Experimental. Crystal data

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1 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN Ethyl N-[4-(3-methyl-4,5-dihydrobenzo- [g]indazol-1-yl)phenylsulfonyl]thiocarbamate ethanol monosolvate Abdullah M. Asiri, a,b Abdulrahman O. Al-Youbi, a Hassan M. Faidallah, a Seik Weng Ng c and Edward R. T. Tiekink c * a Chemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah,Saudi Arabia, b Center of Excellence for Advanced Materials Research, King Abdulaziz University, PO Box 80203, Jeddah, Saudi Arabia, and c Department of Chemistry, University of Malaya, Kuala Lumpur, Malaysia Correspondence Edward.Tiekink@gmail.com Received 15 August 2011; accepted 19 August 2011 Experimental Crystal data C 21 H 21 N 3 O 3 S 2 C 2 H 6 O M r = Monoclinic, P2 1 =c a = (2) Å b = (8) Å c = (17) Å = (11) Data collection Agilent SuperNova Dual diffractometer with Atlas detector Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) T min = 0.786, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections V = (7) Å 3 Z =8 Mo K radiation = 0.27 mm 1 T = 100 K mm measured reflections independent reflections 4871 reflections with I > 2(I) R int = parameters H-atom parameters constrained max = 0.80 e Å 3 min = 0.67 e Å 3 Key indicators: single-crystal X-ray study; T = 100 K; mean (C C) = Å; R factor = 0.087; wr factor = 0.261; data-to-parameter ratio = Table 1 Hydrogen-bond geometry (Å, ). The title compound, C 21 H 20 N 3 O 3 S 2 CH 3 CH 2 OH, comprises two independent organic molecules and two ethanol solvent molecules. The molecules are related by pseudo-mirror symmetry. In both molecules, the N-bound benzene ring is twisted out of the plane of the pyrazole ring [the dihedral angles are 51.4 (3) and 44.1 (3), respectively]. Similarly, the benzene ring of the 1,2-dihydronaphthalene residue is inclined with respect to the five-membered ring [dihedral angles 18.3 (3) and 22.2 (3) ]. Overall, each molecule has a flattened U shape. Dimeric aggregates mediated by O HN(pyrazole) and amide-n HO hydrogen bonds feature in the crystal packing, whereby the ethanol molecules link the independent organic molecules, leading to fourmolecule aggregates. Related literature For background to the biological activity of species related to the title compound, see: Faidallah et al. (2007); Al-Saadi et al. (2008). D HA D H HA DA D HA N3 H3O (5) 174 N6 H6O (6) 170 O7 H7N (6) 161 O8 H8N (5) 170 Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997), DIAMOND (Brandenburg, 2006) and Qmol (Gans & Shalloway, 2001); software used to prepare material for publication: publcif (Westrip, 2010). The authors are grateful to the Center of Excellence for Advanced Materials Research and the Chemistry Department at King Abdulaziz University for providing research facilities. The authors also thank the University of Malaya for supporting this study. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2343). References Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England. Al-Saadi, M. S., Rostom, S. A. F. & Faidallah, H. M. (2008). Arch. Pharm. Chem. Life Sci, 341, Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Faidallah, H. M., Al-Saadi, M. S., Rostom, S. A. F. & Fahmy, H. T. Y. (2007). Med. Chem. Res. 16, Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. Gans, J. & Shalloway, D. (2001). J. Mol. Graphics Modell. 19, Sheldrick, G. M. (2008). Acta Cryst. A64, Westrip, S. P. (2010). J. Appl. Cryst. 43, Additional correspondence author, aasiri2@kau.edu.sa. o2450 Asiri et al. doi: /s Acta Cryst. (2011). E67, o2450

