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1 metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN {2,2 0 -[(2,2-Dimethylpropane-1,3-diyl)- bis(nitrilomethylidyne)]diphenolato}- palladium(ii) ethanol hemisolvate Wan Nazihah Wan Ibrahim, a Mustaffa Shamsuddin, a Suchada Chantrapromma b and Hoong-Kun Fun c * a Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, UTM Skudai, Johor, Malaysia, b Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, and c X-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, USM, Penang, Malaysia Correspondence hkfun@usm.my Received 11 April 2008; accepted 6 June 2008 Key indicators: single-crystal X-ray study; T = 296 K; mean (C C) = Å; disorder in solvent or counterion; R factor = 0.043; wr factor = 0.130; data-toparameter ratio = The asymmetric unit of the title complex, [Pd(C 19 H 20 N 2 O 2 )]- 0.5C 2 H 5 OH, contains two molecules of a Pd II complex of a Schiff base ligand with an N 2 O 2 donor set and one ethanol molecule. The Pd II centers are in distorted square-planar geometries with the N 2 O 2 donor atoms of the tetradentate Schiff base dianions. The ethanol molecule takes part in an O HO hydrogen bond. In the crystal structure, molecules are stacked approximately along the b-axis direction. The O atom and three H atoms of the solvent molecule are disordered over two positions; the site occupancy factors are ca 0.8 and 0.2. Related literature For related structures, see, for example: Adrian et al. (2008). For background to applications of palladium(ii) complexes, see, for example: Abu-Surrah et al. (1999); Adrian et al. (2008); Ayala et al. (2004); Caselli et al. (2005); Lai et al. (2005); Pou et al. (2007); Ramírez et al. (2008); Roy et al. (2008). For bondlength data, see: Allen et al. (1987). For ring puckering parameters, see: Cremer & Pople (1975). Experimental Crystal data [Pd(C 19 H 20 N 2 O 2 )]0.5C 2 H 6 O M r = Monoclinic, P2 1 =c a = (3) Å b = (3) Å c = (5) Å = (1) Data collection Bruker SMART APEXII CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2005) T min = 0.690, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections Table 1 Hydrogen-bond geometry (Å, ). V = (15) Å 3 Z =8 Mo K radiation = 1.00 mm 1 T = 296 (2) K mm measured reflections independent reflections 8985 reflections with I > 2(I) R int = parameters H-atom parameters constrained max = 0.81 e Å 3 min = 0.66 e Å 3 D HA D H HA DA D HA O5A H5ABO1A i (13) 142 Symmetry code: (i) x; y 1 2 ; z þ 1 2. Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); 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 and PLATON (Spek, 2003). The authors acknowledge financial support from the Ministry of Science Technology and Innovation (MOSTI) for the Science Fund grant No SF0273 (Vot: 79121), the National Science Fellowship (NSF), and the Faculty of Science, UTM Skudai for the research facilities. The authors also thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/ Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: EZ2126). doi: /s Ibrahim et al. m909

2 metal-organic compounds References Abu-Surrah, A. S., Thewalt, U. & Rieger, B. (1999). J. Organomet. Chem. 587, Adrian, R. A., Broker, G. A., Tiekink, E. R. T. & Walmsley, J. A. (2008). Inorg. Chim. Acta, 361, Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1 S19. Ayala, V., Corma, A., Iglesias, M., Rincon, J. A. & Sanchez, F. (2004). J. Catal.. 224, Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Caselli, A., Gallo, E., Ragaini, F., Oppezzo, A. & Cenini, S. (2005). J. Organomet. Chem. 690, Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, Lai, Y. C., Chen, H. Y., Hung, W. C., Lin, C. C. & Hong, F. E. (2005). Tetrahedron. 61, Pou, D., Platero-Prats, A. E., Peŕez, S., López, C., Solans, X., Font-Bardía, M., van Leeuwen, P. W. N. M., van Strijdonck, G. P. F. & Freixa, Z. (2007). J. Organomet. Chem. 692, Ramírez, P., Contreras, R., Valderrama, M., Carmona, D., Lahoz, F. J. & Balana, A. I. (2008). J. Organomet. Chem. 693, Roy, S., Mandal, T. N., Barik, A. K., Gupta, S., Butcher, R. J., Nethaji, M. & Kar, S. K. (2008). Polyhedron. 27, Sheldrick, G. M. (2008). Acta Cryst. A64, Spek, A. L. (2003). J. Appl. Cryst. 36, m910 Ibrahim et al. [Pd(C 19 H 20 N 2 O 2 )]0.5C 2 H 6 O

