5(2) 3(2) 14(3) C26B 68(4) 52(4) 31(3) -6(3) 2(3) 13(3) C27B 46(3) 65(4) 38(3) 2(3) 13(2) 15(3) C28B 45(3) 50(3) 44(3) -6(3) 9(3) 1(3) C29B 34(3) 50(3) 54(3) -10(3) 9(2) 0(3) C30B 41(3) 40(3) 39(3) -6(2) 15(2) 13(2) C31B 50(4) 101(7) 56(4) -10(4) 16(3) -26(4) C32B 65(4) 72(5) 38(3) 6(3) 10(3) -5(4) C33B 52(4) 60(4) 51(4) -17(3) 3(3) 17(3) C35B 64(4) 50(4) 42(3) 2(3) 2(3) 6(3) C36B 99(7) 104(7) 42(4) -23(4) 1(4) -15(6) C34B 183(11) 51(4) 38(4) 4(3) 27(5) -8(6) 1C 30.8(17) 25.7(17) 49(2) 0.5(15) 19.8(15) -5.3(14) 2C 24.4(16) 33.0(18) 52(2) -9.4(16) 22.0(15) -5.2(15) 3C 29.3(17) 31.4(19) 62(2) -3.1(17) 22.8(17) -7.3(15) 4C 26.3(16) 30.8(18) 39.8(18) -7.9(15) 18.1(14) -3.7(14) 5C 36.1(18) 47(2) 33.4(18) -7.1(16) 20.0(15) 4.4(16) 6C 28.2(17) 35.2(19) 41.1(19) -7.0(15) 21.1(15) -3.4(14) 7C 26.4(16) 26.2(17) 34.9(17) 2.0(14) 11.5(14) -0.5(13) 8C 66(3) 56(3) 63(3) 14(2) 36(2) 5(2) 9C 121(5) 54(3) 50(3) 24(2) 41(3) 30(3) 10C 67(3) 60(3) 29.2(19) 3.6(18) 20.3(18) 14(2) 11C 58(3) 84(3) 37(2) 14(2) 21(2) 21(3) 12C 58(3) 74(3) 31(2) 5(2) 18.6(19) 2(2) N1C 31(2) 21.8(19) 39(2) 4.9(17) 18.1(17) 1.0(16) N2C 22.7(19) 23(2) 39(2) -2.3(17) 14.4(17) -1.0(17) C1C 26(2) 26(2) 31(2) 6.1(18) 12.4(18) -2.4(19) C2C 26(2) 24(2) 31(2) 2.7(18) 11.5(18) 0.8(18) C3C 24(2) 28(2) 26(2) 3.3(17) 11.4(17) 1.2(18) C4C 23(2) 25(2) 25(2) -0.7(17) 11.3(17) -2.8(18) C5C 22(2) 33(2) 26(2) 4.3(18) 10.1(17) 1.5(18) C6C 29(2) 31(2) 28(2) -0.1(18) 13.9(19) 2.7(19) C7C 22(2) 37(3) 42(3) 1(2) 14(2) -4.9(19) C8C 25(2) 32(2) 40(3) 1(2) 15(2) -4.7(19) C9C 23(2) 29(2) 30(2) 2.6(18) 8.8(18) -1.7(18) C10C 23(2) 27(2) 28(2) 0.7(18) 11.6(17) -3.1(18) C11C 21(2) 33(2) 25(2) -0.4(18) 10.9(17) 4.3(18) C12C 24(2) 35(3) 30(2) -3.3(19) 14.3(18) -0.4(19) C13C 28(2) 34(3) 40(3) -6(2) 20(2) 2(2) C14C 26(2) 43(3) 60(3) -1(3) 23(2) -2(2) C15C 22(2) 24(2) 36(2) 2.4(18) 11.7(18) -1.7(18) C16C 30(2) 23(2) 43(3) 1.5(19) 21(2) -1.8(19) C17C 30(2) 19(2) 48(3) 2.2(19) 18(2) 3.4(19) C18C 34(2) 22(2) 44(3) -1.4(19) 16(2) 2.9(19) C19C 39(3) 20(2) 52(3) 3(2) 20(2) 3(2) C20C 39(3) 31(3) 45(3) 3(2) 10(2) 7(2)

38 SI-38 C21C 49(3) 41(3) 45(3) 5(2) 16(3) 13(3) C22C 67(4) 53(4) 38(3) 3(3) 11(3) 29(3) C23C 86(5) 55(4) 37(3) 10(3) 19(3) 33(4) C24C 58(3) 46(3) 33(3) 9(2) 19(3) 17(3) C25C 65(4) 47(3) 34(3) 11(2) 22(3) 13(3) C26C 61(4) 51(3) 34(3) 10(2) 26(3) 16(3) C27C 52(3) 57(4) 36(3) -1(3) 22(3) 6(3) C28C 43(3) 53(3) 33(3) -4(2) 19(2) 2(3) C29C 42(3) 62(3) 32(3) -3(2) 22(2) 5(3) C30C 31(2) 26(2) 47(3) 0(2) 17(2) 2(2) C31C 48(3) 42(3) 53(3) -7(3) 13(3) -7(3) C32C 96(6) 86(6) 47(4) 0(4) -2(4) 48(5) C33C 52(3) 47(3) 39(3) 3(2) 19(3) 12(3) C35C 56(4) 73(4) 38(3) 13(3) 27(3) 23(3) C36C 67(5) 93(5) 40(3) 0(3) 20(3) 7(4) C34C 68(4) 69(4) 32(3) 1(3) 13(3) 24(4) 1D 26.2(16) 24.9(17) 52(2) 5.1(15) 14.4(15) -0.6(14) 2D 21.9(15) 23.9(16) 33.5(17) -1.2(13) 12.3(13) -0.6(13) 3D 27.0(17) 25.0(18) 64(3) 5.5(17) 20.5(17) -0.9(15) 4D 21.2(15) 25.2(16) 32.9(17) 0.7(13) 8.9(13) -1.7(13) 5D 24.3(16) 32.4(18) 34.5(17) 1.9(14) 5.9(13) 2.5(14) 6D 19.1(15) 24.4(17) 45.5(19) 2.4(14) 12.0(14) 4.3(13) 7D 24.3(16) 27.5(17) 34.0(17) -3.1(14) 9.0(13) 0.2(13) 8D 39(2) 75(3) 47(2) -11(2) 1(2) 15(2) 9D 51(3) 70(3) 50(3) -13(2) 0(2) 20(2) 10D 63(3) 61(3) 21.5(18) 4.1(17) 9.6(17) 12(2) 11D 58(3) 112(5) 49(3) 10(3) -7(2) -11(3) 12D 40(2) 51(2) 46(2) -13.2(19) 10.0(18) -3.8(18) N1D 23.6(19) 23.8(19) 33(2) -3.5(17) 7.1(16) 2.1(16) N2D 23.0(19) 23(2) 37(2) 1.6(17) 13.4(16) 3.5(17) C1D 25(2) 26(2) 34(2) 1.5(19) 9.8(18) 2.4(19) C2D 22(2) 26(2) 28(2) -1.6(17) 9.1(17) 1.1(18) C3D 17.9(19) 27(2) 24(2) -1.1(17) 6.4(16) 1.1(17) C4D 23(2) 27(2) 19.9(19) 3.4(17) 8.4(16) 0.6(18) C5D 21(2) 30(2) 24(2) 0.7(18) 8.3(16) -0.9(18) C6D 21(2) 25(2) 32(2) -1.4(18) 7.4(17) 2.6(18) C7D 24(2) 30(2) 40(3) 0(2) 16(2) -1.6(19) C8D 24(2) 27(2) 38(3) 1.5(19) 14.7(19) -3.3(18) C9D 23(2) 27(2) 29(2) 1.2(17) 11.6(17) 2.4(18) C10D 21(2) 25(2) 22(2) 0.9(17) 7.7(16) -0.9(17) C11D 19(2) 24(2) 28(2) -1.5(17) 8.4(17) 0.1(17) C12D 16(2) 28(2) 34(2) 3.0(18) 6.7(17) 1.7(17) C13D 23(2) 28(2) 37(2) 2.0(19) 14.7(19) 3.0(18) C14D 25(2) 33(3) 63(4) 2(2) 21(2) -1(2) C15D 21(2) 26(2) 33(2) -1.5(18) 9.4(18) 0.5(18) C16D 22(2) 25(2) 37(2) -4.0(19) 4.2(18) 4.2(18)

