metal-organic compounds

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1 metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN Bis(tetrabutylammonium) bis(3,4,5- trioxocyclopent-1-ene-1,2-dithiolatoj 2 S,S 0 )cadmate(ii) 0.25-hydrate Hong-Yu Chen, a Guang-Ming Xia, b * Zhen-Wei Zhang b and Ping Li a a School of Chemistry and Chemical Engineering, TaiShan Medical University, Tai an , People s Republic of China, and b Shandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials, School of Chemistry and Chemical Engineering, University of Jinan, Ji nan , People s Republic of China Correspondence Binboll@126.com Received 1 October 2010; accepted 29 November 2010 Key indicators: single-crystal X-ray study; T = 293 K; mean (C C) = Å; disorder in main residue; R factor = 0.050; wr factor = 0.144; data-to-parameter ratio = Experimental Crystal data (C 16 H 36 N) 2 [Cd(C 5 O 3 S 2 ) 2 ]0.25H 2 O M r = Triclinic, P1 a = (5) Å b = (5) Å c = (5) Å = (5) = (5) Data collection Oxford Diffraction CCD areadetector diffractometer Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) T min = 0.775, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 534 parameters = (5) V = (17) Å 3 Z =2 Mo K radiation = 0.65 mm 1 T = 293 K mm measured reflections independent reflections 6510 reflections with I > 2(I) R int = restraints H-atom parameters constrained max = 0.72 e Å 3 min = 0.42 e Å 3 The title compound, (C 16 H 36 N) 2 [Cd(C 5 O 3 S 2 ) 2 ]0.25H 2 O, contains two disordered tetrabutylammonium cations, a complex [Cd(C 5 O 3 S 2 ) 2 ] 2 anion and a 0.25-hydrate water. The anion is composed of a bidentate coordinated 3,4,5- trioxocyclopent-1-ene-1,2-dithiolate (dtcroc) group forming a distorted tetrahedral configuration around the Cd II ion. The dihedral angle between the least-squares planes of the tenatom sulfur-substituted croconate groups in the anion is (8). The crystal packing is stabilized by weak C HO and C HS cation anion hydrogen-bond interactions. In each of the two cations one butyl group is disordered over two positions in the ratios (11):0.411 (11) and (12): (12). Related literature For the delocalized electronic structures, redox chemistry and range of coordination geometries of metal complexes of chelating ethylene-1,2-dithiolato ligands, see: Eisenberg (1970); Kato (2004). For the coordination behavior of the dtcroc dianion, see: Deplano et al. (2005, 2006). For related structures, see: Dunitz et al. (2001); Castro et al. (2002); Maji et al. (2004). Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA C12 H12AO6 i (6) 161 C14 H14CS2 ii (10) 137 C16 H16BO2 iii (7) 163 Symmetry codes: (i) x; y þ 1; z þ 2; (ii) x þ 1; y þ 1; z þ 2; (iii) x 1; y þ 1; z. Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999). This work was supported by the Shandong Key Scientific and Technological Project (2008 GG ), the Project of the Key Laboratory of Photochemical Conversion and Optoelectronic Materials, the TIPC and the Chinese Academy of Sciences Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: JJ2066). References Altomare, A., Burla, M. C., Camalli, M., Cascarano, G., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, Castro, I., Calatayud, M. L., Lloret, F., Sletten, J. & Julve, M. (2002). J. Chem. Soc. Dalton Trans. pp Deplano, P., Mercuri, M. L., Marchio, L., Pilia, L., Salidu, M. & Serpe, A. (2006). Dalton Trans. pp Deplano, P., Mercuri, M. L., Marchio, L., Pilia, L., Salidu, M., Serpe, A., Congiu, F. & Sanna, S. (2005). Eur. J. Inorg. Chem. pp m12 Chen et al. doi: /s

2 metal-organic compounds Dunitz, J. D., Seiler, P. & Czechtizky, W. (2001). Angew. Chem. Int. Ed. 40, Eisenberg, R. (1970). Prog. Inorg. Chem. 12, Farrugia, L. J. (1999). J. Appl. Cryst. 32, Kato, R. (2004). Chem. Rev. 11, Maji, T. K., Ghoshal, D., Zangrando, E., Ribas, J. & Chaudhuri, N. R. (2004). CrystEngComm, 6, Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England Sheldrick, G. M. (2008). Acta Cryst. A64, Chen et al. (C 16 H 36 N) 2 [Cd(C 5 O 3 S 2 ) 2 ]0.25H 2 O m13