3 [doi: /s ] {2,2 -[(2,2-Dimethylpropane-1,3-diyl)bis(nitrilomethylidyne)]diphenolato}palladium(II) ethanol hemisolvate Wan Nazihah Wan Ibrahim, Mustaffa Shamsuddin, Suchada Chantrapromma and Hoong-Kun Fun S1. Comment In the field of coordination chemistry, the unique properties of Schiff bases as chelating ligands have attracted significant attention (Caselli et al., 2005; Pou et al., 2007; Ramírez et al., 2008; Roy et al., 2008). Their complexes with palladium(ii) ions are found to be efficient catalysts in organic synthesis, especially in C C bond formation (Abu-Surrah et al., 1999; Ayala et al., 2004; Lai et al., 2005). In the present paper, the preparation and crystal structure of the complex N,N -bis-salicylidene-2,2-dimethylpropane-1,3-diamine palladium(ii) is described. The asymmetric unit of the title complex (Fig. 1) contains two molecules of the Pd II complex (A and B) of the Schiff base ligand and one solvated ethanol molecule. The ethanol molecule shows disorder. The Pd II ion in both A and B has a distorted square-planar environment in which the ligand is coordinated to the Pd II ion as a tetradentate chelating ligand via the two phenolic oxygen atoms and two imine nitrogen atoms, yielding three six-membered rings. In A, two rings are essentially planar (Pd1A/N1A/C2A/C3A/C8A/O1A and Pd1A/N2A/C9A/C14A/C15A/O2A) and one adopts a half-chair conformation; Pd1A/N1A/C1A/C17A/C16A/N2A with atom C17A displaced from the Pd1A/N1A/C1A/C16A/N2A plane by (4) Å and with Cremer & Pople (1975) puckering parameters: Q = (4) Å, θ = (3) and φ = 11.1 (5). In B, one ring is essentially planar (Pd1B/N1B/C2B/C3B/C8B/O1B) and two rings have half-chair conformations; Pd1B/N1B/C1B/C17B/C16B/N2B with atom C17B displaced from the Pd1B/N1B/C1B/C16B/N2B plane by (4) Å and with Cremer & Pople (1975) puckering parameters: Q = (5) Å, θ = (4) and φ = (5) ; Pd1B/N2B/C9B/C14B/C15B/O2B with atom O2B deviated from the Pd1B/N2B/C9B/C14B/C15B plane by (4) Å and with Cremer & Pople (1975) puckering parameters: Q = (5) Å, θ = 62.9 (14) and φ = 24.4 (17). The Pd II ions are coordinated in a cis-planar fashion by the two phenolic oxygen atoms and two imine nitrogen atoms. The Pd O distances are in the range (3) (4) Å with Pd N distances (3) (3) Å, which are typical of the square-planar Pd II complexes of Schiff base ligands (Adrian et al., 2008). The bond angles around Pd II ions indicate that the complex has a distorted square-planar geometry as indicated by the angles O Pd O in the range (11) (16), O Pd N in the range (13) (11) and N Pd N in the range (12) (15), deviating substantially from that expected for a regular square-planar geometry. The distortion can be attributed to the restricted bite angle of the Schiff base ligand. Other bond lengths and angles observed in the structure are normal (Allen et al., 1987). The dihedral angles between the two phenolate rings [(C3 C8) and (C9 C14)] of the tetradentate Schiff base ligand are 8.3 (2) in A and 18.5 (3) in B. In the crystal packing (Fig. 2), the neighbouring complex molecules are stacked approximately along the b direction by π π interactions between the Pd1A/N1A/C2A/C3A/C8A/O1A and Pd1B/N1B/C2B/C3B/C8B/O1B rings with the Cg Cg distance of (19) Å. The crystal is stabilized by O H O hydrogen bonds involving the solvated ethanol sup-1