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3 Acta Cryst. (2011). E67, o2450 [ doi: /s ] Ethyl N-[4-(3-methyl-4,5-dihydrobenzo[g]indazol-1-yl)phenylsulfonyl]thiocarbamate ethanol monosolvate A. M. Asiri, A. O. Al-Youbi, H. M. Faidallah, S. W. Ng and E. R. T. Tiekink Comment The structural analysis of the title compound, (I), was conducted in the context of on-going investigations into the biological activity of related species (Faidallah et al., 2007; Al-Saadi et al., 2008). Two independent organic molecules and two solvent ethanol molecules comprise the crystallographic asymmetric unit in (I), Fig. 1. As seen from the overlay diagram, Fig. 2, the molecules are related by a pseudo mirror plane but there are measurable conformational differences between them. Focusing upon N-bound-benzene rings first, the dihedral angle formed between it and the pyrazole ring is 51.4 (3) and 44.1 (3), respectively for the S1- and S2-containing molecules. With respect to the 1,2-dihydronaphthalene residue, the β-methylene groups lie to opposite sides of the plane through the pyrazole ring in the two molecules but to approximately the same extent as reflected in the dihedral angles formed between the five-membered ring and the benzene rings of 18.3 (3) and 22.2 (3), respectively. Globally, the molecules have a flattened U-shape as the terminal ethoxycarbothioamide group is orientated to the same side of the molecule as the 1,2-dihydronaphthalene residue, with both directed over the N-bound benzene ring. As anticipated there is hydrogen bonding in operation in the crystal structure of (I), Table 1. Thus, there are close associations between the ethanol and organic molecules with each solvent molecule forming a hydrogen bond to a pyrazole-n and at the same time accepting a hydrogen bond from an amide-h. As shown in Fig. 3, the ethanol molecules link the independent organic molecules into four-molecule aggregates. Experimental A mixture of 3-methyl-2-(p-sulfamylphenyl)-4,5-dihydronaphtho[1,2-c]pyrazole (10 mmol) and anhydrous K 2 CO 3 (20 mmol) in dry acetone (25 ml) was stirred and treated with phenylisothiocyanate (12 mmol). After the mixture was stirred and refluxed for 10 h, acetone was removed under pressure. The isolated solid mass dissolved in water and acidified with 2 N HCl. The crude product was purified by recrystallization from ethanol as colourless plates m.p K. Refinement Carbon-bound H atoms were placed in calculated positions [O H = 0.84 Å, N H = 0.88 Å and C H 0.95 to 0.99 Å, U iso (H) 1.2 to 1.5U eq (parent atom)] and were included in the refinement in the riding model approximation. sup-1

4 Figures Fig. 1. The molecular structures of the two independent organic molecules and two independent ethanol molecules that comprise the crystallographic asymmetric unit in (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. Fig. 2. Overlay diagram of the two independent organic molecules. The image in red contains the S1 atom. Fig. 3. Four-molecule aggregate in (I) mediated by O H N and N H O hydrogen bonding, shown as orange and blue dashed lines, respectively. Ethyl N-[4-(3-methyl-4,5-dihydrobenzo[g]indazol- 1-yl}phenylsulfonyl]thiocarbamate ethanol monosolvate Crystal data C 21 H 21 N 3 O 3 S 2 C 2 H 6 O F(000) = 2000 M r = D x = Mg m 3 Monoclinic, P2 1 /c Mo Kα radiation, λ = Å Hall symbol: -P 2ybc Cell parameters from 2528 reflections a = (2) Å θ = b = (8) Å µ = 0.27 mm 1 c = (17) Å T = 100 K β = (11) Plate, colourless V = (7) Å mm Z = 8 Data collection Agilent SuperNova Dual diffractometer with Atlas detector Radiation source: SuperNova (Mo) X-ray Source mirror R int = independent reflections 4871 reflections with I > 2σ(I) Detector resolution: pixels mm -1 θ max = 27.5, θ min = 2.3 ω scans Absorption correction: multi-scan h = k = sup-2