3 supporting information [ Bis(tetrabutylammonium) bis(3,4,5-trioxocyclopent-1-ene-1,2-dithiolatoκ 2 S,S )cadmate(ii) 0.25-hydrate Hong-Yu Chen, Guang-Ming Xia, Zhen-Wei Zhang and Ping Li S1. Comment Metal complexes of chelating ethylene-1,2-dithiolato ligands (metal dithiolene)are of continuing interest owing to their delocalized electronic structures, rich redox chemistry and range of coordination geometries (Eisenberg,1970; Kato, 2004). They have also proven useful as precursors for the preparation ofnovel molecular conductors, non-linear optical materials and magnetic charge-transfer salts. Accordingly, we have interests in investigating the solid chemistry based on 2- the 3,4,5-trioxo-cyclopent-1 ene-ene-1, 2-dithiolate ion (C 5 O 3 S 2 ), also abbreviated as dtcroc (alternative name sulfursubstituted croconate). The coordination behavior of the dtcroc dianion (C 5 O 3 S 2 ) towards d 8 transition metal ions, such 2- as Pt 2+ (Deplano, et al. 2005) and Ni 2+ (Deplano, et al. 2006), have been investigated and all show a planar configuration. We present here the synthesis and characterization of a new Cd(II) coordination compound of dtcroc, which shows a distorted tetrahedral coordination conformation. The asymmetric unit of title compound, (C 16 H 36 N) 2, [C 10 CdO 6 S 4 ], 0.25(H 2 O) contains two disordered tetrabutylammonium cations, a coordinated [Cd(C 5 O 3 S 2 ) 2 ] 2- anion, and a 0.25 hydrate water (Fig. 1). The [Cd(C 5 O 3 S 2 ) 2 ] 2- anion is composed of a bidentate coordinated dtcroc group forming a distorted tetrahedral configuration around a Cd (II) ion with Cd S bonds between (13) (12)Å and six S Cd S angles between adjacent sulfur atoms in the coordination sphere close to The dihedral angle between the least-square-planes of the ten atom sulfur-substituted 2- croconate group in the (C 5 O 3 S 2 ) anion is (8). 2- Deviations of oxygen atoms, sulfur atoms and the cyclic five-membered ring in C 5 O 3 S 2 are less than 0.09 Å, indicating a planar molecular geometry for both ligands. The C O bonds in the title compound, vary by (5) (5)Å and show typical Csp 2 double bond character, while the C S bonds are in the range of (4) (4) Å, which are intermediate between the lengths of typical single C S and double C S bonds. The difference among C C distances within the ligands are in the range of (5) (6) Å, establishing a π-electron localized C 2v molecular symmetry which compares well with similar structure croconate anions (Dunitz, et al., 2001; Castro, et al., 2002; Maji, et al.2004). The tetrabutlyammionium cations are disordered in the title crystal and a few solvent water molecules were cocrystalized to stabilize the structure. The [Cd(C 5 O 3 S 2 ) 2 ] 2- units form stacks along [1 0 0], surrounded by tetrabutylamonium cations (Fig.2). Crystal packing is stabilized by weak C H O, C H S cation anion hydrogen bond interactions (Table 1). S2. Experimental To a solution containing K 2 dtcroc (0.2 g, 0.8 mmol) in H 2 O (20 ml) was addedto a solution containing Cd(NO 3 ).4H 2 O (0.12 g, 0.4 mmol) in H 2 O (5 ml). The resulting mixture was heated to 70 C for 1 h, then filtered into a solution of NBu 4 Br (0.40 g, 0.95 mmol) in ethanol (5 ml). Solid product was collected by suction filtration, washed with water and sup-1

