Experimental. Crystal data

Transcription

1 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN ,11,17,23-Tetra-tert-butyl-25,27-bis[2- (4-nitrophenoxy)ethoxy]calix[4]arene- 26,28-diol acetonitrile tetrasolvate Jiu-Mao Yuan, Yong-Hong Gao, Jian-Ping Ma and Dian-Shun Guo* Department of Chemistry, Shandong Normal University, Jinan , People s Republic of China Correspondence chdsguo@sdnu.edu.cn Received 17 April 2009; accepted 14 May 2009 Key indicators: single-crystal X-ray study; T = 173 K; mean (C C) = Å; disorder in main residue; R factor = 0.114; wr factor = 0.349; data-to-parameter ratio = Experimental Crystal data C 60 H 70 N 2 O 10 4C 2 H 3 N M r = Triclinic, P1 a = (3) Å b = (3) Å c = (5) Å = (3) = (3) = (3) V = (13) Å 3 Z =2 Mo K radiation = 0.08 mm 1 T = 173 K mm In the crystal structure of the title compound, C 60 H 70 N 2 O 10-4CH 3 CN, the calix[4]arene molecule adopts an open-cone conformation with two intramolecular O HO hydrogen bonds. The four benzene rings of the calix[4]arene are twisted to the mean plane defined by four methylene C atoms bridging the benzene rings, with dihedral angles ranging from (10) to (12). Two pendant nitrophenyl rings are nearly perpendicular to each other, the dihedral angle being 70.9 (3). The asymmetric unit of the crystal structure contains four acetonitrile solvent molecules, one of which lies in the calix cavity and makes C H interactions and another links with the calix[4]arene via C HO hydrogen bonding. One tert-butyl group is disordered over two sets of sites, with a (13):0.264 (13) occupancy ratio. Related literature For general background to the chemistry of calix[4]arenes, see: Gutsche (1998). For related crystal structures, see: Singh et al. (2004); Bolte et al. (2003); Zeng et al. (2002); Gale et al. (1998); Drew et al. (1997); Böhmer et al. (1993); Bugge et al. (1992). For C H contacts, see: Tsuzuki et al. (2000); Umezawa et al. (1998). For inclusion complexes, see: McKervey et al. (1986). Data collection Bruker SMART CCD area-detector diffractometer Absorption correction: none measured reflections Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 775 parameters Table 1 Hydrogen-bond geometry (Å, ) independent reflections 7114 reflections with I > 2(I) R int = restraints H-atom parameters constrained max = 0.78 e Å 3 min = 0.64 e Å 3 D HA D H HA DA D HA O1 H1O (6) 171 O2 H2O (4) 176 C50 H50CO7 i (10) 156 C68 H68BO (13) 148 C65 H65ACg (6) 163 Symmetry code: (i) x þ 1; y þ 1; z þ 1. Cg1 is the centroid of the C42 C47 ring. Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL. Financial support from the National Natural Science Foundation of China (grant No ) and the Natural Science Foundation of Shandong Province, China (grant No. Y2006B30) is gratefully acknowledged. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2512). o1336 Yuan et al. doi: /s

2 organic compounds References Böhmer, V., Ferguson, G., Gallagher, J. F., Lough, A. J., McKervey, M. A., Madigan, E., Moran, M. B., Phillips, J. & Williams, J. (1993). J. Chem. Soc. Perkin Trans. 1, pp Bolte, M., Danila, C. & Böhmer, V. (2003). Acta Cryst. E59, o533 o534. Bruker (1999). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Bugge, K.-E., Verboom, W., Reinhoudt, D. N. & Harkema, S. (1992). Acta Cryst. C48, Drew, M. G. B., Beer, P. D. & Ogden, M. I. (1997). Acta Cryst. C53, Gale, P. A., Chen, Z., Drew, M. G. B., Heath, J. A. & Beer, P. D. (1998). Polyhedron, 17, Gutsche, C. D. (1998). Calixarenes Revisited. RSC Monographs in Chemistry. Cambridge: Royal Society of Chemistry. McKervey, M. A., Seward, E. M., Ferguson, G. & Ruhl, B. L. (1986). J. Org. Chem. 51, Sheldrick, G. M. (2008). Acta Cryst. A64, Singh, N., Kumar, M. & Hundal, G. (2004). Tetrahedron 60, Tsuzuki, S., Honda, K., Uchimaru, T., Mikami, M. & Tanabe, K. (2000). J. Am. Chem. Soc. 122, Umezawa, Y., Tsuboyama, S., Honda, K., Uzawa, J. & Nishio, M. (1998). Bull. Chem. Soc. Jpn, 71, Zeng, X.-S., Weng, L.-H., Chen, L.-X., Xu, F.-B., Li, Q.-S., Leng, X.-B., He, X.- W. & Zhang, Z.-Z. (2002). Tetrahedron, 58, Yuan et al. C 60 H 70 N 2 O 10 4C 2 H 3 N o1337