39 SI-39 C17D 25(2) 31(3) 41(3) -9(2) 2.1(19) 9(2) C18D 30(2) 38(3) 39(3) -8(2) 5(2) 8(2) C19D 35(3) 50(3) 40(3) -11(2) 5(2) 12(2) C20D 43(3) 77(5) 36(3) -8(3) 12(2) 18(3) C21D 46(3) 66(4) 32(3) -7(3) 14(2) 16(3) C22D 61(4) 105(6) 32(3) 5(3) 22(3) 37(4) C23D 54(3) 81(5) 34(3) 9(3) 22(3) 29(3) C24D 48(3) 55(3) 36(3) 7(2) 20(2) 5(3) C25D 40(3) 53(3) 26(2) 6(2) 12(2) 9(2) C26D 37(3) 47(3) 25(2) 5(2) 7(2) 4(2) C27D 40(3) 55(3) 28(2) 1(2) 5(2) 9(3) C28D 35(3) 46(3) 29(2) 1(2) 3(2) 3(2) C29D 28(2) 38(3) 31(2) 0(2) 0.3(19) 2(2) C30D 27(2) 25(2) 46(3) -3(2) 8(2) 6(2) C31D 55(4) 106(7) 51(4) 5(4) 10(3) 2(4) C32D 105(7) 164(11) 39(4) -6(5) 24(4) 78(8) C33D 48(4) 81(5) 78(5) 24(4) 35(4) 7(3) C35D 51(3) 73(4) 31(3) 3(3) 9(2) 16(3) C36D 92(6) 82(5) 33(3) 5(3) 9(3) 29(5) C34D 38(3) 41(3) 28(2) 1(2) 7(2) 6(2) (8) 133(10) 118(9) 24(8) 17(7) 48(7) C50 230(30) 170(20) 150(20) 44(16) 87(19) 120(20) 53 44(2) 71(3) 42(2) -8(2) 5.3(18) -15(2) C53 50(4) 68(5) 63(4) 8(4) 12(3) -2(3) 60 82(4) 102(5) 73(4) 15(3) 33(3) -13(4) C60 113(9) 120(9) 77(7) 33(6) -6(6) -40(7) 57 49(2) 67(3) 45(2) -9(2) 2.3(19) -1(2) C57 57(4) 123(8) 54(4) 4(5) 8(3) -20(5) 56 55(5) 62(6) 76(6) 15(5) 15(4) -14(4) C56 136(15) 75(10) 67(7) 25(7) 25(8) -61(10) 58 62(3) 60(3) 91(4) -19(3) 43(3) -8(2) C58 57(5) 51(4) 150(9) -21(5) 49(5) -9(4) 61 58(3) 54(3) 57(3) -5(2) 26(2) -19(2) C61 53(4) 65(5) 98(6) -9(4) 42(4) 2(3) (20) 112(13) 33(6) -7(7) 42(9) -105(14) C59 120(20) 99(18) 130(20) -11(17) 49(19) -37(15) (6) 148(8) 77(4) 15(4) 55(4) 47(6) C51 241(19) 208(18) 75(7) 35(9) 89(10) 104(16) 63 68(8) 250(20) 82(9) 41(12) 38(7) 41(11) C63 76(11) 86(12) 77(11) 3(9) 21(8) -11(9) 52 65(3) 53(3) 42(2) 4.5(19) 6(2) 11(2) C52 89(6) 74(6) 77(6) 20(5) 9(5) 27(5) C55 40(7) 78(9) 70(9) -14(8) 20(6) 3(7) 55 66(8) 105(9) 185(17) -84(10) 60(9) -22(7) 62 84(4) 80(4) 91(5) 7(4) 18(4) 11(4) 10' 37(8) 35(10) 26.8(18) -3(4) 14(4) 4(6)

40 SI-40 C35' 50(9) 35(12) 24(6) -3(7) 17(7) 0(9) 11' 48(10) 48(3) 28(3) -1(2) 16(7) 3(10) C36' 60(11) 72(15) 53(9) 21(10) 31(8) 14(10) 54A 104(12) 155(19) 65(9) 51(11) 59(9) 95(13) 54B 97(10) 95(12) 61(9) 39(9) 46(8) 52(9) C54B 83(14) 45(10) 69(13) -3(9) 42(12) 5(10) C54A 116(17) 220(40) 73(17) -40(20) 27(15) 50(20)

41 Table 4 Bond Lengths for platon_sq. SI-41 Atom Atom Length/Å Atom Atom Length/Å 1A C1A 1.261(6) 8C C21C 1.446(9) 2A C4A 1.216(6) 9C C23C 1.486(11) 3A C8A 1.335(6) 10C C25C 1.461(8) 4A C11A 1.197(6) 10C C35C 1.337(8) 5A C6A 1.369(6) 11C C35C 1.224(9) 5A C12A 1.443(6) 12C C27C 1.438(8) 6A C12A 1.409(6) N1C C2C 1.411(7) 6A C29A 1.385(7) N1C C15C 1.359(7) 7A C15A 1.222(6) N2C C3C 1.323(6) 8A C21A 1.453(7) C1C C2C 1.413(7) 9A C23A 1.440(6) C1C C9C 1.483(7) 10A C25A 1.49(4) C2C C3C 1.382(7) 10A C35A 1.333(17) C3C C4C 1.509(7) 11A C35A 1.220(19) C4C C10C 1.493(6) 12A C27A 1.420(8) C5C C6C 1.399(7) N1A C2A 1.426(6) C5C C10C 1.402(7) N1A C15A 1.352(6) C5C C11C 1.492(7) N2A C3A 1.326(7) C6C C7C 1.381(8) C1A C2A 1.427(7) C7C C8C 1.401(8) C1A C9A 1.482(7) C7C C14C 1.503(7) C2A C3A 1.365(7) C8C C9C 1.416(7) C3A C4A 1.513(6) C9C C10C 1.395(7) C4A C10A 1.480(7) C11C C12C 1.557(6) C5A C6A 1.385(7) C12C C13C 1.513(7) C5A C10A 1.417(7) C15C C16C 1.508(7) C5A C11A 1.481(7) C16C C17C 1.340(7) C6A C7A 1.382(7) C16C C30C 1.495(7) C7A C8A 1.394(7) C17C C18C 1.456(8) C7A C14A 1.501(7) C18C C19C 1.325(8) C8A C9A 1.424(7) C19C C20C 1.513(8) C9A C10A 1.399(7) C20C C21C 1.540(9) C11A C12A 1.559(7) C20C C31C 1.526(9) C12A C13A 1.506(7) C21C C22C 1.521(9) C15A C16A 1.510(7) C22C C23C 1.517(10) C16A C17A 1.321(8) C22C C32C 1.563(9) C16A C30A 1.514(7) C23C C24C 1.557(8) C17A C18A 1.471(7) C24C C25C 1.538(9) C18A C19A 1.325(8) C24C C33C 1.524(9) C19A C20A 1.526(8) C25C C26C 1.536(9) C20A C21A 1.541(8) C26C C27C 1.539(8) C20A C31A 1.531(10) C26C C34C 1.534(11) C21A C22A 1.522(8) C27C C28C 1.516(9) C22A C23A 1.532(8) C28C C29C 1.292(9)

