metal-organic compounds

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1 metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN Hexaaquacadmium(II) bis{[n-(2- oxidobenzylidene)glycyl-l-leucinato]- cuprate(ii)} dihydrate Guolin Zhang, Lihua Ye, Yanyan Zhang and Wenlong Liu* College of Chemistry and Chemical Engineering, Yangzhou Universitry, Yangzhou, , People s Republic of China Correspondence liuwl@yzu.edu.cn Received 19 November 2007; accepted 26 November 2007 Key indicators: single-crystal X-ray study; T = 296 K; mean (C C) = Å; R factor = 0.024; wr factor = 0.054; data-to-parameter ratio = The title compound, [Cd(H 2 O) 6 ][Cu(C 15 H 17 N 2 O 4 )] 2 2H 2 O, has a chiral structure. Copper has a square-planar coordination with two N and two O atoms of the quadridentate chiral Schiff base ligand. The Cd 2+ ion is coordinated by six aqua ligands with a slightly distorted octahedral configuration. Ions are linked by O HO hydrogen bonds, and the [Cd(H 2 O) 6 ] 2+ cations and [CuL] anions (L = Schiff base derived from glycyl-l-leucine and salicylaldehyde) occupy a stacking structure within well separated columns along the a axis. The two crystallographically independent copper Schiff base anions each have a chiral carbon centre with an S configuration. They are related by a non-crystallographic twofold rotation axis parallel to the [010] direction. Related literature For related literature, see: Liu et al. (2004). Data collection Bruker SMART APEX CCD diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 2004) T min = 0.602, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 494 parameters 361 restraints Table 1 Selected geometric parameters (Å, ). Cd1 O (2) Cd1 O (3) Cd1 O (2) Cd1 O (2) Cd1 O (2) Cd1 O (2) Cu1 O (2) O1 Cu1 N (11) O1 Cu1 N (11) N2 Cu1 N (11) O1 Cu1 O (10) N2 Cu1 O (11) N1 Cu1 O (11) Table 2 Hydrogen-bond geometry (Å, ) measured reflections 6936 independent reflections 6430 reflections with I > 2(I) R int = H atoms treated by a mixture of independent and constrained refinement max = 0.33 e Å 3 min = 0.28 e Å 3 Absolute structure: Flack (1983), 3005 Friedel pairs Flack parameter: (9) Cu1 N (2) Cu1 N (3) Cu1 O (2) Cu2 O (2) Cu2 N (3) Cu2 N (3) Cu2 O (2) O5 Cu2 N (11) O5 Cu2 N (11) N4 Cu2 N (11) O5 Cu2 O (10) N4 Cu2 O (10) N3 Cu2 O (12) D HA D H HA DA D HA O16 H16BO8 i (4) 171 O16 H16AO4 ii (4) 165 O15 H15BO (18) 1.91 (2) (3) 164 (4) O15 H15AO14 iii (19) (19) (4) 168 (4) O14 H14DO4 iv (18) 1.86 (2) (4) 171 (3) O14 H14EO (17) (18) (3) 177 (3) O12 H12BO8 v (3) 144 O10 H10AO6 vi (3) 147 O10 H10BO (3) 147 O9 H9AO (4) 167 O9 H9BO (3) 166 Symmetry codes: (i) x þ 1; y þ 1 2 ; z þ 1; (ii) x þ 1; y þ 1 2 ; z þ 2; (iii) x þ 1; y; z; (iv) x; y þ 1 2 ; z þ 2; (v) x; y þ 1 2 ; z þ 1; (vi) x 1; y; z. Experimental Crystal data [Cd(H 2 O) 6 ][Cu(C 15 H 17 N 2 O 4 )] 2-2H 2 O M r = Monoclinic, P2 1 a = (6) Å b = (14) Å c = (13) Å = (1) V = (3) Å 3 Z =2 Mo K radiation = 1.71 mm 1 T = 296 (2) K mm Data collection: SMART (Bruker, 2002); cell refinement: SAINT- Plus (Bruker, 2003); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL. This work was supported by the Natural Science Foundation of the Education Department of Jiangsu Province (No. 06KJD150208). m94 Zhang et al. doi: /s Acta Cryst. (2008). E64, m94 m95