4 molecule (Table 1). S2. Experimental The title complex was synthesized by dissolving the N,N -bis-salicylidene-2,2-dimethylpropane-1,3-diamine ligand ( g, 3 mmol) in dry ethanol (10 ml). Palladium(II) acetate ( g, 3 mmol) was then added to the resulting solution and refluxed under nitrogen atmosphere for 5 hr. An orange solid was obtained and washed with cold acetonitrile. Yellow single crystals suitable for X-ray structure determination were obtained by recrystallization from a mixture of chloroform/hexane (1:1 v/v) by slow evaporation of the solvent at room temperature over several weeks. Yield: 80%, M.p K. S3. Refinement All H atoms were placed in calculated positions with d(o H) = 0.82 Å, U iso =1.2U eq, d(c H) = 0.93 Å, U iso =1.2U eq (C) for CH and aromatic, 0.96 Å, U iso = 1.5U eq (C) for CH 3 atoms. A rotating group model was used for the methyl groups. A large peak on the difference electron density map indicated that the oxygen atom (O5) in the ethanol molecule was disordered. The occupancies of the two disorder components were refined to full convergence yielding a ratio of the major-to-minor components of 0.77 (2):0.23 (2).The highest residual electron density peak is located at 1.17 Å from H19D and the deepest hole is located at 0.76 Å from Pd1A. Figure 1 The asymmetric unit of (I), showing 50% probability displacement ellipsoids and the atomic numbering. Disorder of the ethanol molecule is shown. sup-2

5 Figure 2 Crystal packing of (I), viewed along the a axis showing the stacking of the molecules along the b direction. The disordered ethanol molecule is omitted for clarity. {2,2 -[(2,2-Dimethylpropane-1,3- diyl)bis(nitrilomethylidyne)]diphenolato}palladium(ii) ethanol hemisolvate Crystal data [Pd(C 19 H 20 N 2 O 2 )] 0.5C 2 H 6 O M r = Monoclinic, P2 1 /c Hall symbol: -P 2ybc a = (3) Å b = (3) Å c = (5) Å β = (1) V = (15) Å 3 Z = 8 Data collection Bruker SMART APEXII CCD area-detector diffractometer Radiation source: fine-focus sealed tube Graphite monochromator Detector resolution: 8.33 pixels mm -1 ω scans F(000) = 1784 D x = Mg m 3 Melting point = K Mo Kα radiation, λ = Å Cell parameters from reflections θ = µ = 1.00 mm 1 T = 296 K Block, yellow mm Absorption correction: multi-scan (SADABS; Bruker, 2005) T min = 0.690, T max = measured reflections independent reflections 8985 reflections with I > 2σ(I) R int = sup-3

6 θ max = 30.0, θ min = 1.7 h = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 474 parameters 0 restraints Primary atom site location: structure-invariant direct methods 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 ) + (0.0432P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.81 e Å 3 Δρ min = 0.66 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 Occ. (<1) Pd1A (2) (2) (11) (8) O1A (2) (2) (12) (7) O2A (2) (2) (12) (7) N1A (2) (2) (13) (6) N2A (3) (2) (13) (6) C1A (3) (3) (17) (9) H1A * H1B * C2A (3) (3) (16) (7) H2A * C3A (3) (3) (16) (8) C4A (4) (4) (19) (11) H4A * C5A (5) (4) (2) (16) H5A * C6A (5) (4) (2) (16) H6A * C7A (4) (4) (18) (11) H7A * C8A (3) (3) (16) (8) C9A (3) (3) (18) (8) C10A (4) (3) (2) (10) H10A * sup-4

7 C11A (4) (3) (2) (12) H11A * C12A (4) (4) (2) (12) H12A * C13A (4) (3) (2) (10) H13A * C14A (3) (3) (17) (8) C15A (3) (3) (16) (8) H15A * C16A (3) (3) (17) (9) H16A * H16B * C17A (3) (3) (16) (8) C18A (4) (4) (2) (12) H18A * H18B * H18C * C19A (4) (3) (2) (12) H19A * H19B * H19C * C20A (9) (7) (5) (3) H20A * 0.77 (2) H20B * 0.77 (2) H20C * 0.23 (2) H20D * 0.23 (2) C21A (10) (9) (4) (5) H21A * H21B * H21C * O5A (10) (10) (6) (6) 0.77 (2) H5AB * 0.77 (2) O5B (19) (2) (14) (11) 0.23 (2) H5BA * 0.23 (2) Pd1B (3) (2) (14) (9) O1B (2) (2) (15) (8) O2B (3) (3) (15) (10) N1B (3) (2) (15) (7) N2B (3) (3) (18) (9) C1B (4) (3) (2) (12) H1C * H1D * C2B (3) (3) (2) (9) H2B * C3B (3) (3) (2) (10) C4B (5) (4) (3) (14) H4B * C5B (6) (4) (4) (2) sup-5