5 (CrysAlis PRO; Agilent, 2010) T min = 0.786, T max = measured reflections l = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained S = 1.03 w = 1/[σ 2 (F 2 o ) + (0.0853P) P] where P = (F 2 o + 2F 2 c )/ reflections (Δ/σ) max = parameters Δρ max = 0.80 e Å 3 0 restraints Δρ min = 0.67 e Å 3 Special details Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > σ(f 2 ) is used only for calculating R- factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq S (6) (9) (7) (3) S (6) (10) (8) (3) S (6) (10) (8) (3) S (7) (13) (11) (4) O (16) (3) (2) (8) O (15) (3) (19) (8) O (15) (2) (2) (8) O (15) (3) (2) (9) O (16) (3) (2) (9) O (16) (3) (2) (10) O (2) (3) (2) (11) H * O (17) (3) (2) (9) H * N (19) (3) (3) (11) sup-3

6 N (18) (3) (2) (9) N (16) (3) (2) (9) H * N (17) (3) (2) (9) N (18) (3) (2) (9) N (18) (3) (3) (10) H * C (3) (5) (4) (19) H1A * H1B * H1C * C (2) (4) (4) (14) C (2) (4) (4) (14) C (3) (5) (4) (16) H4A * H4B * C (2) (5) (4) (16) H5A * H5B * C (2) (4) (3) (12) C (2) (4) (3) (12) H7A * C (2) (4) (3) (12) H8A * C (2) (4) (3) (13) H * C (2) (4) (3) (11) H * C (2) (4) (3) (11) C (2) (4) (3) (11) C (2) (4) (3) (11) C (2) (4) (3) (12) H * C (2) (4) (3) (12) H * C (2) (4) (3) (10) C (2) (4) (3) (11) H * C (2) (4) (3) (11) H * C (2) (4) (3) (11) C (2) (4) (3) (11) H20A * H20B * C (2) (4) (4) (14) H21A * H21B * H21C * C (2) (4) (3) (12) sup-4

7 H22A * H22B * H22C * C (2) (4) (3) (10) C (2) (4) (3) (10) C (2) (4) (3) (12) H25A * H25B * C (2) (4) (3) (12) H26A * H26B * C (2) (4) (3) (11) C (2) (4) (3) (12) H * C (3) (4) (3) (13) H * C (2) (4) (3) (12) H * C (2) (4) (3) (12) H * C (2) (4) (3) (11) C (2) (4) (3) (10) C (2) (4) (3) (10) C (2) (4) (3) (11) H * C (2) (4) (3) (11) H * C (2) (4) (3) (11) C (2) (4) (3) (11) H * C (2) (4) (3) (11) H * C (2) (4) (4) (13) C (3) (5) (4) (17) H41A * H41B * C (3) (6) (5) (2) H42A * H42B * H42C * C (3) (5) (4) (15) H43A * H43B * C (3) (5) (4) (15) H44A * H44B * H44C * C (3) (4) (4) (15) H45A * sup-5

8 H45B * C (3) (5) (4) (16) H46A * H46B * H46C * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 S (6) (6) (7) (5) (5) (5) S (7) (8) (8) (6) (6) (6) S (7) (7) (8) (5) (6) (6) S (9) (10) (12) (7) (8) (8) O (19) (19) (2) (16) (16) (15) O (19) (2) (19) (15) (15) (14) O (18) (18) (2) (15) (16) (15) O (2) (19) (3) (16) (18) (17) O (2) (2) (2) (17) (17) (17) O (2) (3) (3) (19) (19) (2) O (3) (2) (3) (2) (2) (19) O (2) (19) (2) (17) (18) (16) N (2) (3) (3) (2) (2) (2) N (2) (2) (2) (18) (18) (18) N (2) (2) (2) (17) (18) (17) N (2) (2) (2) (18) (17) (18) N (2) (2) (2) (17) (17) (17) N (2) (2) (3) (18) (2) (2) C (3) (4) (5) (3) (3) (4) C (3) (3) (4) (3) (3) (3) C (3) (3) (4) (2) (3) (3) C (3) (4) (4) (3) (3) (3) C (3) (4) (4) (3) (3) (3) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (3) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (2) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (2) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (2) (3) (3) (2) (2) (2) C (2) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (4) (3) (3) (3) sup-6