3 supporting information [doi: /s ] 5,11,17,23-Tetra-tert-butyl-25,27-bis[2-(4-nitrophenoxy)ethoxy]- calix[4]arene-26,28-diol acetonitrile tetrasolvate Jiu-Mao Yuan, Yong-Hong Gao, Jian-Ping Ma and Dian-Shun Guo S1. Comment Calix[4]arenes have been attracting much interest because they possess a versatile three-dimensional cavity and are ideal scaffolds for the construction of supramolecular systems. In particular, the lower or upper rim of a calix[4]arene platform can be modified to achieve more sophisticated receptors with a specific affinity and selectivity for ion recognition (Gutsche, 1998). Several crystal structures of 1,3-substituted cone calix[4]arene derivatives (Singh et al., 2004; Bolte et al., 2003; Zeng et al., 2002; Gale et al., 1998; Drew et al., 1997; Böhmer et al., 1993; Bugge et al., 1992) have been described. We report here the crystal structure of a new 1,3-substituted calix[4]arene, C 60 H 70 N 2 O 10.4CH 3 CN, namely 5,11,17,23-tetra-tert-butyl-25,27-bis[2-(4-nitrophenoxy)ethoxy]-26,28-dihydroxycalix[4]arene acetonitrile tetrasolvate. In the crystal structure of the title compound, as shown in Fig. 1, the molecule of the calix[4]arene adopts an open-cone conformation, in which either phenol hydroxy group links with one neighboring ethereal O atom via an intramolecular O H O hydrogen bond (Table 1) and one t-butyl group shows rotational disorder. The four benzene rings of the calix[4]arene are twisted to the virtual plane defined by four methylene C atoms bridging the phenolic rings with dihedral angles ranging from (10) to (12). Two pendant nitrophenyl rings are nearly perpendicular to each other, the dihedral angle being 70.9 (3). This conformation results in a distance of (6) Å between diametrically opposed atoms O1 and O2, almost same as (6) Å between O3 and O4. There are four acetonitrile solvate molecules in the asymmetric unit of the crystal structure, one of which lies in the calix cavity with C H π contacts (Umezawa et al., 1998; Tsuzuki et al., 2000) and another links with the calix[4]arene via C H O hydrogen bonding (Table 1). The apolar end of the acetonitrile is held in the cavity, while the polar one remains outside, similar to the related cone calix[4]arene system (McKervey et al., 1986) where an acetonitrile molecule is included. The intermolecular C H O hydrogen bonds (Table 1) and the remaining acetonitrile molecules stabilize the molecular packing. S2. Experimental To a refluxing suspension of p-tert-butylcalix[4]arene (1.112 g, 1.50 mmol) and anhydrous potassium carbonate (0.228 g, 1.65 mmol) in dry acetonitrile (15 ml) was added 2-(4-nitrophenoxy)ethyl-4-methylbenzenesulfonate (1.144 g, 3.00 mmol) in dry acetonitrile (15 ml) dropwise. The mixture was stirred and refluxed under a nitrogen atmosphere for 46 h and cooled to room temperature. The solvent was removed under reduced pressure. The residue was neutralized with diluted hydrochloric acid and extracted with dichloromethane. The organic layer was washed with saturated sodium hydrogen carbonate and brine, and dried over anhydrous magnesium sulfate. Removal of the solvent under reduced pressure, the residue was purified by flash column chromatography (silica gel, ethyl acetate/hexane/dichloromethane = 1:12:4, R F = 1/2) to give the title compound in 88% yield as a white solid, m.p K. Single crystals suitable for X- ray diffraction analysis were obtained from slow evaporation of a solution in acetonitrile at 298 K. sup-1