2 metal-organic compounds Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2059). References Bruker (2000). SHELXTL. Version Bruker AXS Inc., Madison, Wisconsin, USA. Bruker (2002). SMART for WNT/2000. Version Bruker AXS Inc., Madison, Wisconsin, USA. Bruker (2003). SAINT-Plus. Version Bruker AXS Inc., Madison, Wisconsin, USA. Flack, H. D. (1983). Acta Cryst. A39, Liu, W. L., Song, Y., Li, Y. Z., Zou, Y., Dang, D. B., Ni, C. L. & Meng, Q. J. (2004). Chem. Commun. pp Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Acta Cryst. (2008). E64, m94 m95 Zhang et al. [Cd(H 2 O) 6 ][Cu(C 15 H 17 N 2 O 4 )] 2 2H 2 O m95

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4 Acta Cryst. (2008). E64, m94-m95 [ doi: /s ] Hexaaquacadmium(II) bis{[n-(2-oxidobenzylidene)glycyl-l-leucinato]cuprate(ii)} dihydrate G. Zhang, L. Ye, Y. Zhang and W. Liu Comment We are making a systematic investigation of chiral complexes of Schiff base derived from chiral dipeptides to which little attention has been given, and recently reported a chiral Cu(II) Sr(II) Na(I) complex of a Schiff base ligand resulting from the condensation of glycyl-l-tyrosine with N-5-bromosalicylaldehyde (Liu et al., 2004). Herein, we report the synthesis and structure of a Cu(II) Cd(II) chiral Schiff base complex derived from glycyl-l-leucine and salicylaldehyde. The asymmetric unit consists of two [CuL] anions ([Cu1L] and [Cu2L] )(L is a Schiff base derived from glycyl-l-leucine and salicylaldehyde), one cation [CdII, O9, O10, O11, O12, O13 and O14]2+, and two uncoordinated water molecules (O15 and O16) (Fig. 1). [CuL] has an approximate square-planar structure. The two crystallographically independent copper-schiff base anions each have a chiral carbon centre (C10 and C25) with S-configuration. They are related by a non-crystallographic twofold rotation axis parallel to the [0 1 0] direction (Fig. 2). The deprotonated Schiff base ligand is a triple negatively charged quadridentate ONNO chelant, coordinating to the CuII ion via one phenolic oxygen, one deprotonated amide nitrogen atom, one imino nitrogen atom and one carboxylate oxygen. The Cu O and Cu N bond distances are in the range of (2) (2) Å and (3) (3) Å, respectively (Table 1). The best-fit least-squares plane through the four basal and Cu atoms shows these atoms to be nearly coplanar. The CdII is coordinated by six aqua ligands with a slightly distorted octahedral geometry. The six Cd O bonds in the structure are in the range of (2) (2) Å. The anions and cations linked by O H O hydrogen bonds (Table 2) form well separated columns along the a-axis in the stacking structure of (Fig. 3). The intermolecular and intramolecular hydrogen bonds in the title compound play an important role in the stabilization of the whole structure. Experimental Glycyl-L-leucine (5 mmol), salicylaldehyde (5 mmol) and LiOH (10 mmol) were dissolved in MeOH/H2O (30 ml, v:v = 1:1) and refluxed for 30 min. Then Cu(ClO4)2 6H2O (5 mmol) was added to the solution and the resulting solution was adjusted to the ph 9 11 by using 5 mol L 1 NaOH solution. After stirring at room temperature (25 C) for 1 hr, CdCl2 6H2O (2.5 mmol) was added. A violet precipitate was obtained immediately. After stirring for 30 min and then filtered, the precipitate was recrystallized in water. The violet crystals suitable for X-ray diffraction were obtained after 1 week. Refinement The water H atoms were located in a difference Fourier map and refined in riding mode, with a distance restraint of O H = Å and Uiso(H) = 1.5Ueq(O). All other H atoms were positioned geometrically and constrained as riding atoms, with C H distances of Å and Uiso(H) set to 1.2 or 1.5eq(C) of the parent atom. The refinement of the structure was performed using 361 least-squares restraints by applying SIMU and DFIX instructions of SHELXTL. sup-1