4 dried in air. Red block crystals were obtained by recrystallization from acetone. S3. Refinement All H atoms were geometrically fixed and allowed to ride on their attached atoms, which O H = 0.85Å with U iso (H)= 1.5U eq (O) and C H = Å with U iso (H)= U eq (C). Butyl groups are disordered in title structure. Some butyl groups were refined as a rigid body, which C C bond are fixed to 1.54Å and the distances between alternate C atom are fixed to 2.54 Å. Terminal ethyl group C13 C14 is refined to a rigid model around the bond C11 C12 with ethyl group C13 -C14 in the ratio 0.59:0.41 and C41 C42 is refined to a rigid model around the bond C39 C40 with ethyl group C41 -C42 in the ratio 0.80:0.20. Figure 1 Coordination configuration of the title compound with thermal ellipsoids at 30% probability levels. Hydrogen atoms have been omiitted for clarity. Dashed lines indicate disordered butyl groups. sup-2

5 Figure 2 A packing diagram viewed down the b axis. symmetry code: a(-x, 1-y, 2-z); b(1-x, 1-y, 2-z); c(-1+x, 1+y, z); Bis(tetrabutylammonium) bis(3,4,5-trioxocyclopent-1-ene-1,2-dithiolato- κ 2 S,S )cadmate(ii) 0.25-hydrate Crystal data (C 16 H 36 N) 2 [Cd(C 5 O 3 S 2 ) 2 ] 0.25H 2 O M r = Triclinic, P1 Hall symbol: -P 1 a = (5) Å b = (5) Å c = (5) Å α = (5) β = (5) γ = (5) V = (17) Å 3 Data collection Oxford Diffraction CCD area-detector diffractometer Radiation source: fine-focus sealed tube Graphite monochromator φ and ω scans Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) T min = 0.775, T max = Z = 2 F(000) = 1001 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 6268 reflections θ = µ = 0.65 mm 1 T = 293 K Prism, red mm measured reflections independent reflections 6510 reflections with I > 2σ(I) R int = θ max = 26.4, θ min = 3.1 h = k = l = sup-3

6 Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 534 parameters 54 restraints 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 w = 1/[σ 2 (F o2 ) + (0.0756P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.72 e Å 3 Δρ min = 0.42 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) C (3) (2) (19) (8) C (4) (2) (2) (8) C (4) (3) (2) (10) C (4) (3) (3) (10) C (4) (3) (2) (9) C (4) (2) (2) (9) C (4) (2) (2) (8) C (5) (3) (3) (11) C (4) (3) (3) (11) C (4) (3) (3) (11) C (4) (3) (2) (11) H11A * H11B * C (5) (3) (2) (13) (11) H12A * (11) H12B * (11) C (11) (10) (6) (5) (11) H13A * (11) H13B * (11) C (11) (6) (5) (4) (11) H14A * (11) H14B * (11) H14C * (11) C (5) (3) (2) (13) (11) H12C * (11) sup-4

7 H12D * (11) C (16) (13) (11) (8) (11) H13C * (11) H13D * (11) C (15) (11) (10) (6) (11) H14D * (11) H14E * (11) H14F * (11) C (4) (3) (2) (11) H15A * H15B * C (5) (4) (2) (13) H16A * H16B * C (5) (4) (2) (15) H17A * H17B * C (6) (5) (3) (2) H18A * H18B * H18C * C (4) (3) (3) (11) H19A * H19B * C (5) (3) (3) (18) H20A * H20B * C (7) (3) (4) (2) H21A * H21B * C (7) (5) (5) (3) H22A * H22B * H22C * C (4) (3) (2) (11) H23A * H23B * C (5) (3) (3) (13) H24A * H24B * C (5) (4) (3) (16) H25A * H25B * C (7) (4) (4) (2) H26A * H26B * H26C * C (4) (3) (2) (10) sup-5

8 H27A * H27B * C (5) (3) (2) (11) H28A * H28B * C (6) (3) (2) (14) H29A * H29B * C (6) (4) (3) (17) H30A * H30B * H30C * C (4) (2) (2) (9) H31A * H31B * C (4) (3) (2) (10) H32A * H32B * C (4) (3) (3) (12) H33A * H33B * C (5) (3) (3) (16) H34A * H34B * H34C * C (4) (3) (2) (10) H35A * H35B * C (4) (3) (2) (11) H36A * H36B * C (5) (4) (3) (15) H37A * H37B * C (5) (4) (3) (18) H38A * H38B * H38C * C (4) (2) (2) (10) H39A * H39B * C (5) (3) (3) (14) (12) H40A * (12) H40B * (12) C (7) (4) (5) (3) (12) H41A * (12) H41B * (12) C (7) (4) (5) (2) (12) sup-6