42 C22A C32A 1.535(8) C35C C36C 1.509(12) C23A C24A 1.541(7) 1D C1D 1.254(6) C24A C25A 1.536(8) 2D C4D 1.212(6) C24A C33A 1.527(8) 3D C8D 1.326(6) C25A C26A 1.547(7) 4D C11D 1.210(6) C26A C27A 1.546(8) 5D C12D 1.424(6) C26A C34A 1.539(8) 5D C29D 1.392(7) C27A C28A 1.504(8) 6D C6D 1.368(6) C28A C29A 1.315(9) 6D C12D 1.449(6) C35A C36A 1.477(17) 7D C15D 1.230(6) 1B C1B 1.262(6) 8D C21D 1.445(9) 2B C4B 1.217(6) 9D C23D 1.441(10) 3B C8B 1.341(7) 10D C25D 1.482(6) 4B C11B 1.215(7) 10D C35D 1.336(9) 5B C6B 1.365(7) 11D C35D 1.219(10) 5B C12B 1.453(7) 12D C27D 1.433(8) 6B C15B 1.236(6) N1D C2D 1.416(6) 7B C21B 1.448(7) N1D C15D 1.352(6) 8B C23B 1.440(8) N2D C3D 1.317(6) 9B C25B 1.460(7) C1D C2D 1.443(6) 9B C35B 1.376(8) C1D C9D 1.475(7) 10B C35B 1.183(11) C2D C3D 1.380(7) 11B C27B 1.411(8) C3D C4D 1.510(6) 12B C12B 1.392(7) C4D C10D 1.484(6) 12B C29B 1.449(8) C5D C6D 1.396(6) N1B C2B 1.410(7) C5D C10D 1.401(7) N1B C15B 1.351(7) C5D C11D 1.463(7) N2B C3B 1.325(7) C6D C7D 1.390(7) C1B C2B 1.430(7) C7D C8D 1.403(7) C1B C9B 1.479(7) C7D C14D 1.490(7) C2B C3B 1.381(7) C8D C9D 1.436(6) C3B C4B 1.504(7) C9D C10D 1.377(7) C4B C10B 1.480(7) C11D C12D 1.549(6) C5B C6B 1.399(7) C12D C13D 1.499(7) C5B C10B 1.404(7) C15D C16D 1.509(7) C5B C11B 1.454(8) C16D C17D 1.333(8) C6B C7B 1.377(8) C16D C30D 1.513(7) C7B C8B 1.408(8) C17D C18D 1.455(8) C7B C14B 1.516(8) C18D C19D 1.326(8) C8B C9B 1.411(8) C19D C20D 1.496(10) C9B C10B 1.401(7) C20D C21D 1.540(8) C11B C12B 1.554(7) C20D C31D 1.519(12) C12B C13B 1.507(8) C21D C22D 1.523(9) C15B C16B 1.497(7) C22D C23D 1.541(9) C16B C17B 1.329(8) C22D C32D 1.552(11) C16B C30B 1.512(7) C23D C24D 1.553(9) SI-42

43 C17B C18B 1.452(8) C24D C25D 1.504(8) C18B C19B 1.333(8) C24D C33D 1.525(10) C19B C20B 1.511(9) C25D C26D 1.515(8) C20B C21B 1.534(9) C26D C27D 1.552(8) C20B C31B 1.543(10) C26D C34D 1.542(7) C21B C22B 1.533(8) C27D C28D 1.508(8) C22B C23B 1.538(10) C28D C29D 1.307(8) C22B C32B 1.529(9) C35D C36D 1.472(10) C23B C24B 1.541(9) 50 C (13) C24B C25B 1.537(10) 53 C (9) C24B C33B 1.536(9) 60 C (12) C25B C26B 1.511(9) 57 C (10) C26B C27B 1.538(11) 56 C (2) C26B C34B 1.511(10) 58 C (10) C27B C28B 1.480(10) 61 C (9) C28B C29B 1.274(10) 59 C (14) C35B C36B 1.478(13) 51 C (14) 1C C1C 1.272(6) 63 C (3) 2C C4C 1.201(6) 52 C (9) 3C C8C 1.342(6) C (19) 4C C11C 1.197(6) 10' C35' 1.335(16) 5C C12C 1.405(6) C35' 11' 1.227(19) 5C C29C 1.392(7) C35' C36' 1.482(19) 6C C6C 1.363(6) 54A C54A 1.437(15) 6C C12C 1.445(6) 54B C54B 1.439(14) 7C C15C 1.218(6) SI-43

44 Table 5 Bond Angles for platon_sq. SI-44 Atom Atom Atom Angle/ Atom Atom Atom Angle/ C6A 5A C12A 108.3(4) C35C 10C C25C 119.9(6) C29A 6A C12A 117.7(4) C15C N1C C2C 124.6(4) C35A 10A C25A 116(3) 1C C1C C2C 119.9(5) C15A N1A C2A 125.0(4) 1C C1C C9C 119.0(4) 1A C1A C2A 120.4(4) C2C C1C C9C 121.1(4) 1A C1A C9A 119.8(4) N1C C2C C1C 118.2(4) C2A C1A C9A 119.7(4) C3C C2C N1C 121.1(4) N1A C2A C1A 116.4(4) C3C C2C C1C 120.5(4) C3A C2A N1A 121.6(4) N2C C3C C2C 125.3(5) C3A C2A C1A 121.9(4) N2C C3C C4C 114.3(4) N2A C3A C2A 126.3(5) C2C C3C C4C 120.3(4) N2A C3A C4A 114.2(4) 2C C4C C3C 118.7(4) C2A C3A C4A 119.3(4) 2C C4C C10C 122.8(4) 2A C4A C3A 118.0(4) C10C C4C C3C 118.4(4) 2A C4A C10A 122.9(4) C6C C5C C10C 118.8(5) C10A C4A C3A 119.0(4) C6C C5C C11C 105.5(4) C6A C5A C10A 117.8(4) C10C C5C C11C 135.3(4) C6A C5A C11A 106.7(4) 6C C6C C5C 115.7(4) C10A C5A C11A 135.1(4) 6C C6C C7C 119.9(4) 5A C6A C5A 114.7(4) C7C C6C C5C 124.4(5) 5A C6A C7A 119.5(5) C6C C7C C8C 115.8(4) C7A C6A C5A 125.8(5) C6C C7C C14C 123.2(5) C6A C7A C8A 115.8(5) C8C C7C C14C 121.0(5) C6A C7A C14A 122.4(5) 3C C8C C7C 117.3(4) C8A C7A C14A 121.7(5) 3C C8C C9C 120.8(5) 3A C8A C7A 117.2(4) C7C C8C C9C 121.9(5) 3A C8A C9A 121.4(4) C8C C9C C1C 119.2(4) C7A C8A C9A 121.4(4) C10C C9C C1C 120.5(4) C8A C9A C1A 118.7(4) C10C C9C C8C 120.1(5) C10A C9A C1A 120.7(4) C5C C10C C4C 122.2(4) C10A C9A C8A 120.4(4) C9C C10C C4C 118.7(4) C5A C10A C4A 122.3(4) C9C C10C C5C 118.9(4) C9A C10A C4A 118.8(4) 4C C11C C5C 133.7(4) C9A C10A C5A 118.8(4) 4C C11C C12C 121.3(4) 4A C11A C5A 134.1(5) C5C C11C C12C 104.9(4) 4A C11A C12A 121.3(4) 5C C12C 6C 110.4(4) C5A C11A C12A 104.6(4) 5C C12C C11C 111.8(4) 5A C12A C11A 105.6(4) 5C C12C C13C 107.4(4) 5A C12A C13A 109.3(4) 6C C12C C11C 105.9(4) 6A C12A 5A 110.2(4) 6C C12C C13C 108.8(4) 6A C12A C11A 112.3(4) C13C C12C C11C 112.4(4) 6A C12A C13A 106.7(4) 7C C15C N1C 123.3(4) C13A C12A C11A 112.8(4) 7C C15C C16C 122.6(4)