5 Figures Fig. 1. The molecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids. Fig. 2. View of the title structure in ac projection showing the non-crystallographic twofold rotation symmetry between the [CuL] anions. Fig. 3. The packing of the title compound, viewed down the a axis, showing a separated columns stacking structure connected by O H O hydrogen bonds, indicated by dashed lines. Hexaaquacadmium(II) bis{[n-(2-oxidobenzylidene)glycyl-l-leucinato]cuprate(ii)} dihydrate Crystal data [Cd(H2O)6][Cu(C15H17N2O4)]2 2H2O F000 = 984 Mr = Dx = Mg m 3 Monoclinic, P21 Hall symbol: P 2yb a = (6) Å b = (14) Å c = (13) Å β = (1)º V = (3) Å3 Z=2 Mo Kα radiation λ = Å Cell parameters from 7167 reflections θ = º µ = 1.71 mm 1 T = 296 (2) K Block, violet mm Data collection Bruker SMART APEX CCD diffractometer Radiation source: sealed tube 6936 independent reflections Monochromator: graphite 6430 reflections with I > 2σ(I) Rint = T = 296(2) K θmax = 26.0º φ and ω scans θmin = 2.3º Absorption correction: multi-scan h = 8 8 sup-2

6 (SADABS; Sheldrick, 2004) Tmin = 0.602, Tmax = k = measured reflections l = Refinement Hydrogen site location: inferred from neighbouring sites H atoms treated by a mixture of independent and constrained refinement Refinement on F2 Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0201P)2] R[F2 > 2σ(F2)] = where P = (Fo2 + 2Fc2)/3 wr(f2) = (Δ/σ)max = S = 1.01 Δρmax = 0.33 e Å reflections Δρmin = 0.27 e Å parameters Extinction correction: none 361 restraints Absolute structure: Flack (1983), 3005 Friedel pairs Primary atom site location: structure-invariant direct Flack parameter: (9) methods Secondary atom site location: difference Fourier map 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 F2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 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 (Å2) Cd1 Cu1 Cu2 C1 H1 C2 H2 C3 H3 C4 H4 C5 x y z Uiso*/Ueq (3) (5) (6) (5) (5) (5) (5) (5) (13) (2) (2) (2) (2) (2) (2) (2) (13) (2) (2) (2) (2) (2) (2) (2) (6) (9) (10) (8) 0.047* (9) 0.051* (9) 0.054* (8) 0.047* (7) sup-3

7 C6 C7 H7 C8 H8A H8B C9 C10 H10 C11 H11A H11B C12 H12 C13 H13A H13B H13C C14 H14A H14B H14C C15 C16 H16 C17 H17 C18 H18 C19 H19 C20 C21 C22 H22 C23 H23A H23B C24 C25 H25 C26 H26A H26B C27 H27 C28 H28A H28B sup (4) (4) (5) (4) (5) (5) (5) (5) (6) (4) (5) (5) (5) (5) (5) (4) (5) (5) (4) (5) (5) (5) (6) (2) (19) (18) (18) (18) (2) (2) (2) (3) (18) (2) (2) (2) (2) (19) (19) (19) (18) (19) (18) (2) (2) (3) (2) (2) (2) (2) (2) (2) (2) (2) (3) (2) (2) (2) (2) (2) (2) (2) (2) (2) (2) (2) (2) (2) (3) (7) (7) 0.040* (7) 0.039* 0.039* (7) (7) 0.037* (8) 0.043* 0.043* (8) 0.048* (10) 0.077* 0.077* 0.077* (11) 0.094* 0.094* 0.094* (7) (8) 0.051* (8) 0.052* (9) 0.052* (8) 0.047* (7) (7) (7) 0.040* (7) 0.040* 0.040* (7) (7) 0.037* (8) 0.044* 0.044* (8) 0.052* (11) 0.092* 0.092*