4 S3. Refinement All H atoms were placed in geometrically idealized positions and refined using a riding model, with C H distances of Å, and with U iso (H) values of 1.5U eq (C) for methyl H atoms and 1.2U eq (C) for the other H atoms. In the title compound, one tert-butyl group (C1 C4) is rotational disordered over two sites; the site-occupancies were refined to (13):0.264 (13). The C C bond lengths involving the disordered atoms were restrained to be similar. The C67 C68 and C67 N6 bond lengths were restrained. As the quality of the crystal is poor the accuracy of the determination is low. Figure 1 The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. The minor disordered component and H atoms have been omitted for clarity. sup-2

5 5,11,17,23-Tetra-tert-butyl-25,27-bis[2-(4- nitrophenoxy)ethoxy]calix[4]arene-26,28-diol acetonitrile tetrasolvate Crystal data C 60 H 70 N 2 O 10 4C 2 H 3 N M r = Triclinic, P1 Hall symbol: -P 1 a = (3) Å b = (3) Å c = (5) Å α = (3) β = (3) γ = (3) V = (13) Å 3 Data collection Bruker SMART CCD area-detector diffractometer Radiation source: fine-focus sealed tube Graphite monochromator φ and ω scans measured reflections independent reflections Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 775 parameters 5 restraints Primary atom site location: structure-invariant direct methods Z = 2 F(000) = 1224 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 4717 reflections θ = µ = 0.08 mm 1 T = 173 K Block, colourless mm 7114 reflections with I > 2σ(I) R int = θ max = 25.0, θ min = 1.6 h = k = l = Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.1473P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.78 e Å 3 Δρ min = 0.64 e Å 3 Special details Experimental. 1 H NMR (300 MHz, CDCl 3 ): δ 8.19 (d, 4H, J = 9.20 Hz), 7.09 (s, 2H), 7.06 (s, 4H), 6.99 (d, 4H, J = 9.20 Hz), 6.82 (s, 4H), 4.35 (s, 8H), 4.33 (d, 4H, J = Hz), 3.31 (d, 4H, J = Hz), 1.29 (s, 18H), 0.98 (s, 18H). 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 Occ. (<1) C (7) (10) (5) (3) (13) sup-3

6 H1A * (13) H1B * (13) H1C * (13) C (11) (10) (6) (4) (13) H2A * (13) H2B * (13) H2C * (13) C (10) (7) (5) (4) (13) H3A * (13) H3B * (13) H3C * (13) C (5) (5) (3) (15) C (4) (4) (3) (13) C (4) (4) (3) (12) H * C (4) (4) (3) (11) C (4) (4) (2) (11) C (4) (4) (3) (11) C (4) (4) (3) (12) H * C (4) (4) (3) (11) H11A * H11B * C (3) (4) (3) (11) C (3) (4) (2) (10) C (3) (4) (3) (10) C (3) (4) (3) (11) H * C (4) (4) (3) (11) C (4) (4) (3) (11) H * C (4) (4) (3) (13) C (5) (6) (3) (18) H19A * H19B * H19C * C (5) (6) (3) (17) H20A * H20B * H20C * C (6) (5) (3) (2) H21A * H21B * H21C * C (4) (4) (3) (12) H22A * H22B * C (4) (4) (3) (11) sup-4

7 H23A * H23B * C (3) (4) (3) (11) C (5) (5) (3) (15) H * C (5) (5) (3) (16) H * C (4) (4) (3) (12) C (4) (4) (3) (12) H * C (4) (4) (3) (11) H * C (3) (4) (3) (10) H30A * H30B * C (3) (4) (2) (10) C (4) (4) (2) (10) C (4) (4) (2) (11) C (4) (4) (3) (12) H * C (4) (4) (3) (12) C (4) (4) (3) (11) H * C (5) (4) (3) (14) C (6) (5) (4) (19) H38A * H38B * H38C * C (6) (5) (3) (18) H39A * H39B * H39C * C (5) (6) (4) (2) H40A * H40B * H40C * C (4) (4) (3) (12) H41A * H41B * C (3) (4) (3) (11) C (4) (4) (3) (12) H * C (4) (4) (3) (12) C (4) (4) (3) (12) H * C (3) (4) (2) (11) C (3) (4) (2) (11) C (4) (5) (3) (15) sup-5