9 H42A * (12) H42B * (12) H42C * (12) C (5) (3) (3) (14) (12) H40C * (12) H40D * (12) C (3) (7) (9) (9) (12) H41C * (12) H41D * (12) C (7) (4) (5) (2) (12) H42D * (12) H42E * (12) H42F * (12) Cd (3) (19) (17) (13) N (3) (2) (17) (8) N (3) (19) (16) (7) O (3) (2) (2) (10) O (4) (2) (3) (12) O (3) (19) (2) (9) O (4) (2) (2) (11) O (4) (2) (2) (11) O (4) (3) (2) (14) S (11) (7) (7) (3) S (11) (7) (7) (3) S (14) (7) (7) (3) S (11) (7) (6) (3) O (12) (8) (7) (3) 0.25 H1O * 0.25 H2O * 0.25 Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 C (19) (19) (19) (15) (15) (15) C (2) (2) (2) (17) (16) (16) C (2) (2) (3) (19) (2) (2) C (2) (2) (3) (18) (2) (19) C (2) (2) (2) (18) (18) (18) C (2) (2) (2) (17) (17) (17) C (2) (2) (2) (17) (16) (16) C (3) (2) (3) (2) (2) (2) C (3) (2) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (2) (3) (2) (2) (2) C (4) (3) (3) (3) (3) (2) C (13) (6) (9) (7) (8) (5) C (9) (5) (7) (5) (6) (4) C (4) (3) (3) (3) (3) (2) sup-7

10 C (13) (11) (14) (10) (10) (8) C (11) (12) (13) (9) (10) (10) C (3) (3) (3) (2) (2) (2) C (3) (4) (3) (3) (2) (2) C (4) (4) (3) (3) (2) (3) C (6) (6) (3) (5) (4) (4) C (3) (3) (3) (2) (2) (2) C (4) (3) (5) (3) (4) (3) C (5) (3) (6) (3) (5) (4) C (7) (6) (7) (5) (6) (5) C (2) (3) (2) (2) (19) (2) C (3) (3) (3) (3) (3) (3) C (4) (4) (4) (3) (3) (3) C (6) (5) (6) (4) (4) (4) C (3) (2) (2) (2) (19) (17) C (3) (3) (2) (2) (2) (2) C (4) (3) (3) (3) (3) (2) C (5) (4) (3) (3) (3) (3) C (2) (2) (2) (18) (17) (17) C (3) (2) (2) (2) (2) (18) C (3) (3) (3) (2) (2) (2) C (4) (3) (4) (3) (3) (3) C (2) (2) (3) (19) (19) (19) C (3) (3) (3) (2) (2) (2) C (3) (4) (4) (3) (3) (3) C (4) (5) (4) (3) (3) (3) C (3) (2) (2) (2) (2) (18) C (4) (3) (4) (3) (3) (2) C (5) (4) (8) (3) (5) (4) C (6) (5) (7) (4) (5) (5) C (4) (3) (4) (3) (3) (2) C (19) (17) 0.11 (2) (14) (15) (15) C (6) (5) (7) (4) (5) (5) Cd (2) (19) (2) (14) (15) (14) N (19) (2) (18) (16) (14) (15) N (19) (16) (17) (14) (14) (13) O (2) (2) (3) (17) (19) (2) O (2) (19) (4) (17) (2) (2) O (2) (17) (3) (15) (18) (18) O (3) (2) (2) (2) (2) (18) O (3) (2) (3) (2) (2) (2) O (3) (3) (3) (2) (3) (2) S (6) (6) (7) (5) (5) (5) S (7) (6) (9) (5) (6) (6) S (9) (6) (7) (6) (6) (5) S (7) (6) (6) (5) (5) (5) O (8) (8) (8) (7) (6) (7) sup-8