8 H28C C29 H29A H29B H29C C30 N1 N2 N3 N4 O1 O2 O3 O4 O5 O6 O7 O8 O9 H9A H9B O10 H10B H10A O11 H11D H11C O12 H12A H12B O13 H13E H13D O14 H14D H14E O15 H15A H15B O16 H16A H16B (6) (4) (4) (3) (4) (4) (3) (3) (4) (3) (3) (4) (3) (3) (4) (4) (3) (3) (4) (3) (5) (5) (4) (4) (6) (4) (3) (19) (16) (15) (16) (14) (13) (12) (13) (13) (12) (13) (13) (13) (15) (14) (17) (14) (15) (16) (10) (17) (15) (2) (14) (19) (3) (2) (17) (15) (16) (16) (13) (14) (16) (15) (13) (15) (15) (14) (15) (17) (14) (15) (18) (14) (2) (15) (2) (3) (3) (18) * (13) 0.106* 0.106* 0.106* (8) (7) (5) (6) (6) (5) (6) (6) (6) (6) (6) (6) (6) (7) 0.074* 0.074* (7) 0.075* 0.075* (6) 0.073* 0.073* (7) 0.074* 0.074* (7) 0.076* 0.076* (5) 0.057* 0.057* (7) 0.082* 0.082* (9) 0.098* 0.098* Atomic displacement parameters (Å2) Cd1 Cu1 U (11) (2) U (12) (2) U (12) (19) U (11) (18) U (8) (16) U (12) (17) sup-5

9 Cu2 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 N1 N2 N3 N4 O1 O2 O3 O4 O5 O6 O7 O8 O9 O10 O11 O12 O13 O14 sup (2) (18) (2) (19) (18) (16) (15) (17) (18) (16) (17) (18) (18) (2) (2) (16) (18) (18) (19) (17) (16) (16) (17) (18) (15) (16) (19) (18) (2) (2) (16) (16) (13) (15) (14) (14) (15) (15) (15) (14) (16) (15) (16) (14) (16) (14) (15) (18) (12) (2) (19) (2) (2) (18) (18) (18) (16) (16) (17) (16) (17) (18) (2) (3) (17) (2) (2) (2) (18) (17) (17) (16) (17) (18) (17) (18) (2) (3) (3) (19) (16) (13) (15) (15) (12) (13) (13) (13) (14) (13) (13) (14) (17) (14) (14) (16) (16) (12) (2) (18) (18) (19) (19) (17) (16) (18) (17) (17) (17) (17) (19) (2) (2) (19) (18) (18) (19) (19) (17) (16) (18) (18) (18) (17) (17) (2) (3) (3) (19) (15) (13) (16) (14) (11) (13) (15) (13) (12) (13) (15) (13) (14) (15) (14) (14) (17) (12) (18) (15) (17) (17) (14) (14) (13) (13) (14) (13) (13) (15) (15) (18) (2) (13) (16) (17) (16) (15) (13) (13) (13) (13) (13) (13) (15) (15) (2) (2) (14) (12) (12) (11) (10) (11) (11) (11) (11) (10) (11) (11) (12) (12) (12) (16) (12) (13) (14) (16) (15) (15) (15) (15) (13) (12) (14) (14) (13) (13) (14) (15) (17) (19) (14) (15) (14) (15) (15) (13) (13) (14) (14) (13) (13) (15) (15) (19) (2) (14) (12) (10) (12) (11) (10) (11) (12) (11) (10) (11) (12) (11) (11) (13) (11) (11) (14) (10) (18) (15) (17) (17) (15) (14) (14) (15) (14) (14) (14) (14) (16) (2) (2) (14) (16) (17) (17) (15) (14) (14) (15) (14) (14) (13) (14) (16) (2) (2) (16) (12) (12) (13) (11) (11) (10) (12) (11) (10) (10) (11) (10) (13) (12) (15) (12) (14) (14)