8 C (7) (6) (5) (3) H49A * H49B * H49C * C (5) (7) (4) (2) H50A * H50B * H50C * C (5) (6) (3) (2) H51A * H51B * H51C * C (4) (4) (3) (12) H52A * H52B * C (4) (5) (3) (13) H53A * H53B * C (4) (4) (3) (12) H54A * H54B * C (4) (4) (3) (11) C (4) (4) (3) (15) H * C (5) (5) (4) (19) H * C (4) (4) (3) (14) C (4) (4) (3) (13) H * C (4) (4) (3) (11) H * C (8) (8) (6) (3) H61A * H61B * H61C * C (6) (7) (6) (3) C (10) (8) (4) (4) H63A * H63B * H63C * C (6) (6) (4) (2) C (4) (5) (3) (15) H65A * H65B * H65C * C (5) (5) (4) (17) C (10) (11) (9) (8) C (8) (10) (6) (4) sup-6

9 H68A * H68B * H68C * C (2) (3) (12) (11) (13) H * (13) H * (13) H * (13) C (3) (16) (16) (14) (13) H * (13) H * (13) H * (13) C (18) (16) (13) (9) (13) H * (13) H * (13) H * (13) N (4) (4) (3) (16) N (4) (4) (3) (14) N (6) (7) (5) (3) N (6) (6) (5) (3) N (7) (6) (4) (2) N (18) (2) (2) 0.45 (3) O (2) (3) (18) (8) H * O (3) (3) (17) (9) H * O (2) (3) (16) (8) O (2) (2) (16) (7) O (3) (3) (17) (8) O (2) (3) (18) (8) O (6) (4) (3) (15) O (6) (4) (3) (15) O (4) (5) (4) (16) O (4) (5) (4) (16) Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 C (6) (9) (5) (6) (4) (5) C (10) (7) (6) (7) (6) (6) C (10) (6) (5) (5) (5) (4) C (4) (4) (3) (3) (2) (3) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (2) (2) (3) (19) (2) (2) C (3) (2) (2) (2) (2) (19) C (3) (2) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) sup-7

10 C (2) (2) (3) (19) (19) (2) C (2) (3) (2) (19) (18) (2) C (2) (2) (3) (18) (18) (2) C (2) (2) (3) (19) (2) (2) C (2) (3) (3) (2) (2) (2) C (2) (3) (3) (2) (19) (2) C (3) (3) (3) (2) (2) (2) C (4) (5) (3) (3) (3) (3) C (4) (5) (3) (3) (3) (3) C (6) (4) (3) (4) (3) (3) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (2) (3) (3) (2) (19) (2) C (4) (3) (3) (3) (3) (2) C (5) (4) (3) (3) (3) (3) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (2) (2) (3) (19) (19) (2) C (2) (2) (2) (19) (19) (2) C (2) (2) (2) (19) (19) (2) C (2) (3) (2) (2) (19) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (4) (3) (3) (2) (3) (2) C (5) (3) (4) (3) (4) (3) C (5) (4) (3) (3) (3) (3) C (4) (4) (5) (3) (4) (4) C (3) (3) (3) (2) (2) (2) C (2) (3) (3) (2) (19) (2) C (3) (3) (3) (2) (2) (2) C (2) (3) (3) (2) (19) (2) C (2) (3) (3) (2) (2) (2) C (2) (3) (2) (2) (19) (2) C (2) (3) (2) (2) (18) (2) C (3) (4) (3) (3) (2) (3) C (7) (6) (6) (5) (5) (5) C (3) (8) (4) (4) (3) (4) C (4) (6) (3) (4) (3) (3) C (2) (3) (3) (2) (19) (2) C (3) (4) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (2) (3) (3) (2) (19) (2) C (3) (3) (3) (2) (3) (3) C (4) (3) (4) (3) (3) (3) C (3) (3) (4) (2) (2) (3) C (3) (3) (3) (2) (2) (3) sup-8