9 C (3) (3) (3) (2) (2) (2) C (3) (3) (2) (2) (2) (2) C (2) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (3) (2) C (3) (3) (3) (3) (3) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (2) (3) (3) (2) (2) (2) C (2) (2) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (2) (2) (3) (2) (2) (2) C (2) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (4) (2) (2) (3) C (4) (4) (5) (3) (3) (3) C (4) (5) (7) (4) (4) (4) C (4) (4) (4) (3) (3) (3) C (3) (4) (3) (3) (3) (3) C (4) (3) (4) (3) (3) (3) C (3) (5) (4) (3) (3) (3) Geometric parameters (Å, ) S1 O (3) C17 C (6) S1 O (3) C17 H S1 N (4) C18 H S1 C (5) C20 C (7) S2 C (5) C20 H20A S3 O (4) C20 H20B S3 O (4) C21 H21A S3 N (4) C21 H21B S3 C (5) C21 H21C S4 C (5) C22 C (7) O3 C (6) C22 H22A O3 C (5) C22 H22B O6 C (6) C22 H22C O6 C (7) C23 C (7) O7 C (7) C24 C (6) O7 H C24 C (6) O8 C (6) C25 C (7) O8 H C25 H25A N1 C (6) C25 H25B N1 N (5) C26 C (7) N2 C (6) C26 H26A sup-7

10 N2 C (6) C26 H26B N3 C (6) C27 C (7) N3 H C27 C (7) N4 C (6) C28 C (7) N4 N (5) C28 H N5 C (6) C29 C (7) N5 C (6) C29 H N6 C (6) C30 C (7) N6 H C30 H C1 C (7) C31 C (7) C1 H1A C31 H C1 H1B C32 C (6) C1 H1C C34 C (6) C2 C (8) C34 C (6) C3 C (7) C35 C (7) C3 C (7) C35 H C4 C (8) C36 C (7) C4 H4A C36 H C4 H4B C37 C (7) C5 C (7) C38 C (6) C5 H5A C38 H C5 H5B C39 H C6 C (7) C41 C (9) C6 C (7) C41 H41A C7 C (7) C41 H41B C7 H7A C42 H42A C8 C (7) C42 H42B C8 H8A C42 H42C C9 C (7) C43 C (8) C9 H C43 H43A C10 C (6) C43 H43B C10 H C44 H44A C11 C (7) C44 H44B C13 C (7) C44 H44C C13 C (7) C45 C (8) C14 C (7) C45 H45A C14 H C45 H45B C15 C (7) C46 H46A C15 H C46 H46B C16 C (6) C46 H46C O1 S1 O (2) C20 C21 H21C O1 S1 N (2) H21A C21 H21C O2 S1 N (19) H21B C21 H21C O1 S1 C (2) C23 C22 H22A O2 S1 C (2) C23 C22 H22B N3 S1 C (2) H22A C22 H22B O4 S3 O (2) C23 C22 H22C O4 S3 N (2) H22A C22 H22C O5 S3 N (2) H22B C22 H22C sup-8