10 O15 O (16) (17) (16) (2) (2) (17) (13) (16) (14) (13) (15) (16) Geometric parameters (Å, ) Cd1 O10 Cd1 O13 Cd1 O12 Cd1 O9 Cd1 O11 Cd1 O14 Cu1 O1 Cu1 N2 Cu1 N1 Cu1 O2 Cu2 O5 Cu2 N4 Cu2 N3 Cu2 O6 C1 C2 C1 C6 C1 H1 C2 C3 C2 H2 C3 C4 C3 H3 C4 C5 C4 H4 C5 C6 C5 C7 C6 O1 C7 N1 C7 H7 C8 N1 C8 C9 C8 H8A C8 H8B C9 O4 C9 N2 C10 N2 C10 C11 C10 C15 C10 H10 C11 C12 C11 H11A C11 H11B C12 C13 C12 C14 C12 H (2) (3) (2) (2) (2) (2) (2) (2) (3) (2) (2) (3) (3) (2) (5) (4) (5) (5) (5) (5) (4) (4) (4) (4) (4) (4) (4) (4) (4) (4) (5) (5) (5) C16 C21 C16 H16 C17 C18 C17 H17 C18 C19 C18 H18 C19 C20 C19 H19 C20 C21 C20 C22 C21 O5 C22 N3 C22 H22 C23 N3 C23 C24 C23 H23A C23 H23B C24 O8 C24 N4 C25 N4 C25 C26 C25 C30 C25 H25 C26 C27 C26 H26A C26 H26B C27 C28 C27 C29 C27 H27 C28 H28A C28 H28B C28 H28C C29 H29A C29 H29B C29 H29C C30 O7 C30 O6 O9 H9A O9 H9B O10 H10B O10 H10A O11 H11D O11 H11C O12 H12A (4) (5) (5) (5) (5) (5) (4) (4) (4) (4) (4) (4) (4) (4) (5) (5) (5) (5) (4) (4) sup-7

11 C13 H13A C13 H13B C13 H13C C14 H14A C14 H14B C14 H14C C15 O3 C15 O2 C16 C (4) (4) (5) O12 H12B O13 H13E O13 H13D O14 H14D O14 H14E O15 H15A O15 H15B O16 H16A O16 H16B (18) (17) (19) (18) O10 Cd1 O13 O10 Cd1 O12 O13 Cd1 O12 O10 Cd1 O9 O13 Cd1 O9 O12 Cd1 O9 O10 Cd1 O11 O13 Cd1 O11 O12 Cd1 O11 O9 Cd1 O11 O10 Cd1 O14 O13 Cd1 O14 O12 Cd1 O14 O9 Cd1 O14 O11 Cd1 O14 O1 Cu1 N2 O1 Cu1 N1 N2 Cu1 N1 O1 Cu1 O2 N2 Cu1 O2 N1 Cu1 O2 O5 Cu2 N4 O5 Cu2 N3 N4 Cu2 N3 O5 Cu2 O6 N4 Cu2 O6 N3 Cu2 O6 C2 C1 C6 C2 C1 H1 C6 C1 H1 C1 C2 C3 C1 C2 H2 C3 C2 H2 C2 C3 C4 C2 C3 H3 C4 C3 H3 C3 C4 C5 C3 C4 H4 C5 C4 H4 C4 C5 C (11) (9) (10) (9) (10) (9) (10) (10) (9) (9) (10) (10) (9) (8) (8) (11) (11) (11) (10) (11) (11) (11) (11) (11) (10) (10) (12) (3) (3) (3) (3) (3) C18 C17 H17 C19 C18 C17 C19 C18 H18 C17 C18 H18 C18 C19 C20 C18 C19 H19 C20 C19 H19 C19 C20 C21 C19 C20 C22 C21 C20 C22 O5 C21 C16 O5 C21 C20 C16 C21 C20 N3 C22 C20 N3 C22 H22 C20 C22 H22 N3 C23 C24 N3 C23 H23A C24 C23 H23A N3 C23 H23B C24 C23 H23B H23A C23 H23B O8 C24 N4 O8 C24 C23 N4 C24 C23 N4 C25 C26 N4 C25 C30 C26 C25 C30 N4 C25 H25 C26 C25 H25 C30 C25 H25 C27 C26 C25 C27 C26 H26A C25 C26 H26A C27 C26 H26B C25 C26 H26B H26A C26 H26B C28 C27 C26 C28 C27 C29 C26 C27 C (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) sup-8