11 C (3) (3) (3) (2) (2) (2) C (6) (7) (8) (5) (6) (6) C (4) (6) (8) (4) (5) (5) C (12) (7) (5) (7) (6) (5) C (5) (5) (5) (4) (4) (4) C (3) (4) (3) (3) (3) (3) C (3) (4) (4) (3) (3) (3) C (12) (11) 0.26 (2) (10) (13) (12) C (7) (11) (8) (7) (6) (8) C (3) 0.09 (3) (13) 0.01 (2) (15) (16) C (2) 0.12 (3) (18) 0.01 (2) (17) (18) C (17) 0.10 (2) (15) (15) (12) (15) N (3) (3) (4) (3) (3) (3) N (3) (3) (4) (2) (3) (3) N (5) (7) (7) (5) (5) (6) N (5) (5) (7) (4) (5) (5) N (7) (6) (5) (5) (4) (4) N (3) 0.28 (2) 0.72 (6) 0.06 (2) 0.35 (4) 0.03 (3) O (18) (19) (2) (14) (15) (16) O (19) (2) (18) (16) (14) (16) O (17) (2) (17) (15) (13) (15) O (16) (17) (17) (13) (13) (14) O (2) (19) (18) (16) (15) (15) O (17) (19) (19) (14) (14) (15) O (5) (2) (2) (2) (3) (19) O (5) (2) (2) (2) (3) (19) O (2) (3) (4) (2) (2) (3) O (2) (3) (4) (2) (2) (3) Geometric parameters (Å, º) C1 C (11) C38 H38B C1 H1A C38 H38C C1 H1B C39 H39A C1 H1C C39 H39B C2 C (12) C39 H39C C2 H2A C40 H40A C2 H2B C40 H40B C2 H2C C40 H40C C3 C (11) C41 C (7) C3 H3A C41 H41A C3 H3B C41 H41B C3 H3C C42 C (7) C4 C (7) C42 C (7) C4 C (11) C43 C (8) C4 C (11) C43 H C4 C (11) C44 C (8) C5 C (8) C44 C (7) sup-9

12 C5 C (8) C45 C (7) C6 C (7) C45 H C6 H C46 C (7) C7 C (7) C46 C (7) C7 C (7) C47 O (5) C8 O (5) C48 C (10) C8 C (7) C48 C (9) C9 C (7) C48 C (9) C9 C (7) C49 H49A C10 H C49 H49B C11 C (7) C49 H49C C11 H11A C50 H50A C11 H11B C50 H50B C12 C (7) C50 H50C C12 C (7) C51 H51A C13 O (5) C51 H51B C13 C (7) C51 H51C C14 C (7) C52 H52A C14 C (7) C52 H52B C15 C (7) C53 O (6) C15 H C53 C (7) C16 C (7) C53 H53A C16 C (7) C53 H53B C17 H C54 O (6) C18 C (9) C54 H54A C18 C (8) C54 H54B C18 C (9) C55 O (5) C19 H19A C55 C (7) C19 H19B C55 C (7) C19 H19C C56 C (8) C20 H20A C56 H C20 H20B C57 C (8) C20 H20C C57 H C21 H21A C58 C (8) C21 H21B C58 N (7) C21 H21C C59 C (7) C22 O (5) C59 H C22 C (7) C60 H C22 H22A C61 C (13) C22 H22B C61 H61A C23 O (6) C61 H61B C23 H23A C61 H61C C23 H23B C62 N (11) C24 O (6) C63 C (11) C24 C (7) C63 H63A C24 C (8) C63 H63B C25 C (8) C63 H63C C25 H C64 N (9) sup-10