11 O4 S3 C (2) N4 C23 C (4) O5 S3 C (2) N4 C23 C (4) N6 S3 C (2) C24 C23 C (4) C19 O3 C (4) C33 C24 C (4) C40 O6 C (4) C33 C24 C (4) C43 O7 H C23 C24 C (4) C45 O8 H C24 C25 C (4) C2 N1 N (4) C24 C25 H25A N1 N2 C (4) C26 C25 H25A N1 N2 C (4) C24 C25 H25B C12 N2 C (4) C26 C25 H25B C19 N3 S (3) H25A C25 H25B C19 N3 H C27 C26 C (4) S1 N3 H C27 C26 H26A C23 N4 N (4) C25 C26 H26A C33 N5 N (4) C27 C26 H26B C33 N5 C (4) C25 C26 H26B N4 N5 C (4) H26A C26 H26B C40 N6 S (4) C28 C27 C (5) C40 N6 H C28 C27 C (4) S3 N6 H C32 C27 C (4) C2 C1 H1A C27 C28 C (5) C2 C1 H1B C27 C28 H H1A C1 H1B C29 C28 H C2 C1 H1C C28 C29 C (5) H1A C1 H1C C28 C29 H H1B C1 H1C C30 C29 H N1 C2 C (5) C31 C30 C (5) N1 C2 C (5) C31 C30 H C3 C2 C (5) C29 C30 H C12 C3 C (5) C30 C31 C (5) C12 C3 C (5) C30 C31 H C2 C3 C (5) C32 C31 H C3 C4 C (5) C31 C32 C (5) C3 C4 H4A C31 C32 C (4) C5 C4 H4A C27 C32 C (4) C3 C4 H4B N5 C33 C (4) C5 C4 H4B N5 C33 C (4) H4A C4 H4B C24 C33 C (4) C6 C5 C (5) C35 C34 C (4) C6 C5 H5A C35 C34 N (4) C4 C5 H5A C39 C34 N (4) C6 C5 H5B C36 C35 C (4) C4 C5 H5B C36 C35 H H5A C5 H5B C34 C35 H C7 C6 C (5) C37 C36 C (5) C7 C6 C (5) C37 C36 H C11 C6 C (5) C35 C36 H C6 C7 C (5) C36 C37 C (4) sup-9

12 C6 C7 H7A C36 C37 S (4) C8 C7 H7A C38 C37 S (3) C9 C8 C (5) C39 C38 C (4) C9 C8 H8A C39 C38 H C7 C8 H8A C37 C38 H C8 C9 C (5) C38 C39 C (5) C8 C9 H C38 C39 H C10 C9 H C34 C39 H C9 C10 C (5) O6 C40 N (4) C9 C10 H O6 C40 S (4) C11 C10 H N6 C40 S (4) C10 C11 C (5) O6 C41 C (5) C10 C11 C (4) O6 C41 H41A C6 C11 C (4) C42 C41 H41A N2 C12 C (4) O6 C41 H41B N2 C12 C (4) C42 C41 H41B C3 C12 C (5) H41A C41 H41B C14 C13 C (4) C41 C42 H42A C14 C13 N (4) C41 C42 H42B C18 C13 N (4) H42A C42 H42B C15 C14 C (4) C41 C42 H42C C15 C14 H H42A C42 H42C C13 C14 H H42B C42 H42C C14 C15 C (5) O7 C43 C (5) C14 C15 H O7 C43 H43A C16 C15 H C44 C43 H43A C17 C16 C (4) O7 C43 H43B C17 C16 S (3) C44 C43 H43B C15 C16 S (4) H43A C43 H43B C16 C17 C (4) C43 C44 H44A C16 C17 H C43 C44 H44B C18 C17 H H44A C44 H44B C17 C18 C (4) C43 C44 H44C C17 C18 H H44A C44 H44C C13 C18 H H44B C44 H44C O3 C19 N (4) O8 C45 C (4) O3 C19 S (4) O8 C45 H45A N3 C19 S (4) C46 C45 H45A O3 C20 C (4) O8 C45 H45B O3 C20 H20A C46 C45 H45B C21 C20 H20A H45A C45 H45B O3 C20 H20B C45 C46 H46A C21 C20 H20B C45 C46 H46B H20A C20 H20B H46A C46 H46B C20 C21 H21A C45 C46 H46C C20 C21 H21B H46A C46 H46C H21A C21 H21B H46B C46 H46C C2 N1 N2 C (6) C20 O3 C19 N (4) C2 N1 N2 C (4) C20 O3 C19 S2 3.5 (6) sup-10