11 Geometric parameters (Å, º) C1 C (5) C24 C (6) C1 C (5) C24 H24A C1 S (4) C24 H24B C2 C (5) C25 C (6) C2 S (4) C25 H25A C3 O (5) C25 H25B C3 C (6) C26 H26A C4 O (4) C26 H26B C4 C (5) C26 H26C C5 O (4) C27 C (6) C6 C (5) C27 N (4) C6 C (5) C27 H27A C6 S (4) C27 H27B C7 C (5) C28 C (5) C7 S (4) C28 H28A C8 O (5) C28 H28B C8 C (6) C29 C (6) C9 O (5) C29 H29A C9 C (6) C29 H29B C10 O (5) C30 H30A C11 C (5) C30 H30B C11 N (5) C30 H30C C11 H11A C31 C (5) C11 H11B C31 N (5) C12 C (8) C31 H31A C12 H12A C31 H31B C12 H12B C32 C (5) C13 C (9) C32 H32A C13 H13A C32 H32B C13 H13B C33 C (6) C14 H14A C33 H33A C14 H14B C33 H33B C14 H14C C34 H34A C13 C (10) C34 H34B C13 H13C C34 H34C C13 H13D C35 C (5) C14 H14D C35 N (5) C14 H14E C35 H35A C14 H14F C35 H35B C15 C (5) C36 C (6) C15 N (5) C36 H36A C15 H15A C36 H36B C15 H15B C37 C (7) C16 C (5) C37 H37A C16 H16A C37 H37B C16 H16B C38 H38A sup-9

12 C17 C (6) C38 H38B C17 H17A C38 H38C C17 H17B C39 C (5) C18 H18A C39 N (4) C18 H18B C39 H39A C18 H18C C39 H39B C19 N (5) C40 C (6) C19 C (4) C40 H40A C19 H19A C40 H40B C19 H19B C41 C (7) C20 C (4) C41 H41A C20 H20A C41 H41B C20 H20B C42 H42A C21 C (5) C42 H42B C21 H21A C42 H42C C21 H21B C41 H41C C22 H22A C41 H41D C22 H22B Cd1 S (13) C22 H22C Cd1 S (13) C23 C (5) Cd1 S (15) C23 N (5) Cd1 S (12) C23 H23A O7 H1O C23 H23B O7 H2O C2 C1 C (3) H25A C25 H25B C2 C1 S (3) C25 C26 H26A C5 C1 S (3) C25 C26 H26B C1 C2 C (3) H26A C26 H26B C1 C2 S (3) C25 C26 H26C C3 C2 S (3) H26A C26 H26C O1 C3 C (4) H26B C26 H26C O1 C3 C (4) C28 C27 N (3) C2 C3 C (3) C28 C27 H27A O2 C4 C (4) N2 C27 H27A O2 C4 C (4) C28 C27 H27B C5 C4 C (3) N2 C27 H27B O3 C5 C (4) H27A C27 H27B O3 C5 C (3) C27 C28 C (3) C1 C5 C (3) C27 C28 H28A C7 C6 C (3) C29 C28 H28A C7 C6 S (3) C27 C28 H28B C10 C6 S (3) C29 C28 H28B C6 C7 C (3) H28A C28 H28B C6 C7 S (3) C28 C29 C (4) C8 C7 S (3) C28 C29 H29A O4 C8 C (4) C30 C29 H29A O4 C8 C (4) C28 C29 H29B C7 C8 C (3) C30 C29 H29B sup-10