13 C26 C (8) C65 C (9) C26 H C65 H65A C27 C (8) C65 H65B C27 N (7) C65 H65C C28 C (7) C66 N (9) C28 H C67 N (3) C29 H C67 C (18) C30 C (7) C68 H68A C30 H30A C68 H68B C30 H30B C68 H68C C31 C (7) C1 H C31 C (7) C1 H C32 O (5) C1 H C32 C (7) C2 H C33 C (7) C2 H C33 C (7) C2 H C34 C (8) C3 H C34 H C3 H C35 C (7) C3 H C35 C (7) N1 O (7) C36 H N1 O (7) C37 C (8) N2 O (7) C37 C (9) N2 O (7) C37 C (9) O1 H C38 H38A O2 H C4 C1 H1A H38A C38 H38C C4 C1 H1B H38B C38 H38C H1A C1 H1B C37 C39 H39A C4 C1 H1C C37 C39 H39B H1A C1 H1C H39A C39 H39B H1B C1 H1C C37 C39 H39C C4 C2 H2A H39A C39 H39C C4 C2 H2B H39B C39 H39C H2A C2 H2B C37 C40 H40A C4 C2 H2C C37 C40 H40B H2A C2 H2C H40A C40 H40B H2B C2 H2C C37 C40 H40C C4 C3 H3A H40A C40 H40C C4 C3 H3B H40B C40 H40C H3A C3 H3B C42 C41 C (4) C4 C3 H3C C42 C41 H41A H3A C3 H3C C33 C41 H41A H3B C3 H3C C42 C41 H41B C2 C4 C (6) C33 C41 H41B C2 C4 C (8) H41A C41 H41B C5 C4 C (5) C47 C42 C (5) C2 C4 C (19) C47 C42 C (4) sup-11

14 C2 C4 C (18) C43 C42 C (5) C1 C4 C3 99 (2) C42 C43 C (5) C2 C4 C (8) C42 C43 H C5 C4 C (5) C44 C43 H C3 C4 C (7) C45 C44 C (4) C6 C5 C (5) C45 C44 C (5) C6 C5 C (5) C43 C44 C (5) C10 C5 C (5) C44 C45 C (5) C5 C6 C (5) C44 C45 H C5 C6 H C46 C45 H C7 C6 H C45 C46 C (5) C6 C7 C (5) C45 C46 C (5) C6 C7 C (4) C47 C46 C (4) C8 C7 C (4) C42 C47 C (4) O2 C8 C (4) C42 C47 O (4) O2 C8 C (4) C46 C47 O (4) C9 C8 C (4) C49 C48 C (6) C10 C9 C (5) C49 C48 C (5) C10 C9 C (5) C51 C48 C (5) C8 C9 C (4) C49 C48 C (6) C9 C10 C (5) C51 C48 C (6) C9 C10 H C44 C48 C (5) C5 C10 H C48 C49 H49A C12 C11 C (4) C48 C49 H49B C12 C11 H11A H49A C49 H49B C9 C11 H11A C48 C49 H49C C12 C11 H11B H49A C49 H49C C9 C11 H11B H49B C49 H49C H11A C11 H11B C48 C50 H50A C17 C12 C (4) C48 C50 H50B C17 C12 C (5) H50A C50 H50B C13 C12 C (4) C48 C50 H50C O4 C13 C (4) H50A C50 H50C O4 C13 C (4) H50B C50 H50C C14 C13 C (4) C48 C51 H51A C15 C14 C (4) C48 C51 H51B C15 C14 C (4) H51A C51 H51B C13 C14 C (4) C48 C51 H51C C14 C15 C (5) H51A C51 H51C C14 C15 H H51B C51 H51C C16 C15 H C46 C52 C (4) C15 C16 C (4) C46 C52 H52A C15 C16 C (5) C7 C52 H52A C17 C16 C (5) C46 C52 H52B C12 C17 C (5) C7 C52 H52B C12 C17 H H52A C52 H52B C16 C17 H O3 C53 C (4) C21 C18 C (5) O3 C53 H53A sup-12