13 O1 S1 N3 C (4) S1 N3 C19 O3 5.8 (6) O2 S1 N3 C (4) S1 N3 C19 S (3) C16 S1 N3 C (4) C19 O3 C20 C (4) C23 N4 N5 C (5) N5 N4 C23 C (5) C23 N4 N5 C (4) N5 N4 C23 C (4) O4 S3 N6 C (4) N4 C23 C24 C (5) O5 S3 N6 C (5) C22 C23 C24 C (5) C37 S3 N6 C (5) N4 C23 C24 C (5) N2 N1 C2 C3 0.3 (6) C22 C23 C24 C (9) N2 N1 C2 C (5) C33 C24 C25 C (6) N1 C2 C3 C (7) C23 C24 C25 C (5) C1 C2 C3 C (6) C24 C25 C26 C (5) N1 C2 C3 C (6) C25 C26 C27 C (5) C1 C2 C3 C4 3.0 (12) C25 C26 C27 C (6) C12 C3 C4 C (7) C32 C27 C28 C (7) C2 C3 C4 C (6) C26 C27 C28 C (5) C3 C4 C5 C (7) C27 C28 C29 C (8) C4 C5 C6 C (5) C28 C29 C30 C (8) C4 C5 C6 C (8) C29 C30 C31 C (8) C11 C6 C7 C8 0.8 (8) C30 C31 C32 C (7) C5 C6 C7 C (5) C30 C31 C32 C (5) C6 C7 C8 C9 1.6 (8) C28 C27 C32 C (7) C7 C8 C9 C (8) C26 C27 C32 C (4) C8 C9 C10 C (8) C28 C27 C32 C (4) C9 C10 C11 C6 2.5 (7) C26 C27 C32 C (7) C9 C10 C11 C (5) N4 N5 C33 C (5) C7 C6 C11 C (7) C34 N5 C33 C (4) C5 C6 C11 C (5) N4 N5 C33 C (5) C7 C6 C11 C (5) C34 N5 C33 C (8) C5 C6 C11 C (7) C23 C24 C33 N5 0.2 (5) N1 N2 C12 C3 0.5 (6) C25 C24 C33 N (4) C13 N2 C12 C (5) C23 C24 C33 C (4) N1 N2 C12 C (5) C25 C24 C33 C (7) C13 N2 C12 C (9) C31 C32 C33 N (8) C2 C3 C12 N2 0.6 (6) C27 C32 C33 N (5) C4 C3 C12 N (5) C31 C32 C33 C (5) C2 C3 C12 C (5) C27 C32 C33 C (7) C4 C3 C12 C (8) C33 N5 C34 C (7) C10 C11 C12 N (9) N4 N5 C34 C (4) C6 C11 C12 N (5) C33 N5 C34 C (5) C10 C11 C12 C (5) N4 N5 C34 C (6) C6 C11 C12 C (7) C39 C34 C35 C (7) N1 N2 C13 C (5) N5 C34 C35 C (4) C12 N2 C13 C (7) C34 C35 C36 C (7) N1 N2 C13 C (6) C35 C36 C37 C (7) C12 N2 C13 C (5) C35 C36 C37 S (3) C18 C13 C14 C (7) O4 S3 C37 C (4) N2 C13 C14 C (4) O5 S3 C37 C (4) C13 C14 C15 C (7) N6 S3 C37 C (4) sup-11

14 C14 C15 C16 C (7) O4 S3 C37 C (4) C14 C15 C16 S (4) O5 S3 C37 C (3) O1 S1 C16 C (4) N6 S3 C37 C (4) O2 S1 C16 C (4) C36 C37 C38 C (7) N3 S1 C16 C (4) S3 C37 C38 C (4) O1 S1 C16 C (4) C37 C38 C39 C (7) O2 S1 C16 C (4) C35 C34 C39 C (7) N3 S1 C16 C (4) N5 C34 C39 C (4) C15 C16 C17 C (7) C41 O6 C40 N (5) S1 C16 C17 C (4) C41 O6 C40 S4 1.7 (8) C16 C17 C18 C (7) S3 N6 C40 O6 1.3 (7) C14 C13 C18 C (7) S3 N6 C40 S (3) N2 C13 C18 C (4) C40 O6 C41 C (6) Hydrogen-bond geometry (Å, ) D H A D H H A D A D H A N3 H3 O (5) 174 N6 H6 O (6) 170 O7 H7 N (6) 161 O8 H8 N (5) 170 sup-12

15 Fig. 1 sup-13

16 Fig. 2 sup-14

17 Fig. 3 sup-15