45 7A C15A N1A 123.4(4) N1C C15C C16C 114.1(4) 7A C15A C16A 122.7(4) C17C C16C C15C 122.4(5) N1A C15A C16A 113.9(4) C17C C16C C30C 123.8(5) C15A C16A C30A 114.5(4) C30C C16C C15C 113.8(4) C17A C16A C15A 122.0(4) C16C C17C C18C 127.4(5) C17A C16A C30A 123.5(5) C19C C18C C17C 123.3(5) C16A C17A C18A 126.3(5) C18C C19C C20C 124.7(5) C19A C18A C17A 124.3(5) C19C C20C C21C 108.5(5) C18A C19A C20A 123.0(6) C19C C20C C31C 112.3(5) C19A C20A C21A 110.0(5) C31C C20C C21C 110.8(5) C19A C20A C31A 110.9(5) 8C C21C C20C 108.4(5) C31A C20A C21A 111.1(6) 8C C21C C22C 108.6(6) 8A C21A C20A 110.8(5) C22C C21C C20C 116.0(6) 8A C21A C22A 107.8(4) C21C C22C C32C 112.4(6) C22A C21A C20A 114.8(5) C23C C22C C21C 114.2(6) C21A C22A C23A 113.2(5) C23C C22C C32C 109.6(6) C21A C22A C32A 112.8(5) 9C C23C C22C 110.5(6) C23A C22A C32A 110.0(5) 9C C23C C24C 106.0(6) 9A C23A C22A 110.9(4) C22C C23C C24C 115.4(5) 9A C23A C24A 109.8(4) C25C C24C C23C 111.2(5) C22A C23A C24A 114.9(4) C33C C24C C23C 111.2(6) C25A C24A C23A 109.2(4) C33C C24C C25C 111.3(5) C33A C24A C23A 110.6(5) 10C C25C C24C 108.7(6) C33A C24A C25A 113.2(5) 10C C25C C26C 107.8(5) 10A C25A C24A 101.5(17) C26C C25C C24C 114.7(5) 10A C25A C26A 113(2) C25C C26C C27C 111.2(5) C24A C25A C26A 114.2(4) C34C C26C C25C 110.9(5) C27A C26A C25A 112.2(4) C34C C26C C27C 110.8(6) C34A C26A C25A 109.0(4) 12C C27C C26C 110.3(5) C34A C26A C27A 111.0(5) 12C C27C C28C 107.3(5) 12A C27A C26A 111.9(5) C28C C27C C26C 111.6(5) 12A C27A C28A 108.5(5) C29C C28C C27C 120.6(6) C28A C27A C26A 111.0(5) C28C C29C 5C 127.3(6) C29A C28A C27A 120.4(6) 10C C35C C36C 111.1(6) C28A C29A 6A 126.6(5) 11C C35C 10C 123.2(7) 10A C35A C36A 112(3) 11C C35C C36C 125.7(6) 11A C35A 10A 124(3) C29D 5D C12D 113.4(4) 11A C35A C36A 124(3) C6D 6D C12D 108.1(3) C6B 5B C12B 108.3(4) C35D 10D C25D 119.6(5) C35B 9B C25B 117.0(6) C15D N1D C2D 123.5(4) C12B 12B C29B 112.5(5) 1D C1D C2D 120.1(4) C15B N1B C2B 125.4(5) 1D C1D C9D 120.1(4) 1B C1B C2B 120.3(5) C2D C1D C9D 119.6(4) 1B C1B C9B 119.3(5) N1D C2D C1D 117.0(4) C2B C1B C9B 120.2(4) C3D C2D N1D 122.1(4) N1B C2B C1B 118.0(4) C3D C2D C1D 120.8(4) SI-45

46 C3B C2B N1B 120.6(5) N2D C3D C2D 125.9(5) C3B C2B C1B 121.4(5) N2D C3D C4D 115.2(4) N2B C3B C2B 126.2(5) C2D C3D C4D 118.9(4) N2B C3B C4B 115.3(4) 2D C4D C3D 119.6(4) C2B C3B C4B 118.5(5) 2D C4D C10D 122.5(4) 2B C4B C3B 119.9(4) C10D C4D C3D 117.8(4) 2B C4B C10B 121.9(5) C6D C5D C10D 118.5(4) C10B C4B C3B 118.1(4) C6D C5D C11D 106.3(4) C6B C5B C10B 118.2(5) C10D C5D C11D 133.9(4) C6B C5B C11B 106.9(5) 6D C6D C5D 114.1(4) C10B C5B C11B 133.9(5) 6D C6D C7D 120.9(4) 5B C6B C5B 113.9(5) C7D C6D C5D 124.9(4) 5B C6B C7B 120.9(5) C6D C7D C8D 115.1(4) C7B C6B C5B 125.0(5) C6D C7D C14D 123.0(5) C6B C7B C8B 115.5(5) C8D C7D C14D 121.8(5) C6B C7B C14B 122.9(5) 3D C8D C7D 117.5(4) C8B C7B C14B 121.6(5) 3D C8D C9D 120.7(4) 3B C8B C7B 117.2(5) C7D C8D C9D 121.7(4) 3B C8B C9B 120.8(5) C8D C9D C1D 118.9(4) C7B C8B C9B 122.0(5) C10D C9D C1D 121.1(4) C8B C9B C1B 120.7(5) C10D C9D C8D 119.9(4) C10B C9B C1B 119.4(5) C5D C10D C4D 121.9(4) C10B C9B C8B 119.8(5) C9D C10D C4D 118.4(4) C5B C10B C4B 122.1(5) C9D C10D C5D 119.7(4) C9B C10B C4B 118.7(5) 4D C11D C5D 131.9(4) C9B C10B C5B 119.2(5) 4D C11D C12D 122.1(4) 4B C11B C5B 132.3(5) C5D C11D C12D 105.7(4) 4B C11B C12B 121.6(5) 5D C12D 6D 108.9(4) C5B C11B C12B 105.6(4) 5D C12D C11D 108.9(4) 5B C12B C11B 104.8(4) 5D C12D C13D 109.2(4) 5B C12B C13B 110.1(5) 6D C12D C11D 104.9(4) 12B C12B 5B 108.6(4) 6D C12D C13D 110.9(4) 12B C12B C11B 110.9(5) C13D C12D C11D 113.9(4) 12B C12B C13B 108.7(5) 7D C15D N1D 123.2(4) C13B C12B C11B 113.5(4) 7D C15D C16D 122.2(4) 6B C15B N1B 122.2(5) N1D C15D C16D 114.5(4) 6B C15B C16B 122.7(4) C15D C16D C30D 113.8(4) N1B C15B C16B 115.1(4) C17D C16D C15D 123.0(5) C15B C16B C30B 112.2(5) C17D C16D C30D 123.2(5) C17B C16B C15B 125.0(5) C16D C17D C18D 128.4(5) C17B C16B C30B 122.7(5) C19D C18D C17D 123.9(6) C16B C17B C18B 128.2(5) C18D C19D C20D 125.5(6) C19B C18B C17B 121.5(5) C19D C20D C21D 110.2(5) C18B C19B C20B 125.6(6) C19D C20D C31D 111.4(5) C19B C20B C21B 111.5(5) C31D C20D C21D 110.6(7) C19B C20B C31B 110.3(5) 8D C21D C20D 106.9(6) SI-46

47 C21B C20B C31B 110.4(6) 8D C21D C22D 110.0(6) 7B C21B C20B 109.5(5) C22D C21D C20D 116.2(5) 7B C21B C22B 109.4(5) C21D C22D C23D 112.9(5) C22B C21B C20B 115.3(5) C21D C22D C32D 112.8(8) C21B C22B C23B 111.7(5) C23D C22D C32D 109.5(6) C32B C22B C21B 113.6(6) 9D C23D C22D 106.5(7) C32B C22B C23B 110.0(5) 9D C23D C24D 110.4(5) 8B C23B C22B 110.4(5) C22D C23D C24D 114.2(6) 8B C23B C24B 109.2(6) C25D C24D C23D 112.6(5) C22B C23B C24B 114.4(5) C25D C24D C33D 114.4(6) C25B C24B C23B 111.5(5) C33D C24D C23D 109.9(6) C33B C24B C23B 110.8(6) 10D C25D C24D 109.1(5) C33B C24B C25B 113.8(5) 10D C25D C26D 105.1(5) 9B C25B C24B 106.5(5) C24D C25D C26D 116.8(5) 9B C25B C26B 108.5(5) C25D C26D C27D 110.5(5) C26B C25B C24B 114.5(5) C25D C26D C34D 111.8(5) C25B C26B C27B 111.4(5) C34D C26D C27D 110.7(5) C25B C26B C34B 112.1(6) 12D C27D C26D 109.9(5) C34B C26B C27B 113.3(7) 12D C27D C28D 109.8(5) 11B C27B C26B 106.2(6) C28D C27D C26D 110.3(5) 11B C27B C28B 114.0(6) C29D C28D C27D 123.9(6) C28B C27B C26B 110.0(5) C28D C29D 5D 121.8(5) C29B C28B C27B 124.1(7) 10D C35D C36D 112.8(7) C28B C29B 12B 121.2(6) 11D C35D 10D 123.4(6) 9B C35B C36B 109.8(7) 11D C35D C36D 123.4(7) 10B C35B 9B 122.2(7) 10' C35' C36' 115(3) 10B C35B C36B 128.0(7) 11' C35' 10' 123(3) C29C 5C C12C 118.0(4) 11' C35' C36' 122(3) C6C 6C C12C 108.0(4) SI-47 Table 6 Hydrogen Bonds for platon_sq. D H A d(d-h)/å d(h-a)/å d(d-a)/å D-H-A/ 3A H3A 1A (5) A H8A (6) A H9A 8A (5) A H12A 11A 0.94(10) 2.01(11) 2.84(7) 146(8) N2A H2AA 7C 0.88(7) 2.06(7) 2.882(6) 155(6) 3B H3B 1B (6) B H7B (7) B H8B 7B (6) N1B H1B (7) 2.22(7) 2.849(7) 150(6) 3C H3C 1C (5) C H12C 9A (5) 141.2