15 C21 C18 C (5) C54 C53 H53A C16 C18 C (4) O3 C53 H53B C21 C18 C (5) C54 C53 H53B C16 C18 C (4) H53A C53 H53B C19 C18 C (5) O6 C54 C (4) C18 C19 H19A O6 C54 H54A C18 C19 H19B C53 C54 H54A H19A C19 H19B O6 C54 H54B C18 C19 H19C C53 C54 H54B H19A C19 H19C H54A C54 H54B H19B C19 H19C O6 C55 C (4) C18 C20 H20A O6 C55 C (4) C18 C20 H20B C60 C55 C (4) H20A C20 H20B C55 C56 C (5) C18 C20 H20C C55 C56 H H20A C20 H20C C57 C56 H H20B C20 H20C C58 C57 C (5) C18 C21 H21A C58 C57 H C18 C21 H21B C56 C57 H H21A C21 H21B C57 C58 C (5) C18 C21 H21C C57 C58 N (5) H21A C21 H21C C59 C58 N (5) H21B C21 H21C C58 C59 C (5) O4 C22 C (4) C58 C59 H O4 C22 H22A C60 C59 H C23 C22 H22A C55 C60 C (5) O4 C22 H22B C55 C60 H C23 C22 H22B C59 C60 H H22A C22 H22B C62 C61 H61A O5 C23 C (4) C62 C61 H61B O5 C23 H23A H61A C61 H61B C22 C23 H23A C62 C61 H61C O5 C23 H23B H61A C61 H61C C22 C23 H23B H61B C61 H61C H23A C23 H23B N3 C62 C (13) O5 C24 C (5) C64 C63 H63A O5 C24 C (4) C64 C63 H63B C29 C24 C (5) H63A C63 H63B C26 C25 C (5) C64 C63 H63C C26 C25 H H63A C63 H63C C24 C25 H H63B C63 H63C C25 C26 C (6) N5 C64 C (9) C25 C26 H C66 C65 H65A C27 C26 H C66 C65 H65B C28 C27 C (5) H65A C65 H65B C28 C27 N (5) C66 C65 H65C C26 C27 N (5) H65A C65 H65C C29 C28 C (5) H65B C65 H65C sup-13

16 C29 C28 H N4 C66 C (8) C27 C28 H N6 C67 C (3) C28 C29 C (5) C67 C68 H68A C28 C29 H C67 C68 H68B C24 C29 H H68A C68 H68B C14 C30 C (4) C67 C68 H68C C14 C30 H30A H68A C68 H68C C31 C30 H30A H68B C68 H68C C14 C30 H30B C4 C1 H C31 C30 H30B C4 C1 H H30A C30 H30B H1 1 C1 H C36 C31 C (4) C4 C1 H C36 C31 C (4) H1 1 C1 H C32 C31 C (4) H1 2 C1 H O1 C32 C (4) C4 C2 H O1 C32 C (4) C4 C2 H C33 C32 C (4) H2 1 C2 H C34 C33 C (5) C4 C2 H C34 C33 C (4) H2 1 C2 H C32 C33 C (4) H2 2 C2 H C35 C34 C (5) C4 C3 H C35 C34 H C4 C3 H C33 C34 H H3 1 C3 H C34 C35 C (5) C4 C3 H C34 C35 C (5) H3 1 C3 H C36 C35 C (5) H3 2 C3 H C31 C36 C (5) O9 N1 O (5) C31 C36 H O9 N1 C (5) C35 C36 H O10 N1 C (5) C35 C37 C (4) O7 N2 O (6) C35 C37 C (5) O7 N2 C (5) C38 C37 C (5) O8 N2 C (5) C35 C37 C (5) C32 O1 H C38 C37 C (5) C8 O2 H C39 C37 C (5) C47 O3 C (4) C37 C38 H38A C13 O4 C (3) C37 C38 H38B C24 O5 C (4) H38A C38 H38B C55 O6 C (4) C37 C38 H38C C2 C4 C5 C (9) C31 C32 C33 C (4) C3 C4 C5 C (7) C32 C33 C34 C (7) C2 C4 C5 C (16) C41 C33 C34 C (5) C1 C4 C5 C (18) C33 C34 C35 C (7) C3 C4 C5 C (14) C33 C34 C35 C (5) C1 C4 C5 C6 2.8 (8) C32 C31 C36 C (7) C2 C4 C5 C (9) C30 C31 C36 C (4) C3 C4 C5 C (8) C34 C35 C36 C (7) sup-14