8 H5B * C6B (5) (4) (4) (2) H6B * C7B (4) (4) (3) (16) H7B * C8B (3) (3) (2) (11) C9B (6) (4) (2) (17) C10B (7) (5) (3) (2) H10B * C11B (11) (7) (4) (5) H11B * C12B (11) (8) (5) (5) H12B * C13B (8) (5) (3) (3) H13B * C14B (6) (4) (3) (18) C15B (5) (3) (3) (15) H15B * C16B (4) (4) (3) (15) H16C * H16D * C17B (4) (3) (2) (10) C18B (4) (4) (3) (17) H18D * H18E * H18F * C19B (4) (3) (2) (13) H19D * H19E * H19F * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Pd1A (14) (14) (13) (10) (10) (10) O1A (16) (18) (13) (14) (12) (12) O2A (15) (18) (14) (13) (11) (12) N1A (14) (15) (14) (12) (11) (12) N2A (16) (14) (14) (12) (12) (11) C1A (19) (2) (2) (17) (15) (18) C2A (18) (19) (17) (15) (14) (15) C3A (2) (19) (17) (16) (15) (14) C4A (3) (3) (2) (2) (19) (19) C5A (4) (4) (2) (3) (2) (2) C6A (4) (4) (2) (3) (2) (2) C7A (3) (3) (2) (2) (19) (19) C8A (2) (2) (17) (16) (15) (15) C9A (2) (17) (2) (15) (16) (15) sup-6

9 C10A (2) (2) (3) (18) (2) (2) C11A (2) (3) (3) (2) (2) (2) C12A (3) (3) (3) (2) (3) (2) C13A (3) (2) (2) (2) (2) (18) C14A (2) (17) (2) (15) (16) (15) C15A (2) (17) (17) (15) (16) (13) C16A (2) (2) (18) (17) (15) (16) C17A (19) (19) (17) (15) (14) (14) C18A (3) (3) (2) (2) (19) (2) C19A (3) (2) (3) (2) (2) (2) C20A (9) (6) (9) (6) (7) (6) C21A (12) (12) (6) (10) (7) (6) O5A (8) (10) (12) (7) (8) (9) O5B (13) 0.12 (2) (19) (12) (11) (14) Pd1B (17) (15) (17) (12) (12) (12) O1B (16) (19) (2) (14) (14) (16) O2B (2) (2) (18) (19) (17) (16) N1B (17) (15) (19) (13) (14) (14) N2B (2) (18) (2) (16) (19) (17) C1B (2) (2) (3) (19) (2) (2) C2B (2) (19) (2) (16) (18) (17) C3B (2) (18) (3) (16) (2) (19) C4B (3) (3) (4) (2) (3) (3) C5B (4) (3) (7) (3) (5) (4) C6B (3) (3) (7) (3) (4) (4) C7B (2) (3) (5) (2) (3) (3) C8B (2) (2) (3) (16) (2) (2) C9B (5) (3) (3) (3) (3) (2) C10B (7) (4) (3) (4) (4) (3) C11B (13) (7) (4) (9) (7) (4) C12B (13) (8) (7) (9) (9) (6) C13B (8) (5) (5) (5) (5) (4) C14B (5) (3) (4) (3) (4) (3) C15B (4) (2) (4) (2) (3) (2) C16B (3) (3) (4) (3) (3) (3) C17B (2) (2) (3) (17) (19) (19) C18B (3) (3) (5) (2) (3) (3) C19B (3) (2) (3) (2) (3) (2) Geometric parameters (Å, º) Pd1A O1A (3) C21A H21A Pd1A O2A (3) C21A H21B Pd1A N2A (3) C21A H21C Pd1A N1A (3) O5A H20C O1A C8A (4) O5A H5AB O2A C9A (4) O5B H5BA N1A C2A (4) Pd1B O2B (3) sup-7