48 N1C H1C (7) 2.05(7) 2.977(7) 168(6) N2C H2CB 7A 0.86(7) 2.08(7) 2.889(6) 156(5) 3D H3D 1D 0.83(9) 1.82(9) 2.507(5) 140(8) 8D H8D 9D 0.83(9) 1.89(8) 2.618(7) 146(8) 9D H9D 11D (8) D H12D (6) N1D H1D (7) 2.04(7) 2.880(6) 157(6) 50 H (18) H53 8D (7) H (2) H (10) H (8) H (10) H55 12A (14) C54B H54C 11C 0.970(14) 1.94(3) 2.767(17) 142(2) C54A H54H 8A (14) 2.19(7) 2.92(3) 130(6) 8C H8C 9C 0.841(15) 2.00(4) 2.753(7) 149(7) 9C H9C 54B 0.962(11) 2.39(3) 2.729(16) 100(2) SI X,+Y,+Z; 2 +X,+Y,-1+Z; 3 1-X,1/2+Y,1-Z; 4-1+X,+Y,-1+Z; 5 1+X,+Y,1+Z; 6 1+X,+Y,+Z

49 Table 7 Torsion Angles for platon_sq. SI-49 A B C D Angle/ A B C D Angle/ 1A C1A C2A N1A 6.4(7) 1C C1C C2C N1C 8.2(7) 1A C1A C2A C3A (4) 1C C1C C2C C3C (4) 1A C1A C9A C8A -3.2(7) 1C C1C C9C C8C -4.1(7) 1A C1A C9A C10A (4) 1C C1C C9C C10C (4) 2A C4A C10A C5A 1.8(7) 2C C4C C10C C5C 0.6(7) 2A C4A C10A C9A 177.7(4) 2C C4C C10C C9C 176.3(5) 3A C8A C9A C1A 7.3(7) 3C C8C C9C C1C 5.6(7) 3A C8A C9A C10A (4) 3C C8C C9C C10C 179.8(5) 4A C11A C12A 5A 177.0(4) 4C C11C C12C 5C 58.5(6) 4A C11A C12A 6A 57.0(6) 4C C11C C12C 6C 178.8(4) 4A C11A C12A C13A -63.6(6) 4C C11C C12C C13C -62.5(6) 5A C6A C7A C8A 175.2(4) 6C C6C C7C C8C 174.8(5) 5A C6A C7A C14A -1.5(8) 6C C6C C7C C14C -2.7(8) 7A C15A C16A C17A (5) 7C C15C C16C C17C (6) 7A C15A C16A C30A 55.2(6) 7C C15C C16C C30C 52.9(6) 8A C21A C22A C23A 54.7(6) 8C C21C C22C C23C 62.1(7) 8A C21A C22A C32A -71.0(6) 8C C21C C22C C32C -63.6(9) 9A C23A C24A C25A -51.4(6) 9C C23C C24C C25C -61.4(7) 9A C23A C24A C33A (5) 9C C23C C24C C33C 173.9(5) 10A C25A C26A C27A 54.6(18) 10C C25C C26C C27C 51.7(7) 10A C25A C26A C34A 177.9(18) 10C C25C C26C C34C 175.5(5) 12A C27A C28A C29A (6) 12C C27C C28C C29C (6) N1A C2A C3A N2A -6.5(8) N1C C2C C3C N2C -7.2(8) N1A C2A C3A C4A 169.0(4) N1C C2C C3C C4C 168.0(4) N1A C15A C16A C17A 57.8(6) N1C C15C C16C C17C 57.7(6) N1A C15A C16A C30A (5) N1C C15C C16C C30C (5) N2A C3A C4A 2A 4.0(6) N2C C3C C4C 2C 4.6(6) N2A C3A C4A C10A (4) N2C C3C C4C C10C (4) C1A C2A C3A N2A 176.6(5) C1C C2C C3C N2C 177.3(5) C1A C2A C3A C4A -8.0(7) C1C C2C C3C C4C -7.5(7) C1A C9A C10A C4A -3.8(7) C1C C9C C10C C4C -3.1(7) C1A C9A C10A C5A 172.3(4) C1C C9C C10C C5C 172.8(4) C2A N1A C15A 7A -3.0(7) C2C N1C C15C 7C -1.7(7) C2A N1A C15A C16A 174.0(4) C2C N1C C15C C16C 176.7(4) C2A C1A C9A C8A 174.8(4) C2C C1C C9C C8C 175.4(5) C2A C1A C9A C10A 0.7(7) C2C C1C C9C C10C 1.2(7) C2A C3A C4A 2A (4) C2C C3C C4C 2C (5) C2A C3A C4A C10A 4.6(6) C2C C3C C4C C10C 5.4(6) C3A C4A C10A C5A (4) C3C C4C C10C C5C (4) C3A C4A C10A C9A 1.3(6) C3C C4C C10C C9C -0.1(6) C5A C6A C7A C8A -3.3(8) C5C C6C C7C C8C -3.3(8) C5A C6A C7A C14A 179.9(5) C5C C6C C7C C14C 179.2(5) C5A C11A C12A 5A -1.8(5) C5C C11C C12C 5C (4)

50 C5A C11A C12A 6A (4) C5C C11C C12C 6C 0.3(5) C5A C11A C12A C13A 117.5(4) C5C C11C C12C C13C 119.0(4) C6A 5A C12A 6A 122.8(4) C6C 6C C12C 5C 120.8(4) C6A 5A C12A C11A 1.3(5) C6C 6C C12C C11C -0.4(5) C6A 5A C12A C13A (4) C6C 6C C12C C13C (4) C6A C5A C10A C4A 175.0(4) C6C C5C C10C C4C 174.2(4) C6A C5A C10A C9A -0.9(7) C6C C5C C10C C9C -1.5(7) C6A C5A C11A 4A (5) C6C C5C C11C 4C (5) C6A C5A C11A C12A 1.6(5) C6C C5C C11C C12C -0.1(5) C6A C7A C8A 3A (5) C6C C7C C8C 3C (5) C6A C7A C8A C9A 0.3(7) C6C C7C C8C C9C 0.2(8) C7A C8A C9A C1A (5) C7C C8C C9C C1C (5) C7A C8A C9A C10A 2.1(7) C7C C8C C9C C10C 2.1(8) C8A C9A C10A C4A (4) C8C C9C C10C C4C (4) C8A C9A C10A C5A -1.7(7) C8C C9C C10C C5C -1.4(7) C9A C1A C2A N1A (4) C9C C1C C2C N1C (4) C9A C1A C2A C3A 5.5(7) C9C C1C C2C C3C 4.3(7) C10A C5A C6A 5A (4) C10C C5C C6C 6C (4) C10A C5A C6A C7A 3.6(8) C10C C5C C6C C7C 4.0(7) C10A C5A C11A 4A -4.4(9) C10C C5C C11C 4C -5.8(10) C10A C5A C11A C12A 174.2(5) C10C C5C C11C C12C 172.5(5) C11A C5A C6A 5A -0.9(6) C11C C5C C6C 6C -0.1(6) C11A C5A C6A C7A 177.7(5) C11C C5C C6C C7C 178.1(5) C11A C5A C10A C4A 3.0(8) C11C C5C C10C C4C 2.4(8) C11A C5A C10A C9A (5) C11C C5C C10C C9C (5) C12A 5A C6A C5A -0.3(6) C12C 5C C29C C28C 51.4(8) C12A 5A C6A C7A (4) C12C 6C C6C C5C 0.4(6) C12A 6A C29A C28A 51.7(8) C12C 6C C6C C7C (4) C14A C7A C8A 3A -2.2(8) C14C C7C C8C 3C -0.1(8) C14A C7A C8A C9A 177.1(5) C14C C7C C8C C9C 177.8(5) C15A N1A C2A C1A (5) C15C N1C C2C C1C (5) C15A N1A C2A C3A 73.0(6) C15C N1C C2C C3C 72.2(7) C15A C16A C17A C18A 1.7(8) C15C C16C C17C C18C -0.6(8) C16A C17A C18A C19A (6) C16C C17C C18C C19C (6) C17A C18A C19A C20A 178.8(5) C17C C18C C19C C20C 179.1(5) C18A C19A C20A C21A -65.9(8) C18C C19C C20C C21C -60.3(7) C18A C19A C20A C31A 57.3(8) C18C C19C C20C C31C 62.5(8) C19A C20A C21A 8A -57.0(6) C19C C20C C21C 8C -56.0(6) C19A C20A C21A C22A (5) C19C C20C C21C C22C (5) C20A C21A C22A C23A 178.7(5) C20C C21C C22C C23C (6) C20A C21A C22A C32A 53.0(7) C20C C21C C22C C32C 58.7(9) C21A C22A C23A 9A -75.4(6) C21C C22C C23C 9C -68.6(7) C21A C22A C23A C24A 49.9(6) C21C C22C C23C C24C 51.6(9) C22A C23A C24A C25A (5) C22C C23C C24C C25C 176.0(7) C22A C23A C24A C33A 57.5(6) C22C C23C C24C C33C 51.3(9) C23A C24A C25A 10A -66(2) C23C C24C C25C 10C -73.2(7) SI-50