12 C4 C5 C7 C6 C5 C7 O1 C6 C1 O1 C6 C5 C1 C6 C5 N1 C7 C5 N1 C7 H7 C5 C7 H7 N1 C8 C9 N1 C8 H8A C9 C8 H8A N1 C8 H8B C9 C8 H8B H8A C8 H8B O4 C9 N2 O4 C9 C8 N2 C9 C8 N2 C10 C11 N2 C10 C15 C11 C10 C15 N2 C10 H10 C11 C10 H10 C15 C10 H10 C12 C11 C10 C12 C11 H11A C10 C11 H11A C12 C11 H11B C10 C11 H11B H11A C11 H11B C13 C12 C14 C13 C12 C11 C14 C12 C11 C13 C12 H12 C14 C12 H12 C11 C12 H12 C12 C13 H13A C12 C13 H13B H13A C13 H13B C12 C13 H13C H13A C13 H13C H13B C13 H13C C12 C14 H14A C12 C14 H14B H14A C14 H14B C12 C14 H14C H14A C14 H14C H14B C14 H14C O3 C15 O2 O3 C15 C (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) C28 C27 H27 C26 C27 H27 C29 C27 H27 C27 C28 H28A C27 C28 H28B H28A C28 H28B C27 C28 H28C H28A C28 H28C H28B C28 H28C C27 C29 H29A C27 C29 H29B H29A C29 H29B C27 C29 H29C H29A C29 H29C H29B C29 H29C O7 C30 O6 O7 C30 C25 O6 C30 C25 C7 N1 C8 C7 N1 Cu1 C8 N1 Cu1 C9 N2 C10 C9 N2 Cu1 C10 N2 Cu1 C22 N3 C23 C22 N3 Cu2 C23 N3 Cu2 C24 N4 C25 C24 N4 Cu2 C25 N4 Cu2 C6 O1 Cu1 C15 O2 Cu1 C21 O5 Cu2 C30 O6 Cu2 Cd1 O9 H9A Cd1 O9 H9B H9A O9 H9B Cd1 O10 H10B Cd1 O10 H10A H10B O10 H10A Cd1 O11 H11D Cd1 O11 H11C H11D O11 H11C Cd1 O12 H12A Cd1 O12 H12B H12A O12 H12B Cd1 O13 H13E Cd1 O13 H13D H13E O13 H13D (3) (3) (3) (3) (2) (2) (3) (2) (2) (3) (2) (2) (3) (2) (19) (2) (2) (2) (2) sup-9

13 O2 C15 C10 C17 C16 C21 C17 C16 H16 C21 C16 H16 C16 C17 C18 C16 C17 H (3) (3) (3) Cd1 O14 H14D Cd1 O14 H14E H14D O14 H14E H15A O15 H15B H16A O16 H16B 98 (3) 120 (3) 109 (3) 103 (3) Hydrogen-bond geometry (Å, ) D H A D H H A D A D H A (4) (4) (18) 1.91 (2) (3) 164 (4) (19) (19) (4) 168 (4) (18) 1.86 (2) (4) 171 (3) (17) (18) (3) 177 (3) iv (4) 112 v (3) 144 vi O12 H12A O7 O11 H11C O (3) (4) 125 i (4) 126 O16 H16B O8 i O16 H16A O4ii O15 H15B O5 O15 H15A O14 O14 H14D O4 O14 H14E O3 iii iv O13 H13E O4 O12 H12B O8 O11 H11D O8 vi (3) 147 O10 H10A O6 O10 H10B O (3) 147 O10 H10B O (3) 136 O9 H9A O (4) 167 O9 H9B O (3) 166 Symmetry codes: (i) x+1, y+1/2, z+1; (ii) x+1, y+1/2, z+2; (iii) x+1, y, z; (iv) x, y+1/2, z+2; (v) x, y+1/2, z+1; (vi) x 1, y, z. sup-10

14 Fig. 1 sup-11

15 Fig. 2 sup-12

16 Fig. 3 sup-13