13 O5 C9 C (4) H29A C29 H29B O5 C9 C (4) C29 C30 H30A C8 C9 C (3) C29 C30 H30B O6 C10 C (4) H30A C30 H30B O6 C10 C (4) C29 C30 H30C C6 C10 C (3) H30A C30 H30C C12 C11 N (3) H30B C30 H30C C12 C11 H11A C32 C31 N (3) N1 C11 H11A C32 C31 H31A C12 C11 H11B N2 C31 H31A N1 C11 H11B C32 C31 H31B H11A C11 H11B N2 C31 H31B C11 C12 C (5) H31A C31 H31B C11 C12 H12A C33 C32 C (3) C13 C12 H12A C33 C32 H32A C11 C12 H12B C31 C32 H32A C13 C12 H12B C33 C32 H32B H12A C12 H12B C31 C32 H32B C14 C13 C (8) H32A C32 H32B C14 C13 H13A C32 C33 C (4) C12 C13 H13A C32 C33 H33A C14 C13 H13B C34 C33 H33A C12 C13 H13B C32 C33 H33B H13A C13 H13B C34 C33 H33B C13 C14 H14A H33A C33 H33B C13 C14 H14B C33 C34 H34A H14A C14 H14B C33 C34 H34B C13 C14 H14C H34A C34 H34B H14A C14 H14C C33 C34 H34C H14B C14 H14C H34A C34 H34C C14 C13 H13C H34B C34 H34C C14 C13 H13D C36 C35 N (3) H13C C13 H13D C36 C35 H35A C13 C14 H14D N2 C35 H35A C13 C14 H14E C36 C35 H35B H14D C14 H14E N2 C35 H35B C13 C14 H14F H35A C35 H35B H14D C14 H14F C37 C36 C (4) H14E C14 H14F C37 C36 H36A C16 C15 N (3) C35 C36 H36A C16 C15 H15A C37 C36 H36B N1 C15 H15A C35 C36 H36B C16 C15 H15B H36A C36 H36B N1 C15 H15B C38 C37 C (4) H15A C15 H15B C38 C37 H37A C15 C16 C (4) C36 C37 H37A C15 C16 H16A C38 C37 H37B C17 C16 H16A C36 C37 H37B sup-11

14 C15 C16 H16B H37A C37 H37B C17 C16 H16B C37 C38 H38A H16A C16 H16B C37 C38 H38B C18 C17 C (4) H38A C38 H38B C18 C17 H17A C37 C38 H38C C16 C17 H17A H38A C38 H38C C18 C17 H17B H38B C38 H38C C16 C17 H17B C40 C39 N (3) H17A C17 H17B C40 C39 H39A C17 C18 H18A N2 C39 H39A C17 C18 H18B C40 C39 H39B H18A C18 H18B N2 C39 H39B C17 C18 H18C H39A C39 H39B H18A C18 H18C C39 C40 C (4) H18B C18 H18C C39 C40 H40A N1 C19 C (3) C41 C40 H40A N1 C19 H19A C39 C40 H40B C20 C19 H19A C41 C40 H40B N1 C19 H19B H40A C40 H40B C20 C19 H19B C42 C41 C (6) H19A C19 H19B C42 C41 H41A C19 C20 C (4) C40 C41 H41A C19 C20 H20A C42 C41 H41B C21 C20 H20A C40 C41 H41B C19 C20 H20B H41A C41 H41B C21 C20 H20B C41 C42 H42A H20A C20 H20B C41 C42 H42B C22 C21 C (5) H42A C42 H42B C22 C21 H21A C41 C42 H42C C20 C21 H21A H42A C42 H42C C22 C21 H21B H42B C42 H42C C20 C21 H21B H41C C41 H41D H21A C21 H21B S3 Cd1 S (4) C21 C22 H22A S3 Cd1 S (5) C21 C22 H22B S4 Cd1 S (4) H22A C22 H22B S3 Cd1 S (4) C21 C22 H22C S4 Cd1 S (4) H22A C22 H22C S2 Cd1 S (3) H22B C22 H22C C19 N1 C (3) C24 C23 N (3) C19 N1 C (3) C24 C23 H23A C23 N1 C (3) N1 C23 H23A C19 N1 C (3) C24 C23 H23B C23 N1 C (3) N1 C23 H23B C11 N1 C (3) H23A C23 H23B C27 N2 C (3) C23 C24 C (4) C27 N2 C (3) C23 C24 H24A C31 N2 C (3) C25 C24 H24A C27 N2 C (3) sup-12

15 C23 C24 H24B C31 N2 C (3) C25 C24 H24B C35 N2 C (3) H24A C24 H24B C1 S1 Cd (12) C26 C25 C (5) C2 S2 Cd (13) C26 C25 H25A C6 S3 Cd (13) C24 C25 H25A C7 S4 Cd (12) C26 C25 H25B H1O7 O7 H2O C24 C25 H25B Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A C12 H12A O6 i (6) 161 C14 H14C S2 ii (10) 137 C16 H16B O2 iii (7) 163 Symmetry codes: (i) x, y+1, z+2; (ii) x+1, y+1, z+2; (iii) x 1, y+1, z. sup-13