10 N1A C1A (5) Pd1B N1B (3) N2A C15A (5) Pd1B O1B (3) N2A C16A (5) Pd1B N2B (4) C1A C17A (5) O1B C8B (6) C1A H1A O2B C9B (7) C1A H1B N1B C2B (5) C2A C3A (5) N1B C1B (5) C2A H2A N2B C15B (6) C3A C8A (5) N2B C16B (7) C3A C4A (5) C1B C17B (6) C4A C5A (6) C1B H1C C4A H4A C1B H1D C5A C6A (7) C2B C3B (6) C5A H5A C2B H2B C6A C7A (6) C3B C8B (7) C6A H6A C3B C4B (7) C7A C8A (5) C4B C5B (8) C7A H7A C4B H4B C9A C14A (6) C5B C6B (10) C9A C10A (6) C5B H5B C10A C11A (6) C6B C7B (9) C10A H10A C6B H6B C11A C12A (7) C7B C8B (6) C11A H11A C7B H7B C12A C13A (7) C9B C14B (9) C12A H12A C9B C10B (8) C13A C14A (5) C10B C11B (12) C13A H13A C10B H10B C14A C15A (5) C11B C12B (15) C15A H15A C11B H11B C16A C17A (5) C12B C13B (13) C16A H16A C12B H12B C16A H16B C13B C14B (8) C17A C18A (5) C13B H13B C17A C19A (6) C14B C15B (9) C18A H18A C15B H15B C18A H18B C16B C17B (7) C18A H18C C16B H16C C19A H19A C16B H16D C19A H19B C17B C19B (6) C19A H19C C17B C18B (6) C20A O5A (13) C18B H18D C20A O5B 1.27 (3) C18B H18E C20A C21A (13) C18B H18F C20A H20A C19B H19D C20A H20B C19B H19E C20A H20C C19B H19F C20A H20D sup-8

11 O1A Pd1A O2A (11) O5B C20A H20D 99.0 O1A Pd1A N2A (12) C21A C20A H20D O2A Pd1A N2A (12) H20A C20A H20D 58.9 O1A Pd1A N1A (11) H20B C20A H20D 56.5 O2A Pd1A N1A (11) H20C C20A H20D N2A Pd1A N1A (12) C20A C21A H21A C8A O1A Pd1A (2) C20A C21A H21B C9A O2A Pd1A (2) H21A C21A H21B C2A N1A C1A (3) C20A C21A H21C C2A N1A Pd1A (3) H21A C21A H21C C1A N1A Pd1A (2) H21B C21A H21C C15A N2A C16A (3) C20A O5A H20C 45.2 C15A N2A Pd1A (3) C20A O5A H5AB C16A N2A Pd1A (2) H20C O5A H5AB 99.3 N1A C1A C17A (3) C20A O5B H5BA N1A C1A H1A O2B Pd1B N1B (15) C17A C1A H1A O2B Pd1B O1B (16) N1A C1A H1B N1B Pd1B O1B (13) C17A C1A H1B O2B Pd1B N2B (17) H1A C1A H1B N1B Pd1B N2B (15) N1A C2A C3A (4) O1B Pd1B N2B (15) N1A C2A H2A C8B O1B Pd1B (3) C3A C2A H2A C9B O2B Pd1B (4) C8A C3A C4A (4) C2B N1B C1B (4) C8A C3A C2A (3) C2B N1B Pd1B (3) C4A C3A C2A (4) C1B N1B Pd1B (3) C5A C4A C3A (4) C15B N2B C16B (5) C5A C4A H4A C15B N2B Pd1B (4) C3A C4A H4A C16B N2B Pd1B (3) C4A C5A C6A (4) N1B C1B C17B (4) C4A C5A H5A N1B C1B H1C C6A C5A H5A C17B C1B H1C C7A C6A C5A (4) N1B C1B H1D C7A C6A H6A C17B C1B H1D C5A C6A H6A H1C C1B H1D C6A C7A C8A (4) N1B C2B C3B (4) C6A C7A H7A N1B C2B H2B C8A C7A H7A C3B C2B H2B O1A C8A C3A (3) C8B C3B C4B (4) O1A C8A C7A (4) C8B C3B C2B (4) C3A C8A C7A (3) C4B C3B C2B (5) O2A C9A C14A (3) C5B C4B C3B (6) O2A C9A C10A (4) C5B C4B H4B C14A C9A C10A (4) C3B C4B H4B C11A C10A C9A (4) C4B C5B C6B (6) C11A C10A H10A C4B C5B H5B C9A C10A H10A C6B C5B H5B sup-9