17 C2 C4 C5 C (15) C37 C35 C36 C (4) C1 C4 C5 C (19) C34 C35 C37 C (6) C3 C4 C5 C (13) C36 C35 C37 C (7) C1 C4 C5 C (6) C34 C35 C37 C (6) C10 C5 C6 C7 0.8 (8) C36 C35 C37 C (7) C4 C5 C6 C (5) C34 C35 C37 C (8) C5 C6 C7 C8 0.7 (7) C36 C35 C37 C (5) C5 C6 C7 C (5) C34 C33 C41 C (5) C6 C7 C8 O (4) C32 C33 C41 C (5) C52 C7 C8 O2 8.0 (7) C33 C41 C42 C (5) C6 C7 C8 C9 0.0 (7) C33 C41 C42 C (5) C52 C7 C8 C (4) C47 C42 C43 C (7) O2 C8 C9 C (4) C41 C42 C43 C (4) C7 C8 C9 C (7) C42 C43 C44 C (7) O2 C8 C9 C (7) C42 C43 C44 C (5) C7 C8 C9 C (4) C43 C44 C45 C (8) C8 C9 C10 C5 0.3 (7) C48 C44 C45 C (5) C11 C9 C10 C (4) C44 C45 C46 C (7) C6 C5 C10 C9 0.3 (7) C44 C45 C46 C (4) C4 C5 C10 C (5) C43 C42 C47 C (7) C10 C9 C11 C (5) C41 C42 C47 C (4) C8 C9 C11 C (5) C43 C42 C47 O (4) C9 C11 C12 C (5) C41 C42 C47 O3 5.1 (7) C9 C11 C12 C (5) C45 C46 C47 C (7) C17 C12 C13 O (4) C52 C46 C47 C (4) C11 C12 C13 O4 5.7 (6) C45 C46 C47 O (4) C17 C12 C13 C (7) C52 C46 C47 O3 6.3 (7) C11 C12 C13 C (4) C45 C44 C48 C (6) O4 C13 C14 C (4) C43 C44 C48 C (8) C12 C13 C14 C (6) C45 C44 C48 C (7) O4 C13 C14 C (7) C43 C44 C48 C (6) C12 C13 C14 C (4) C45 C44 C48 C (7) C13 C14 C15 C (7) C43 C44 C48 C (6) C30 C14 C15 C (4) C45 C46 C52 C (5) C14 C15 C16 C (7) C47 C46 C52 C (5) C14 C15 C16 C (4) C6 C7 C52 C (5) C13 C12 C17 C (7) C8 C7 C52 C (5) C11 C12 C17 C (4) O3 C53 C54 O (6) C15 C16 C17 C (7) O6 C55 C56 C (6) C18 C16 C17 C (4) C60 C55 C56 C (9) C15 C16 C18 C (8) C55 C56 C57 C (10) C17 C16 C18 C (5) C56 C57 C58 C (11) C15 C16 C18 C (6) C56 C57 C58 N (6) C17 C16 C18 C (7) C57 C58 C59 C (9) C15 C16 C18 C (5) N1 C58 C59 C (6) C17 C16 C18 C (6) O6 C55 C60 C (5) O4 C22 C23 O (5) C56 C55 C60 C (8) O5 C24 C25 C (5) C58 C59 C60 C (8) sup-15

18 C29 C24 C25 C (9) C57 C58 N1 O (7) C24 C25 C26 C (10) C59 C58 N1 O9 4.3 (10) C25 C26 C27 C (9) C57 C58 N1 O (10) C25 C26 C27 N (6) C59 C58 N1 O (7) C26 C27 C28 C (8) C28 C27 N2 O7 9.7 (9) N2 C27 C28 C (5) C26 C27 N2 O (7) C27 C28 C29 C (7) C28 C27 N2 O (6) O5 C24 C29 C (5) C26 C27 N2 O8 7.6 (9) C25 C24 C29 C (7) C42 C47 O3 C (5) C15 C14 C30 C (5) C46 C47 O3 C (5) C13 C14 C30 C (5) C54 C53 O3 C (4) C14 C30 C31 C (5) C14 C13 O4 C (6) C14 C30 C31 C (5) C12 C13 O4 C (4) C36 C31 C32 O (4) C23 C22 O4 C (4) C30 C31 C32 O1 5.5 (6) C29 C24 O5 C (7) C36 C31 C32 C (7) C25 C24 O5 C (5) C30 C31 C32 C (4) C22 C23 O5 C (4) O1 C32 C33 C (4) C60 C55 O6 C (4) C31 C32 C33 C (7) C56 C55 O6 C (7) O1 C32 C33 C (7) C53 C54 O6 C (4) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A O1 H1 O (6) 171 O2 H2 O (4) 176 C50 H50C O7 i (10) 156 C68 H68B O (13) 148 C65 H65A Cg (6) 163 Symmetry code: (i) x+1, y+1, z+1. sup-16