51 C23A C24A C25A C26A 172.5(4) C23C C24C C25C C26C 166.1(6) C24A C25A C26A C27A 169.7(5) C24C C25C C26C C27C 172.9(6) C24A C25A C26A C34A -67.1(6) C24C C25C C26C C34C -63.3(7) C25A 10A C35A 11A 10(7) C25C 10C C35C 11C -2.1(9) C25A 10A C35A C36A -174(3) C25C 10C C35C C36C 176.5(6) C25A C26A C27A 12A 69.8(6) C25C C26C C27C 12C 71.5(7) C25A C26A C27A C28A (5) C25C C26C C27C C28C (6) C26A C27A C28A C29A 107.1(7) C26C C27C C28C C29C 109.9(7) C27A C28A C29A 6A (5) C27C C28C C29C 5C (5) C29A 6A C12A 5A -79.6(5) C29C 5C C12C 6C -80.3(5) C29A 6A C12A C11A 37.8(6) C29C 5C C12C C11C 37.4(6) C29A 6A C12A C13A 161.8(5) C29C 5C C12C C13C 161.2(4) C30A C16A C17A C18A (5) C30C C16C C17C C18C (5) C31A C20A C21A 8A 179.9(5) C31C C20C C21C 8C (5) C31A C20A C21A C22A 57.5(7) C31C C20C C21C C22C 57.8(7) C32A C22A C23A 9A 51.8(6) C32C C22C C23C 9C 58.6(9) C32A C22A C23A C24A 177.1(5) C32C C22C C23C C24C 178.7(7) C33A C24A C25A 10A 58(2) C33C C24C C25C 10C 51.4(6) C33A C24A C25A C26A -63.8(6) C33C C24C C25C C26C -69.3(7) C34A C26A C27A 12A -52.3(6) C35C 10C C25C C24C 98.3(6) C34A C26A C27A C28A 69.1(6) C35C 10C C25C C26C (5) C35A 10A C25A C24A 139(3) C34C C26C C27C 12C -52.3(7) C35A 10A C25A C26A -98(4) C34C C26C C27C C28C 66.9(7) 1B C1B C2B N1B 6.6(7) 1D C1D C2D N1D 5.6(7) 1B C1B C2B C3B (5) 1D C1D C2D C3D (5) 1B C1B C9B C8B -3.6(7) 1D C1D C9D C8D -2.3(7) 1B C1B C9B C10B 179.9(5) 1D C1D C9D C10D (5) 2B C4B C10B C5B 24.4(7) 2D C4D C10D C5D 23.0(7) 2B C4B C10B C9B (5) 2D C4D C10D C9D (4) 3B C8B C9B C1B 5.7(8) 3D C8D C9D C1D 4.9(7) 3B C8B C9B C10B (5) 3D C8D C9D C10D (4) 4B C11B C12B 5B 176.1(4) 4D C11D C12D 5D 61.4(6) 4B C11B C12B 12B 59.1(6) 4D C11D C12D 6D 177.9(4) 4B C11B C12B C13B -63.7(7) 4D C11D C12D C13D -60.7(6) 5B C6B C7B C8B 173.2(5) 6D C6D C7D C8D 173.3(4) 5B C6B C7B C14B -5.6(9) 6D C6D C7D C14D -3.8(8) 6B C15B C16B C17B (6) 7D C15D C16D C17D (6) 6B C15B C16B C30B 54.9(7) 7D C15D C16D C30D 53.6(6) 7B C21B C22B C23B 58.2(7) 8D C21D C22D C23D 67.1(8) 7B C21B C22B C32B -66.8(7) 8D C21D C22D C32D -57.7(8) 8B C23B C24B C25B -48.9(7) 9D C23D C24D C25D -49.1(7) 8B C23B C24B C33B (5) 9D C23D C24D C33D (5) 9B C25B C26B C27B 67.5(7) 10D C25D C26D C27D 67.1(6) 9B C25B C26B C34B (8) 10D C25D C26D C34D (5) 11B C27B C28B C29B 1.6(10) 12D C27D C28D C29D -6.8(7) N1B C2B C3B N2B -0.5(8) N1D C2D C3D N2D -0.3(7) SI-51

52 N1B C2B C3B C4B (4) N1D C2D C3D C4D (4) N1B C15B C16B C17B 56.2(7) N1D C15D C16D C17D 58.8(7) N1B C15B C16B C30B (5) N1D C15D C16D C30D (5) N2B C3B C4B 2B -21.1(6) N2D C3D C4D 2D -21.9(6) N2B C3B C4B C10B 162.1(4) N2D C3D C4D C10D 162.1(4) C1B C2B C3B N2B (5) C1D C2D C3D N2D (4) C1B C2B C3B C4B 3.3(7) C1D C2D C3D C4D 6.8(7) C1B C9B C10B C4B -9.9(7) C1D C9D C10D C4D -9.5(7) C1B C9B C10B C5B 170.7(5) C1D C9D C10D C5D 172.5(4) C2B N1B C15B 6B -4.8(8) C2D N1D C15D 7D -4.7(8) C2B N1B C15B C16B 173.4(5) C2D N1D C15D C16D 171.4(4) C2B C1B C9B C8B 171.1(5) C2D C1D C9D C8D 173.6(4) C2B C1B C9B C10B -5.4(7) C2D C1D C9D C10D -3.6(7) C2B C3B C4B 2B 158.3(5) C2D C3D C4D 2D 156.3(4) C2B C3B C4B C10B -18.5(6) C2D C3D C4D C10D -19.7(6) C3B C4B C10B C5B (5) C3D C4D C10D C5D (4) C3B C4B C10B C9B 21.7(7) C3D C4D C10D C9D 20.9(6) C5B C6B C7B C8B -3.0(9) C5D C6D C7D C8D -3.8(7) C5B C6B C7B C14B 178.2(6) C5D C6D C7D C14D 179.1(5) C5B C11B C12B 5B 2.7(5) C5D C11D C12D 5D (4) C5B C11B C12B 12B (5) C5D C11D C12D 6D 4.1(5) C5B C11B C12B C13B 122.9(5) C5D C11D C12D C13D 125.6(4) C6B 5B C12B 12B 112.7(5) C6D 6D C12D 5D 108.3(4) C6B 5B C12B C11B -5.9(5) C6D 6D C12D C11D -8.1(5) C6B 5B C12B C13B (5) C6D 6D C12D C13D (4) C6B C5B C10B C4B (5) C6D C5D C10D C4D (4) C6B C5B C10B C9B 3.9(7) C6D C5D C10D C9D 2.9(6) C6B C5B C11B 4B (5) C6D C5D C11D 4D (5) C6B C5B C11B C12B 1.3(5) C6D C5D C11D C12D 1.3(5) C6B C7B C8B 3B (5) C6D C7D C8D 3D (5) C6B C7B C8B C9B 0.9(8) C6D C7D C8D C9D 1.9(7) C7B C8B C9B C1B (5) C7D C8D C9D C1D (5) C7B C8B C9B C10B 3.5(8) C7D C8D C9D C10D 2.2(7) C8B C9B C10B C4B 173.5(5) C8D C9D C10D C4D 173.3(4) C8B C9B C10B C5B -5.9(7) C8D C9D C10D C5D -4.7(7) C9B C1B C2B N1B (4) C9D C1D C2D N1D (4) C9B C1B C2B C3B 8.8(7) C9D C1D C2D C3D 4.9(7) C10B C5B C6B 5B (4) C10D C5D C6D 6D (4) C10B C5B C6B C7B 0.7(8) C10D C5D C6D C7D 1.5(7) C10B C5B C11B 4B -2.9(10) C10D C5D C11D 4D -5.2(9) C10B C5B C11B C12B 169.5(5) C10D C5D C11D C12D 167.6(5) C11B C5B C6B 5B -5.4(6) C11D C5D C6D 6D -6.9(5) C11B C5B C6B C7B 171.1(5) C11D C5D C6D C7D 170.3(5) C11B C5B C10B C4B 17.4(8) C11D C5D C10D C4D 19.9(8) C11B C5B C10B C9B (5) C11D C5D C10D C9D (5) C12B 5B C6B C5B 7.3(6) C12D 5D C29D C28D (5) SI-52