12 C10A C11A C12A (4) C7B C6B C5B (5) C10A C11A H11A C7B C6B H6B C12A C11A H11A C5B C6B H6B C13A C12A C11A (4) C6B C7B C8B (6) C13A C12A H12A C6B C7B H7B C11A C12A H12A C8B C7B H7B C12A C13A C14A (4) O1B C8B C3B (4) C12A C13A H13A O1B C8B C7B (5) C14A C13A H13A C3B C8B C7B (5) C9A C14A C13A (4) O2B C9B C14B (5) C9A C14A C15A (3) O2B C9B C10B (7) C13A C14A C15A (4) C14B C9B C10B (6) N2A C15A C14A (3) C11B C10B C9B (9) N2A C15A H15A C11B C10B H10B C14A C15A H15A C9B C10B H10B N2A C16A C17A (3) C12B C11B C10B (10) N2A C16A H16A C12B C11B H11B C17A C16A H16A C10B C11B H11B N2A C16A H16B C11B C12B C13B (9) C17A C16A H16B C11B C12B H12B H16A C16A H16B C13B C12B H12B C16A C17A C1A (3) C12B C13B C14B (10) C16A C17A C18A (3) C12B C13B H13B C1A C17A C18A (3) C14B C13B H13B C16A C17A C19A (4) C9B C14B C13B (7) C1A C17A C19A (4) C9B C14B C15B (5) C18A C17A C19A (4) C13B C14B C15B (7) C17A C18A H18A N2B C15B C14B (6) C17A C18A H18B N2B C15B H15B H18A C18A H18B C14B C15B H15B C17A C18A H18C N2B C16B C17B (4) H18A C18A H18C N2B C16B H16C H18B C18A H18C C17B C16B H16C C17A C19A H19A N2B C16B H16D C17A C19A H19B C17B C16B H16D H19A C19A H19B H16C C16B H16D C17A C19A H19C C19B C17B C16B (4) H19A C19A H19C C19B C17B C1B (4) H19B C19A H19C C16B C17B C1B (4) O5A C20A O5B 57.8 (12) C19B C17B C18B (4) O5A C20A C21A (11) C16B C17B C18B (4) O5B C20A C21A (15) C1B C17B C18B (4) O5A C20A H20A C17B C18B H18D O5B C20A H20A 56.1 C17B C18B H18E C21A C20A H20A H18D C18B H18E O5A C20A H20B C17B C18B H18F O5B C20A H20B H18D C18B H18F C21A C20A H20B H18E C18B H18F sup-10