53 C12B 5B C6B C7B (5) C12D 6D C6D C5D 9.8(5) C12B 12B C29B C28B (7) C12D 6D C6D C7D (5) C14B C7B C8B 3B 0.9(8) C14D C7D C8D 3D -0.9(8) C14B C7B C8B C9B 179.7(6) C14D C7D C8D C9D 179.0(5) C15B N1B C2B C1B (6) C15D N1D C2D C1D (5) C15B N1B C2B C3B 69.3(7) C15D N1D C2D C3D 65.3(7) C15B C16B C17B C18B 0.6(9) C15D C16D C17D C18D 1.6(8) C16B C17B C18B C19B (6) C16D C17D C18D C19D (6) C17B C18B C19B C20B (5) C17D C18D C19D C20D 179.5(5) C18B C19B C20B C21B -51.5(8) C18D C19D C20D C21D -61.4(8) C18B C19B C20B C31B 71.6(8) C18D C19D C20D C31D 61.7(8) C19B C20B C21B 7B -54.9(6) C19D C20D C21D 8D -51.5(6) C19B C20B C21B C22B (5) C19D C20D C21D C22D (6) C20B C21B C22B C23B (5) C20D C21D C22D C23D (7) C20B C21B C22B C32B 57.1(7) C20D C21D C22D C32D 63.8(10) C21B C22B C23B 8B -68.2(6) C21D C22D C23D 9D -58.4(8) C21B C22B C23B C24B 55.5(7) C21D C22D C23D C24D 63.6(9) C22B C23B C24B C25B (5) C22D C23D C24D C25D (6) C22B C23B C24B C33B 59.0(7) C22D C23D C24D C33D 62.3(8) C23B C24B C25B 9B -60.1(6) C23D C24D C25D 10D -60.7(7) C23B C24B C25B C26B (6) C23D C24D C25D C26D (5) C24B C25B C26B C27B (5) C24D C25D C26D C27D (5) C24B C25B C26B C34B -45.6(10) C24D C25D C26D C34D -48.1(7) C25B 9B C35B 10B -3.5(11) C25D 10D C35D 11D -12.1(10) C25B 9B C35B C36B 175.9(7) C25D 10D C35D C36D 174.9(6) C25B C26B C27B 11B 69.8(7) C25D C26D C27D 12D 63.1(6) C25B C26B C27B C28B (6) C25D C26D C27D C28D (5) C26B C27B C28B C29B (7) C26D C27D C28D C29D (6) C27B C28B C29B 12B (5) C27D C28D C29D 5D (4) C29B 12B C12B 5B -63.4(6) C29D 5D C12D 6D -60.4(5) C29B 12B C12B C11B 51.3(6) C29D 5D C12D C11D 53.5(5) C29B 12B C12B C13B 176.8(5) C29D 5D C12D C13D 178.4(4) C30B C16B C17B C18B (5) C30D C16D C17D C18D (5) C31B C20B C21B 7B (5) C31D C20D C21D 8D (5) C31B C20B C21B C22B 58.2(7) C31D C20D C21D C22D 61.7(8) C32B C22B C23B 8B 58.8(7) C32D C22D C23D 9D 68.2(9) C32B C22B C23B C24B (6) C32D C22D C23D C24D (8) C33B C24B C25B 9B 66.2(6) C33D C24D C25D 10D 65.7(7) C33B C24B C25B C26B -53.7(8) C33D C24D C25D C26D -53.3(7) C35B 9B C25B C24B 130.7(6) C35D 10D C25D C24D 109.8(6) C35B 9B C25B C26B (7) C35D 10D C25D C26D (6) C34B C26B C27B 11B -57.7(8) C34D C26D C27D 12D -61.2(6) C34B C26B C27B C28B 66.2(9) C34D C26D C27D C28D 60.0(6) SI-53

54 SI-54 Table 8 Hydrogen Atom Coordinates (Å 10 4 ) and Isotropic Displacement Parameters (Å ) for platon_sq. Atom x y z U(eq) H3A H8A H9A H12A 1720(60) 5170(30) 9680(50) 70(20) H1A 370(40) 7060(20) 6440(40) 36(16) H2AA 2310(40) 6860(20) 6210(30) 28(14) H2AB 2840(40) 6420(20) 6320(30) 35(15) H13A H13B H13C H14A H14B H14C H17A H18A H19A H20A H21A H22A H23A H24A H25A H26A H27A H28A H29A H30A H30B H30C H31A H31B H31C H32A H32B H32C H33A H33B H33C H34A H34B H34C H36A

55 SI-55 H36B H36C H3B H7B H8B H11B H1B 5600(40) 4640(20) 5980(30) 23(15) H2BA H2BB H13D H13E H13F H14D H14E H14F H17B H18B H19B H20B H21B H22B H23B H24B H25B H26B H27B H28B H29B H30D H30E H30F H31D H31E H31F H32D H32E H32F H33D H33E H33F H36D H36E H36F H34D H34E H34F

56 SI-56 H3C H12C (40) H1C 2690(40) 7850(20) 4340(40) 39(16) H2CA 1740(40) 6470(30) 4400(40) 35(16) H2CB 1620(40) 6940(20) 4580(30) 24(14) H13G H13H H13I H14G H14H H14I H17C H18C H19C H20C H21C H22C H23C H24C H25C H26C H27C H28C H29C H30G H30H H30I H31G H31H H31I H32G H32H H32I H33G H33H H33I H36G H36H H36I H34G H34H H34I H3D -880(50) 4200(30) 4550(40) 56 H8D 850(60) 3700(30) 1510(50) 50(20) H9D H12D (20)

57 SI-57 H1D 1510(40) 3910(20) 4040(40) 32(15) H2DA 2500(40) 5310(20) 4350(30) 23(14) H2DB 2790(50) 4850(30) 4350(40) 50(20) H13J H13K H13L H14J H14K H14L H17D H18D H19D H20D H21D H22D H23D H24D H25D H26D H27D H28D H29D H30J H30K H30L H31J H31K H31L H32J H32K H32L H33J H33K H33L H36J H36K H36L H34J H34K H34L H H50A H50B H50C H H53A

58 SI-58 H53B H53C H H60A H60B H60C H H57A H57B H57C H H56A H56B H56C H H58A 7540(30) 3788(16) 5980(20) 124 H58B 7650(30) 3912(14) 6813(16) 124 H58C 6712(12) 3811(13) 6230(30) 124 H H61A H61B H61C H H59A 7952(12) 6810(20) 8448(18) 170 H59B 8070(30) 6863(19) 9300(20) 170 H59C 8670(30) 6513(11) 9060(30) 170 H H51A H51B H51C H H63A H63B H63C H H52A H52B H52C H55A H55B H55C H H62A 7040(60) 3503(8) 7970(60) 132 H62B 7260(100) 3110(30) 8430(20) 132 H36M H36N

59 SI-59 H H54A H54B H54C 1050(20) 7563(9) -412(13) 92 H54D 1378(19) 8051(10) -72(16) 92 H54E 840(30) 8000(13) -907(15) 92 H54F 1680(30) 8143(17) 231(14) 206 H54G 1830(30) 8280(40) -490(20) 206 H54H 1760(40) 7760(30) -310(50) 206 H8C 1140(100) 8170(30) 2000(70) 206 H9C 1168(19) 7597(6) 748(12) 206 Table 9 Atomic ccupancy for platon_sq. Atom ccupancy Atom ccupancy Atom ccupancy 10A 0.49(5) 11A 0.49(5) C35A 0.49(5) C36A 0.49(5) H36A 0.49(5) H36B 0.49(5) H36C 0.49(5) H C H50A 0.75 H50B 0.75 H50C (14) H (14) C (14) H56A 0.575(14) H56B 0.575(14) H56C 0.575(14) (14) H (14) C (14) H59A 0.425(14) H59B 0.425(14) H59C 0.425(14) H C H63A 0.5 H63B 0.5 H63C 0.5 C H55A 0.5 H55B 0.5 H55C H ' 0.51(5) C35' 0.51(5) 11' 0.51(5) C36' 0.51(5) H36M 0.51(5) H36N 0.51(5) H (5) 54A H54A B H54B C54B H54C H54D H54E C54A H54F H54G H54H 0.375

60 Table 10 Solvent masks information for platon_sq. Number X Y Z Volume Electron count Content SI-60

61 SI-61 1 H NMR Spectrum of 3-Amino-rifamycin S (2) recorded at 600 MHz in DMS-d 6 Me Ac H NH 2 H H 2 N H

62 SI-62 Expanded 1 H NMR Spectrum of 3-Amino-rifamycin S (2) with peak picking recorded at 600 MHz in DMSd 6 Me Ac H NH 2 H H 2 N H

63 SI-63 Expanded 1 H NMR Spectrum of 3-Amino-rifamycin S (2) with peak picking recorded at 600 MHz in DMSd 6 Me Ac H NH 2 H H 2 N H

64 SI-64 Expanded 1 H NMR Spectrum of 3-Amino-rifamycin S (2) with peak picking recorded at 600 MHz in DMSd 6 Me Ac H NH 2 H H 2 N H

65 gradcsy60 NMR Spectrum of 3-Amino-rifamycin S (2) recorded at 600 MHz in DMS-d 6 SI-65 Me Ac H NH 2 H H 2 N H

66 gradhsqc NMR Spectrum of 3-Amino-rifamycin S (2) recorded at 600 MHz in DMS-d 6 SI-66 Me Ac H NH 2 H H 2 N H

67 gradhmbc NMR Spectrum of 3-Amino-rifamycin S (2) recorded at 600 MHz in DMS-d 6 SI-67 Me Ac H NH 2 H H 2 N H

68 tresy NMR Spectrum of 3-Amino-rifamycin S (2)recorded at 600 MHz in DMS-d 6 SI-68 Me Ac H NH 2 H H 2 N H

69 grad 15 NHSQC NMR Spectrum of 3-Amino-rifamycin S (2) recorded at 600 MHz in DMS-d 6 SI-69 Me Ac H NH 2 H H 2 N H

70 SI-70 1 H NMR Spectrum of Sporalactam A (3) recorded at 600 MHz in DMS-d 6 H H H Ac H N H 3

71 SI-71 Expanded 1 H NMR Spectrum of Sporalactam A (3) with peak picking recorded at 600 MHz in DMS-d 6 H Ac H H H N H 3

72 SI-72 Expanded 1 H NMR Spectrum of Sporalactam A (3) with peak picking recorded at 600 MHz in DMS-d 6 H H H Ac H N H 3

73 SI C NMR Spectrum of Sporalactam A (3) recorded at 150 MHz in DMS-d 6 H H H Ac H N H 3

74 gradcsy60 NMR Spectrum of Sporalactam A (3) recorded at 600 MHz in DMS-d 6 SI-74 H Ac H H H N H 3

75 SI-75 gradhsqc NMR Spectrum of Sporalactam A (3) recorded at 600 MHz in DMS-d 6 H H H Ac H N H 3

76 SI-76 gradhmbc NMR Spectrum of Sporalactam A (3) recorded at 600 MHz in DMS-d 6 H H H Ac H N H 3

77 SI-77 tresy NMR Spectrum of Sporalactam A (3) recorded at 600 MHz in DMS-d 6 H H H Ac H N H 3

78 grad 15 NHSQC NMR Spectrum of Sporalactam A (3) recorded at 600 MHz in DMS-d 6 SI-78 H Ac H H H N H 3

79 SI-79 1 H NMR Spectrum of Sporalactam B (4) recorded at 600 MHz in DMS-d 6 Me H H Ac H N H 4

80 SI-80 Expanded 1 H NMR Spectrum of Sporalactam B (4) with peak picking recorded at 600 MHz in DMS-d 6 Me Ac H H H N H 4

81 SI-81 Expanded 1 H NMR Spectrum of Sporalactam B (4) with peak picking recorded at 600 MHz in DMS-d 6 Me Ac H H H N H 4

82 SI C NMR Spectrum of Sporalactam B (4) recorded at 150 MHz in DMS-d 6 Me H H Ac H N H 4

83 gradcsy60 NMR Spectrum of Sporalactam B (4) recorded at 600 MHz in DMS-d 6 SI-83 Me Ac H H H N H 4

84 SI-84 gradhsqc NMR Spectrum of Sporalactam B (4) recorded at 600 MHz in DMS-d 6 Me H H Ac H N H 4

85 SI-85 gradhmbc NMR Spectrum of Sporalactam B (4) recorded at 600 MHz in DMS-d 6 Me H H Ac H N H 4

86 SI-86 tresy NMR Spectrum of Sporalactam B (4) recorded at 600 MHz in DMS-d 6 Me H H Ac H N H 4

87 SI-87 Table SI4. In vitro broth culture and intracellular MIC90 s in µm >10 >10 >10 > >10 >10 >10 >10 Acinetobacter johnsonii >10 > Candida albicansa >10 >10 >10 >10 >10 > >10 > >50 >50 > MRSA a a Klebsiella pneumoniae Pseudomonas aeruginosaa a Escherichia coli a Enterococcus faecalis a Mycobacterium tuberculosis (Mtb) Mtb in macrophages 17,b Mycobacterium abscessusb b a) 3 biological replicates. b) 2 biological replicates (2x) and for each the assay was in technical triplicates. (3x) Experimental - Minimum Inhibitory Concentration Assay. Seed cultures of targeted pathogens Klebsiella pneumoniae, Pseudomonas aeruginosa, Acinetobacter johnsonii, Candida albicans, Enterococcus faecalis, Escherichia coli #1105 (UBC Collection) and Methicillin Resistant Staphylococcus aureus (MRSA) (ATCC 33591) were incubated in Muller Hinton Broth at 37oC overnight. The assay was conducted in Falcon 96-well plates. Each pathogen culture (100 ul, ~10,000 cells per well) was added to the wells containing 90 ul/well of MH broth, 10 ul/well of DMS and 10 ul/well of tested compound with serial dilution from 20 ng/ml to 0.04 ng/ml (final concentrations). All, including positive controls of 27-demethoxy-27-hydroxyrifamycin S (6) and rifamycin S (7) from 2ng/mL to ng/ml, and blanks with 200 ul/well of MH broth only, were prepared in triplicates. The plates were incubated overnight at 37oC. Next day microbial growth was determined by measuring the optical density at 600 nm using the DTX880 plate reader (Beckman Coulter). The MIC end point is defined as the lowest concentration with complete growth inhibition.

88 SI-88 Genome sequencing. A single colony of Micromonospora sp. RJA4480 was grown in 3 ml marine medium 1 for four days at 28 C with shaking at 250 r.p.m. Genomic DNA was harvested using a GenElute Bacterial Genomic DNA Kit (Sigma), and sequenced at the Farncombe Metagenomics Facility (McMaster University), using an Illumina MiSeq DNA sequencer. Contigs were assembled using the ABySS genome assembly program. Secondary metabolites biosynthetic gene clusters were predicted using PRISM. Figure SI1. Rifamycin analogue cluster in Micromonospora sp. RJA 4480 identified by PRISM. 17 AHBA, 3-amino-5-hydroxybenzoic acid acyl adenylating domain; T, thiolation domain; KS, ketosynthase domain; MeM, methylmalonyl-coa domain; Mal, malonyl-coa domain; DH, dehydratase domain; KR, ketoreductase domain; P450, cytochrome P450 domain; 3,4DH, 3,4-dehydratase domain; C-GT, C-glycosyltransferase domain; E, epimerase domian; 3KR, 3-ketoreductase domain; 2,3DH, 2,3-dehydratase domain; TE, thioesterase domain; MT, -methyltransferase domain.

89 SI-89 Figure SI2. Chem3D Calculated MM2 Energy Minimized Conformations for Sporalactam B (4) C-16 Epimers. A) C-16R Epimer

90 B) C-16S Epimer SI-90

91 C) Sporalactam B (4) [16S]: Planes with Hs 1, 8, 21, and 23. SI-91