13 H20A C20A H20B C17B C19B H19D O5A C20A H20C 67.7 C17B C19B H19E O5B C20A H20C H19D C19B H19E C21A C20A H20C C17B C19B H19F H20A C20A H20C H19D C19B H19F H20B C20A H20C 48.5 H19E C19B H19F O5A C20A H20D O2A Pd1A O1A C8A (4) O2B Pd1B O1B C8B (4) N1A Pd1A O1A C8A 1.0 (3) N1B Pd1B O1B C8B 2.3 (3) N2A Pd1A O2A C9A 5.3 (3) O1B Pd1B O2B C9B (4) O1A Pd1A O2A C9A (3) N2B Pd1B O2B C9B 18.7 (4) O1A Pd1A N1A C2A 2.5 (3) O1B Pd1B N1B C2B 0.9 (3) N2A Pd1A N1A C2A (3) N2B Pd1B N1B C2B (3) O1A Pd1A N1A C1A (3) O1B Pd1B N1B C1B (3) N2A Pd1A N1A C1A 3.1 (3) N2B Pd1B N1B C1B 6.5 (3) O2A Pd1A N2A C15A 4.4 (3) O2B Pd1B N2B C15B 10.8 (4) N1A Pd1A N2A C15A (3) N1B Pd1B N2B C15B (4) O2A Pd1A N2A C16A (3) O2B Pd1B N2B C16B (4) N1A Pd1A N2A C16A 10.7 (3) N1B Pd1B N2B C16B 10.1 (4) C2A N1A C1A C17A (4) C2B N1B C1B C17B (4) Pd1A N1A C1A C17A 30.7 (5) Pd1B N1B C1B C17B 48.2 (5) C1A N1A C2A C3A (4) C1B N1B C2B C3B (4) Pd1A N1A C2A C3A 3.2 (6) Pd1B N1B C2B C3B 0.3 (6) N1A C2A C3A C8A 0.3 (7) N1B C2B C3B C8B 0.4 (7) N1A C2A C3A C4A (4) N1B C2B C3B C4B (4) C8A C3A C4A C5A 0.5 (7) C8B C3B C4B C5B 0.1 (7) C2A C3A C4A C5A (5) C2B C3B C4B C5B (5) C3A C4A C5A C6A 1.7 (9) C3B C4B C5B C6B 1.0 (9) C4A C5A C6A C7A 2.1 (10) C4B C5B C6B C7B 1.5 (10) C5A C6A C7A C8A 0.1 (9) C5B C6B C7B C8B 0.9 (9) Pd1A O1A C8A C3A 4.3 (6) Pd1B O1B C8B C3B 3.0 (6) Pd1A O1A C8A C7A (3) Pd1B O1B C8B C7B (3) C4A C3A C8A O1A (4) C4B C3B C8B O1B (4) C2A C3A C8A O1A 4.4 (6) C2B C3B C8B O1B 1.8 (7) C4A C3A C8A C7A 2.5 (6) C4B C3B C8B C7B 0.6 (6) C2A C3A C8A C7A (4) C2B C3B C8B C7B (4) C6A C7A C8A O1A (5) C6B C7B C8B O1B (5) C6A C7A C8A C3A 2.2 (7) C6B C7B C8B C3B 0.2 (7) Pd1A O2A C9A C14A 1.8 (6) Pd1B O2B C9B C14B 16.8 (7) Pd1A O2A C9A C10A (3) Pd1B O2B C9B C10B (4) O2A C9A C10A C11A (4) O2B C9B C10B C11B (6) C14A C9A C10A C11A 0.6 (6) C14B C9B C10B C11B 1.5 (8) C9A C10A C11A C12A 0.6 (7) C9B C10B C11B C12B 0.3 (13) C10A C11A C12A C13A 0.5 (8) C10B C11B C12B C13B 1.5 (16) C11A C12A C13A C14A 0.9 (7) C11B C12B C13B C14B 2.1 (14) O2A C9A C14A C13A (4) O2B C9B C14B C13B (5) C10A C9A C14A C13A 1.9 (6) C10B C9B C14B C13B 0.9 (7) sup-11

14 O2A C9A C14A C15A 4.6 (6) O2B C9B C14B C15B 1.4 (8) C10A C9A C14A C15A (4) C10B C9B C14B C15B (5) C12A C13A C14A C9A 2.1 (6) C12B C13B C14B C9B 0.8 (10) C12A C13A C14A C15A (4) C12B C13B C14B C15B (7) C16A N2A C15A C14A (4) C16B N2B C15B C14B (5) Pd1A N2A C15A C14A 0.1 (5) Pd1B N2B C15B C14B 0.8 (7) C9A C14A C15A N2A 5.6 (6) C9B C14B C15B N2B 7.3 (8) C13A C14A C15A N2A (4) C13B C14B C15B N2B (5) C15A N2A C16A C17A (3) C15B N2B C16B C17B (4) Pd1A N2A C16A C17A 46.8 (4) Pd1B N2B C16B C17B 15.5 (7) N2A C16A C17A C1A 75.5 (4) N2B C16B C17B C19B 66.4 (6) N2A C16A C17A C18A (4) N2B C16B C17B C1B 59.0 (6) N2A C16A C17A C19A 48.9 (5) N2B C16B C17B C18B (4) N1A C1A C17A C16A 65.9 (4) N1B C1B C17B C19B 47.4 (6) N1A C1A C17A C18A (4) N1B C1B C17B C16B 77.9 (5) N1A C1A C17A C19A 58.9 (5) N1B C1B C17B C18B (4) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A O5A H5AB O1A i (13) 142 Symmetry code: (i) x, y 1/2, z+1/2. sup-12